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MISERALO GIC A L CHE 111 S T R Y . M in e r a1 o g i c a 1 C h e m i s t ry. 109 Native Platinum from Canada. By G. C. HOFFMAN (Jahrb. j : Xin., 1888, ii, Ref., 386, from Geol. Szcrv. Can. Rep., 2, 5).-Native platinum has been found with gold in several rivers in British Columbia. From the bed of Granite Creek, a tributary of t h e Sixnilkameen river, grains were obtained varying in diameter froin 1 to 4 inm., and weighing altogether 18.266 grams. The material was separated into a magnetic (1) and a non-magnetic portion (H), the compositions of which were as follows :- Pt. Pd. Rh. Ir. Cu. Fe. OsIr. Chromite. Total. 1. 78-43 0.09 1.70 1.04 3-89 9.78 3-77 1-27 99.97 11. 68-19 0.26 3-10 1.21 3.09 7.87 14-62 1.95 100.29 The sp. gr. of the magnetic portlion was 16.095, and that of the The Pyroxenites of Morbihan.By C. BARROIS (Jahrb. f. Nin., 1888, ii, Ref., 413-414, from Ann. SOC. ge'ol. du Nod, 15, 69-96). -The pyroxenites of Morbihan form beds 0.1 to 2 metres in thick- ness in gneiss and mica-schists of Archean age. The main con- stituent of these rocks is a pale green augite of the fol1owi:ig composition :- non-magnetic portion 17.01. B. H. B. SiO3 CaO. MgO. Fe20,. Al,O,. Na,O. K,O. Total. 51.5 24.3 11.9 8.3 5.0 1.1 trace 102.3 The augite is accompanied by zircon, titanite, and apatite in small quantities, by garnet and idocrase in varying amounts, and by quartz grains associated with felspar. Irregular grains of orthoclase only occur in certain beds, and microcline is also of exceptional occurrence. A fibrous actinolite is, ho wever, present inlarge quantities, in many cases replacing the augite, so that rocks resembling nephrite are produced.Titaniferous iron ore and ferric hydroxide are also present. By t h e variety of the character and relative proportions of the constituents, numerous distinct types are distinguished, which may occur in the same bed. The author regards these pyroxenites as metamorphic limestones. B. H. B. Riebeckite, and the New Formation of Albite in Granitic Orthoclase. By A. SAUER (Chem. Centr., 1888, 1128, from Zeit. deut. geol. Gess., 40, 138--152).-A new member of the hornblende- granite group has been found by the author in Socotra. This horii- blende, named riebeclzite, has the same composition as arfvedsonite, arid is the analogue of agirin of the augite series.From the analysis (No. 1 below) the formula 5FeSi0,,4Na&3i0,,5Fe,Si3O9 has been calculated.110 ABSTRACTS OF CHEMICAL PAPERS. The Socotra granite is much disintegrated, and the author was thus enabled to examine more completely certain interchanges in the granitic orthoclases. The microscopical examination showed an opalescence from the edge towards the centre of the crystals, occa- sioned by the formation of albite, the crystals having been originally perfectly clenr and without inclosures. The following are tlte analyses of riebeckite (1) and the secondary albite (2) :- SiOP Al,O,. Fe,03. FeO. MgO. MnO. CaO. Ntx20. K,O. (1.) 50.01 - 28.30 9-87 0.34 0.63 1-32 8-79 0.72 - - 6.86 5.19 (2,) 70.24 17.18 0.64 - - J. W. L. The Dachberg, a Volcano of the Rhone.By F. RINNE (Jahrb. f. Min., 1888, ii, Ref., 406-407, from Jahrb. preuss. geol. Landesanst., 1886, 1--22).--Near Rasdorf on the Rhone is situated the Dachberg, on the summit of which is an unniistakeable crater. The unaltered basalt at the edge of the crater is a dense, glassy felspar-basalt, con- sisting of plagioclase, augite, olivine, magnetite, biotite, and apatite. The chemical composition of the basalt is as follows:- SiO,. TiO,. A1,03. Fe203. FeO. MnO. MgO. CaO. Na20. 41.71 3.51 15.80 5.59 7-64 0.16 4.85 10.30 6 . ~ 8 K,O. Li,O. SO3. C1. H20. COP P205. Total. Sp. gr. 1.00 trace 0.12 0.46 2.22 2-01 trace 101.45 2.90 B. H. B. Dolerite of Londorf. By A. STRENG (Jahrb. f. Mirt., 1888, ii, Ilem., 181-229).-The author has made an exhaustive mineralogical nud chemical investigation of the typical dolerites of the Vogelsberg.The dolerite of Londorf, to which he has principally directed his at tention, has the following percentage composition :- SiO,. Ti02. Al,O,. Fe,O,. FeO. CaO. MgO. K,O. 49-08 1-82 13.43 6-49 5.92 8.92 9-58 1-00 Na20. P2O5. H,O. Total: 3.42 0.51 0.32 100.49 From analyses of its constituents, the dolerite is calculated to be composed of 1-18 per cent. of apatite, 56.01 per cent. of andesine, 7980 per cent. of augite, 20.11 per cent. of olivine, and 3.10 per cent. of magnetite and titaniferous iron ore. B. H. B. Porphyrites at Gabian. By P. DE ROUVILLE and A. DELAGE (Cornpt. rend.. 10 7, 663-667) .-Near Gabian in HBrault there is a, dyke which runs north-east and south-west and consists of two porphyrites.One of these, which is by far the more abundant of the two, cuts through Silurian, devonian, and carboniferous beds without producing any noteworthy metamorphism, and then penetrates into coal-MINERALOGICAL CHEMISTRY. 111 measures which have undergone somewhat profound alteration. I t follows that this dyke was formed after the deposition of the coal- measures, and the fact that pebbles in the overlying permian con- glomerate consist of the material of the dyke, shows that it was formed before the deposition of the permian beds. This dyke is not homogeneous : it contains apatite, zircon, magnetite, oligoclase, black mica, orthoclase, amorphous matter, chlorite, calcite, damourite, and quartz. The second porphyrite forms isolated masses in the main dyke, and is of later formation than the lower permian, since the latter beds are somewhat altered where they come in contact with the dyke.It contains large crystals, the nature of which could not, be determined, well developed and distinct microlit,hs of labradorite, magnetite, augite which has to a great extent been converted into chlorite, calcite, chlorite, damourite, quartz, and ferruginous products of decomposition. C. H. B. Composition of the Serpentine Rocks of Colle di Cassi- moreno and Monte Rsgola. By c. MONrEMARTINI (Gnzaetta, 18, 103--112).-At Colle di Cassimoreno and also in the neighbourhood of Monte Ragola, Chistoni found isolated masses of serpentine rock exhibiting strong magnetic polarity. The author is indebted to him for the two specimens he has examined.The serpentiue of Colle di Cassimoreno is massive and compact; of brecciated and porphyritic appearance, witb lustrous, lamellar crystals of enstatite (bronzite) disseminated through the dark-green ground- mass. Besides these crystals, diopside and picotite also occur, together with magnetite, which forms one of the principal constituents of the rock. The hardness of the ground-mass is 6.5 and the sp. gr, at 13" varies from 2.73 to 2.76. The powdered rock is ash-grey in colour, and like all serpentine rocks has a marked alkaline reaction. Heated in contact with the air, it assumes an ochreons tint. It is partly decomposed by the action of hydrochloric or sulphuric acid, with separation of gelatinous silica ; the nnattacked portion consists principally of the crystals of enstatite and picotite.The rock on analysis gave the following results :- Loss on SiOz. Alz03. Fe,OJ. FeO. CaO. MgO. ignition. Total. 41-19 2.77 4.03 4.33 2.32 34-03 10.13 98% The enstatite, separated as far as possible from the other constituents of the rock, was analysed, and the results are given under I. In I1 the composition of the lherzolite from Germagnano in Piedmont is given for comparison :- Si02. AlZO3. FeO. CaO. MgO. H,O. Total. I. 50.65 3.05 7.99 1.68 31-49 2.78 99-59 11. 52.19 2.15 8.85 2.96 31.84 1.77 '39.76 These results show that the enstatite is bronzite.I1 2 ABSTRACTS OF CHEMICAL PAPERS. The rock therefore consists of a serpentine formed by the decompo- sition of peridote togcther with enstatite, diopside, magnetite, and other minerals ; this is also borne out by the microscopical and optical examination, full details of which are given.The rock also contains olivine, diallage, and amphibole. The sample of rock from Monte Ragola, which was from the rock mass of the mountain itself, had no magnetic polarity, and was quite different in appearance from the one just described. The ground-mass is light-peen w i t h dull-green nodules dissemi- nated in it ; these cau easily be separated, and on examination were found to consist- of altered bastite. A microscopical examination showed thatl the rock had all the characters of a serpentine formed by the alteration of a pyroxenic mineral. Neither the enstatite, diop- side, nor spinelle which characterise the Cassimoreno serpentine could be discovered in it.Its sp. gr. at 14" is 2.54. The analyvis gave the following results :- Loss on SiO,. Al,O,. Fe,O,. FeO. CaO. MgO. ignition. Total. 39.18 3.65 '7.26 1.55 0.42 34.79 12.81 99.66 Chromium, nickel, and manganese were also detected. C. E. G.MISERALO GIC A L CHE 111 S T R Y .M in e r a1 o g i c a 1 C h e m i s t ry.109Native Platinum from Canada. By G. C. HOFFMAN (Jahrb. j :Xin., 1888, ii, Ref., 386, from Geol. Szcrv. Can. Rep., 2, 5).-Nativeplatinum has been found with gold in several rivers in BritishColumbia. From the bed of Granite Creek, a tributary of t h eSixnilkameen river, grains were obtained varying in diameter froin1 to 4 inm., and weighing altogether 18.266 grams. The materialwas separated into a magnetic (1) and a non-magnetic portion (H), thecompositions of which were as follows :-Pt.Pd. Rh. Ir. Cu. Fe. OsIr. Chromite. Total.1. 78-43 0.09 1.70 1.04 3-89 9.78 3-77 1-27 99.9711. 68-19 0.26 3-10 1.21 3.09 7.87 14-62 1.95 100.29The sp. gr. of the magnetic portlion was 16.095, and that of theThe Pyroxenites of Morbihan. By C. BARROIS (Jahrb. f. Nin.,1888, ii, Ref., 413-414, from Ann. SOC. ge'ol. du Nod, 15, 69-96).-The pyroxenites of Morbihan form beds 0.1 to 2 metres in thick-ness in gneiss and mica-schists of Archean age. The main con-stituent of these rocks is a pale green augite of the fol1owi:igcomposition :-non-magnetic portion 17.01. B. H. B.SiO3 CaO. MgO. Fe20,. Al,O,. Na,O. K,O. Total.51.5 24.3 11.9 8.3 5.0 1.1 trace 102.3The augite is accompanied by zircon, titanite, and apatite in smallquantities, by garnet and idocrase in varying amounts, and by quartzgrains associated with felspar.Irregular grains of orthoclase onlyoccur in certain beds, and microcline is also of exceptional occurrence.A fibrous actinolite is, ho wever, present inlarge quantities, in many casesreplacing the augite, so that rocks resembling nephrite are produced.Titaniferous iron ore and ferric hydroxide are also present. By t h evariety of the character and relative proportions of the constituents,numerous distinct types are distinguished, which may occur in thesame bed. The author regards these pyroxenites as metamorphiclimestones. B. H. B.Riebeckite, and the New Formation of Albite in GraniticOrthoclase. By A.SAUER (Chem. Centr., 1888, 1128, from Zeit.deut. geol. Gess., 40, 138--152).-A new member of the hornblende-granite group has been found by the author in Socotra. This horii-blende, named riebeclzite, has the same composition as arfvedsonite,arid is the analogue of agirin of the augite series. From the analysis(No. 1 below) the formula 5FeSi0,,4Na&3i0,,5Fe,Si3O9 has beencalculated110 ABSTRACTS OF CHEMICAL PAPERS.The Socotra granite is much disintegrated, and the author wasthus enabled to examine more completely certain interchanges in thegranitic orthoclases. The microscopical examination showed anopalescence from the edge towards the centre of the crystals, occa-sioned by the formation of albite, the crystals having been originallyperfectly clenr and without inclosures.The following are tlteanalyses of riebeckite (1) and the secondary albite (2) :-SiOP Al,O,. Fe,03. FeO. MgO. MnO. CaO. Ntx20. K,O.(1.) 50.01 - 28.30 9-87 0.34 0.63 1-32 8-79 0.72- - 6.86 5.19 (2,) 70.24 17.18 0.64 - -J. W. L.The Dachberg, a Volcano of the Rhone. By F. RINNE (Jahrb.f. Min., 1888, ii, Ref., 406-407, from Jahrb. preuss. geol. Landesanst.,1886, 1--22).--Near Rasdorf on the Rhone is situated the Dachberg,on the summit of which is an unniistakeable crater. The unalteredbasalt at the edge of the crater is a dense, glassy felspar-basalt, con-sisting of plagioclase, augite, olivine, magnetite, biotite, and apatite.The chemical composition of the basalt is as follows:-SiO,.TiO,. A1,03. Fe203. FeO. MnO. MgO. CaO. Na20.41.71 3.51 15.80 5.59 7-64 0.16 4.85 10.30 6 . ~ 8K,O. Li,O. SO3. C1. H20. COP P205. Total. Sp. gr.1.00 trace 0.12 0.46 2.22 2-01 trace 101.45 2.90B. H. B.Dolerite of Londorf. By A. STRENG (Jahrb. f. Mirt., 1888, ii,Ilem., 181-229).-The author has made an exhaustive mineralogicalnud chemical investigation of the typical dolerites of the Vogelsberg.The dolerite of Londorf, to which he has principally directed hisat tention, has the following percentage composition :-SiO,. Ti02. Al,O,. Fe,O,. FeO. CaO. MgO. K,O.49-08 1-82 13.43 6-49 5.92 8.92 9-58 1-00Na20. P2O5. H,O. Total:3.42 0.51 0.32 100.49From analyses of its constituents, the dolerite is calculated to becomposed of 1-18 per cent.of apatite, 56.01 per cent. of andesine,7980 per cent. of augite, 20.11 per cent. of olivine, and 3.10 per cent.of magnetite and titaniferous iron ore. B. H. B.Porphyrites at Gabian. By P. DE ROUVILLE and A. DELAGE(Cornpt. rend.. 10 7, 663-667) .-Near Gabian in HBrault there is a,dyke which runs north-east and south-west and consists of twoporphyrites.One of these, which is by far the more abundant of the two, cutsthrough Silurian, devonian, and carboniferous beds without producingany noteworthy metamorphism, and then penetrates into coalMINERALOGICAL CHEMISTRY. 111measures which have undergone somewhat profound alteration. I tfollows that this dyke was formed after the deposition of the coal-measures, and the fact that pebbles in the overlying permian con-glomerate consist of the material of the dyke, shows that it wasformed before the deposition of the permian beds.This dyke is nothomogeneous : it contains apatite, zircon, magnetite, oligoclase, blackmica, orthoclase, amorphous matter, chlorite, calcite, damourite, andquartz.The second porphyrite forms isolated masses in the main dyke, andis of later formation than the lower permian, since the latter bedsare somewhat altered where they come in contact with the dyke. Itcontains large crystals, the nature of which could not, be determined,well developed and distinct microlit,hs of labradorite, magnetite,augite which has to a great extent been converted into chlorite, calcite,chlorite, damourite, quartz, and ferruginous products of decomposition.C.H. B.Composition of the Serpentine Rocks of Colle di Cassi-moreno and Monte Rsgola. By c. MONrEMARTINI (Gnzaetta, 18,103--112).-At Colle di Cassimoreno and also in the neighbourhoodof Monte Ragola, Chistoni found isolated masses of serpentine rockexhibiting strong magnetic polarity. The author is indebted to himfor the two specimens he has examined.The serpentiue of Colle di Cassimoreno is massive and compact; ofbrecciated and porphyritic appearance, witb lustrous, lamellar crystalsof enstatite (bronzite) disseminated through the dark-green ground-mass. Besides these crystals, diopside and picotite also occur, togetherwith magnetite, which forms one of the principal constituents of therock. The hardness of the ground-mass is 6.5 and the sp.gr, at 13"varies from 2.73 to 2.76.The powdered rock is ash-grey in colour, and like all serpentinerocks has a marked alkaline reaction. Heated in contact with theair, it assumes an ochreons tint. It is partly decomposed by theaction of hydrochloric or sulphuric acid, with separation of gelatinoussilica ; the nnattacked portion consists principally of the crystals ofenstatite and picotite. The rock on analysis gave the followingresults :-Loss onSiOz. Alz03. Fe,OJ. FeO. CaO. MgO. ignition. Total.41-19 2.77 4.03 4.33 2.32 34-03 10.13 98%The enstatite, separated as far as possible from the other constituentsof the rock, was analysed, and the results are given under I. In I1the composition of the lherzolite from Germagnano in Piedmont isgiven for comparison :-Si02. AlZO3. FeO. CaO. MgO. H,O. Total.I. 50.65 3.05 7.99 1.68 31-49 2.78 99-5911. 52.19 2.15 8.85 2.96 31.84 1.77 '39.76These results show that the enstatite is bronziteI1 2 ABSTRACTS OF CHEMICAL PAPERS.The rock therefore consists of a serpentine formed by the decompo-sition of peridote togcther with enstatite, diopside, magnetite, andother minerals ; this is also borne out by the microscopical and opticalexamination, full details of which are given. The rock also containsolivine, diallage, and amphibole.The sample of rock from Monte Ragola, which was from the rockmass of the mountain itself, had no magnetic polarity, and was quitedifferent in appearance from the one just described.The ground-mass is light-peen w i t h dull-green nodules dissemi-nated in it ; these cau easily be separated, and on examination werefound to consist- of altered bastite. A microscopical examinationshowed thatl the rock had all the characters of a serpentine formed bythe alteration of a pyroxenic mineral. Neither the enstatite, diop-side, nor spinelle which characterise the Cassimoreno serpentine couldbe discovered in it. Its sp. gr. at 14" is 2.54.The analyvis gave the following results :-Loss onSiO,. Al,O,. Fe,O,. FeO. CaO. MgO. ignition. Total.39.18 3.65 '7.26 1.55 0.42 34.79 12.81 99.66Chromium, nickel, and manganese were also detected.C. E. G

ISSN:0368-1769    

DOI:10.1039/CA8895600109

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

I1 2 ABSTRACTS OF CHEMICAL PAPERS. Organic Chemistry. Action of Zinc Ethide on Nitroethane. Ry I. BEVAD (J. RUSS. Chem. Soc. 1888 20 125-135). -The object of this investigation was t,n rlwirle whether " nitroethane " is really a ~ ~ ~ ~ Q - C O L D ~ Q U D ~ (V. Meper) a hydroxylamine-derivative CH,.CO.NH,O (Kissel) or an isonitroso-derivative HO.CH,*CH:N*OH (Alexheff). When zinc ethide ether and nitroethane are mixed i n an atmosphere of carbonic anhydride the mixture becomes red and after some time crystals are formed which disappear again in about a fortnight. On decompos- ing the product of reaction with water distilling and treating the distillate with hydrochloric acid a solution is obtained which on evaporation gives crystals of a very hygroscopic salt. On decompos- ing this with alkalis n colourless oil of sp.gr. 0.8935 a t 0" is obtsined which proTed to be triethylhydrox2/laminc! Et,NO. It is somewhat soluble in water and soluble in all proportions in ether alcohol and benzene. Its compounds with hydrochloric snlphuric and acetic acids are extremely hygroscopic. The oxalate (Et2NO),,H,C,04 was obtained by mixing ethereal solutions of its constituents. Triethylhydroxyl- amine and its salts have powerful reducing properties as shown by their behaviour with silver cupric and mercuric salts. The original ethereal distillate contains in addition some unchanged nitroethane,ORGANlC CHEMISTRY. 113 but no other product is formed if the substances employed are in molecular proportion. The author concludes that nitroethane is a true nitro-compound.Ita reaction with zinc ethide takes place in different stages. At first crystals are formed of the formula 2EtN0 + 7ZnEt2 (as shown by zinc determinations). When these crystals disappear the compound Et3N(OZnEt)2 is formed; and this reacts with water as follows Et,N(OZn*C,H,) + 4H20 = Et,N(OH) + 2C2H6 + 2Zn(OH),. The Et,N(OH) being unstable however is converted into the free base with elimination of water. Bitromethane treated in the same way with zinc ethide gives methyldiethylhydroxylamine. When zinc ethide is added to bromo- nitroethane a violent reaction takes place and when this is over if the product is distilied with water secondary nitrobutane CH MeEt-KO boiling a t 138" is formed. In this way from lower nitro-compounds those of higher homologues may be formed by synthesis.Nitro- benzene with zinc ethide gives no higher nitro-compound reduction taking place with formation of aniline. If nitroethane were acet- hydroxamic acid it should be formed from hydroxylamine hydro- chloride and acetic anhydride ; the experiments however made by the author with this object gave a negative result. Action of Chlorine on Isopropylethylene. By I. KONDAKOFF (J. Russ. Chem. See. 1888 20 141-148).-Isopropyiethylene (b. p. 21-22"> was brought in contact with chlorine by passing the gas into the vessel by means of a tube terminating at some distance from the surface of the liquid in order to prevent the action from being too violent and to keep the course of the reaction as uriiform as possible from the beginning to the end. When no more drops were formed on the sides of the vessel the process was stopped. Various temperatures from -20" to + 16" were employed but in all cases the products were the same.After washing and drying the product a liquid was obtained which when submitted to fractional distillation boiled chiefly between 143" and 145". A small part boiling a t 100-143" was proved to be a monochloride. The principal portion boiling at 143-145" was an additive product of isopropylethylene C,H,,CIL. I t s sp. gr. at 0" is 1.1106 and 1.0923 at 17.5". m'hen heated in sealed tubes with fused potassium acetate and acetic acid a t 120" it is converted into a glycol ; this boils a t 91%-219" ; the quantity ob- tained however was so small that no experiments could be made to prove that it was isopropylethylene glycol.Isopropylethylene when acted on by alcoholic potash yields a monochloro-derivative boiling between 91" and 96". These experiments show that isopropyetbylene and chlorine yield additive products only as pointed out by Lwoff. B. B. B. B. Polymeride of Methyl Cyanide. By R. HOLTZWART (J. pr. Qhem. [S] 38 343-344).-When an ethereal solution of methyl cyanide is acted on by sodium a white powder is formed and methane j evolved ; when treated with water the powder yields a yellow oil which can be crystallised in white needles from a mixture of ether114 ABSTRACTS OF CHEMICAL PAPERS and light petroleum. A better yield is obtained by digesting the powder with aqueous ether. The crystals melt at 52-58" are soluble in ether dcohol benzene and chloroform sparingly so in water and light petroleum.The molecular formula is C4H6NL. When digested with water ammonia is evolved and a crystalline precipitate sparingly soluble in cold wat,er is formed having the composition C8H8N20 ; and when treated with acetic chloride in ethereal solution a yellow amorphous precipitate of the composition 2C,H6N,,CO&feCl separates ; this is decomposed by m-ater forming a white crystalline powder of the formula CsHgN3. The investigation is still in progress. Polymeride of Ethyl Cyanide. By E. v. MEYER (J. pr. Chem. [ 21 38 336-343).-The white powder obtained by the action of sodium on ethyl cyanide (Abstr. 1888 802) has been proved to be formed as follows :-(1) Na + 2EtCN = NaCN + C2H6 + C,H,Na.CN ; (2) C,H,Na.CN + EtCN = CGH9NaN2. The oil which it yields on treatment with water cryst allises in tables which melt at 47-48' boil at 257-258" (uncorr.) are little soluble in cold water decomposed by warm water and soluble in ether and alcohol; the molecular formula C,H,,N has been obtained both by Raoult's method and by the vapour-density determination ; when heated at 330-340" for several hours it is converted into ethyl cyanide.Hydrochloric acid decomposes it half the nitrogen appearing as ammonium chloride and half as an oil soluble in ether; the ethereal solution is shaken with sodium hydroxide dried orei- lime and the pure oil precipitated by adding water. This oil has the composition C6HgN0 and is recon- verted into the original substance when heated with strong ammonia.It would thiis appear that the polymeride is a-imidoprojpion2/lethyl cyanide NH:CEt*CHiVe*CN and the oil a-propionylethyl cyanide or cyanodiethyl ketone COEt*CHMe*CN. Tbe former is converted ihto ammonia carbonic anhydride and diethyl ketone when heated with strong hydrochloric acid at 150° and the latter into propionic acid and ammonia when heated with aqueous Dotash. The imido- A. G. B. compound is converted into propylamine by reduction. A. G. B. Ammeline. By A. SMOLKA and A. FRIEDREICH (Monatsh. 9,701- 707) .-When dicyanodiamide (1.5 grams) and carbamide (1.08 grams) are heated at 170-180" for 2+ hours much ammonia is set free and on treating the product with water an inqoluble white residue remains from which ammeline C,H,N,O (yield 1.57 grams) may be obtained by dissolving it in alkali and reprecipitating with acetic acid re- peatedly; finally recrystallising it fi-om a hot aqueous solution of potash.Ammeline can also be prepared by heating dicyanodinmide with cyanic or cyanuric acid. It may therefore be represented by one of the two formulse NiC*NH*C(NH)*NH*CO-NH or C0:N.C (N H)*NH*C (NH)*NH,. The authors consider that the first of these most probably represents the constitution of the compound since ammeline unlike biguanide-ORGANIC CHEMISTRY. 115 derivatives of which the second formula represents a member is not a strong base and does not give coloured compounds with salts of cobalt and copper. By R. NASINI and A. SCALA (Gazzetta 18 62-72).-The authors have been occupied for some time with the examination of organic sulphur compounds especially with the object of proving the tetravdency of sulphnr and the appearance of Klinger and Maassen's work (Abstr.1888 357) whose results are diametrically opposed t o theirs compels them to publish a portion of their researches. Although various sulphur compounds containing a1 kyl radicles have been obtained of the form SM,A and SM,M,A unfortunately their vapour-density cannot be determined and it remains uncertain therefore whether the four monad radicles are united to the sulphur or whether the compounds are molecular compounds. Klinger and Maassen in repeating Kriiger's work found that the sulphine containing one methyl- and two ethyl-groups was the same whether it was prepared by the action of methyl iodide on ethyl sulphide or of ethyl iodide on ethyl methyl sulphide that is they denied Kriiger's statement that two isomeric compounds of the formula E t,MeS existed capable of yielding distinct platinochlorides crjstallising in different forms.Nasini and Scala state that they have prepared the iodides of the sulphine according to Kriiger's directions and converted them into the corresponding platino- chlorides one of which crystallises in the cubic system whilst the other is monoclinic. E t h y lrn et hy 1 e thy lsu lp hin e p latinoc hlorid e (E tM eE t S Cl),,P t C14 melts at 211-212" and fcrms monoclinic crystals G. T. M. Sulphines and the Valency of Sulphur. a b c = 1.15113 1 0.794745 ; p = 49" 17' 56". Forms observed f l l O ) ( i l l ) (OOl) (010) ; combinations (110) (111) (001) arid (llO)(ill) (001)(010).Diet h y lm eth ylsulishine pl atinoch loride ( EtpLMe S Cl) 2 Pt C14 melts at 205" and crystallises in the monometric or cubic system ; combha- tions (100) (1 11). These crystals when auperficially observed may easily be taken for monoclinic owing to the development of one face but their optical properties prove that they belong to the monometric system as when examined by polarised light there are no signs of double refraction. This leaves unsettled the question as to whether sulphur is tetravalent or not. C. E. G. Trimethylethyleneglycol from Methyl Isopropenyl Carbinol. By I. KONDAKOFF (J. Busr. Chern. SOC. 1888 20 32-34).-1n a former paper the author has shown that methyl isopropenyl car- binol when heated with dilute sulpburic acid (1 per cent.H,SO,) becomes converted into trimethylethylene glycol whilst hydrocbloric acid is without action at the ordinary temperature but gives rise to products of condensation at a higher temperature. The author now finds that chlorine-derivatives of trimethylethylene yield trimethyl-116 ABSTRACTS OF CHEMICAL PAPERS. ethylene glycol if left in contact with water in a closed flask a t the ordinary temperature for several months. B. B. Combination of Benzaldehyde with Polyhydric Alcohols. By MAQCENNE ( Compt. rend. 107 658-659).-The dibenzoic acetal of perseitol (perseiie) previously described (this vol. p. 32) was made with alcohol of 85" to go" without addition of zinc chloride. T t is assumed to be an acetal becausa it resembles the product obtained by Mennier by the action of benzaldehyde on mannitol and Friedel has pointed out that in all probability this is an acetal.When a polyhydric alcohol containing an odd number of hydroxyl- groups is converted into an acetal one of the hydroxyl-groups is left unattacked and since the difference in composition between the acetals of two successive homolopes can be detected by analysis the conversion into acetals affords a convenient method of determining the number of hydroxyl-groups in a polyhydric alcohol. I2 C. H. B. Constitution of Sorbinose. By H. KILIANI and C. SCHEIBLER (Be?.. 21 3276-3281).-Sorbinose behaves towards bromine and water similarly to levulose and remains practically unchanged after a week it contains therefore no aldehyde-group. When heated with nitric acid (sp.gr. = 139 2 parts) for 40 hours at 35O trihydroxy- glutaric acid COOHfCH(OH)]3*COOH (this vol. p. 32) is formed. Potassium trihydroxyglutarate crystallises in monoclinic plates ; a b c = 1.4641 1 0.7094; p = 101" 3'. When sorbinose is reduced with hydriodic acid and amorphoiis phosphorus it is converted almost quantitatively into hexyl iodide. Sorbinose has probably the constitution OH.CH,.[ C H (OK)],*CO.C E,*OH. N. H. M. Changes suffered by Starch when Dissolved in Hot Glycerol. By K. ZULKOWSKI (Ohem. Centr. 1888 1060 from B e y . Oestwr. Gess. Chcm. Ind. 10 2-4).-Starch when heated in glycerol at 200° produces a solution which gives a blue coloration with iodinc at first but which gradually changes to red.Addition of alcohol at this point precipitates erythrodextrin. If the heating is continued up to 210c until the red coloration gives place to a brown one glcohol precipitates achroodextrin. Other compounds are formed besides the t w o above named and were separated by precipitation with barium hydroxide &c. but were not further characterised. J. W. L. Derivatives of Allylamine. By C. PAAL (Rer. 21 3190-3196 ; compare Gabriel Abstr. 1888 1267) .-Bromallylamine CJH4Br.NH 1s prepared b,r adding dibromopropylamine hydrochloride to excess of alcoholic potash diluting the product with water and distilling with stearn. It is a colourless mobile very unstable oil boils a t 125" with partial decomposition and mixes i n all proportions with all ordinary solvents.When mixed with potassium carbonate it is decomposedORGANIC CHEMISTRY. 117 with separation of potassium bromide. When boiled for a long time with alcoholic potash i t seems to be for the greater part transformed into a hydroxy-base but when the temperature is raised to 120-130" it is completely decomposed. C3H4Br.NH.C3H1.NH2,HBr is formed when bromallylamine is kept for a long time ; the same salt remains when bromallylamine is distilled. Silver nitrate produces a white amorphous and mercuric chloride a white crystalline precipi- tate in an aqueous solution of free bromallylamine. The hytlroch Zoride C3H4Bi*-NH2,HCl crystallises in large needles or prisms melts at 177-180" and is readily soluble in water or hot alcohol. The plntinochloride (C,,H,Br.NH,),,H,PtCl crystallises in yellow plates and is readily soluble in hot water but almost insoluble in absolute alcohol. The awochloride C3H1Br*NHZ,HAuCl4 crystallises in sniall yellow needles and decomposes when kept for some time in aqueous solution.The hydrobromide C3H4Br*NH,,HBr crystallises in large colourless quadratic prisms melts a t 223-224" and is more sparingly soluble in alcohol and water than the hydrochloride. The oxaZatP C3H,Br.NH,,C,H,04 crystallises in colourless plates melts a t 136-138" and i s readily soluble in water but insoluble in alcohol and ether. TribrornopropylamirLe hydrochloride C3H4Br3NH,,HC1 prepared by adding bromine (1 mol.) to a well-cooled concentrated aqueous solu- tion of bromallylamine hydrochloride crystallises from absolute alcoliol in colourless needles.The free base is a heavy yellow very unstable oil with a pungent smell. The aurochloride C3E1Br3*NH2,HAuCl4 crystallises from water in which it is moderately soluble in golden-yellow plates melting a t 170". The PZatinochZoride ( C,H,Br3*NH,),,H,PtC16 crystallises from hot water in orange plates and is decomposed when heated at 245". Isob ut y l d i b rornoprop y laniine hydrobromide C4Hg*NH*C3H,Br,HBr prepared by adding bromine (1 mol.) to a well-cooled glacial acetic acid solution of isobutylallylamine crystallises from hot water in which it is readily soluble in slender needles and is sparingly soluble in alcohol. The free base is a heavy almost colourless very unstable oil with a feeble basic smell. When auric chloride is added to an aquecus solution of the hydrobromide the aurochZoride separates as a yellow oil and then solidifies.BzLty Zdibronaopro~y Zamine hydrobromide C4H,*NH-C3H5Br2,HBr can be prepared by treating bntylbromallylamine with excess of dilute hydrobromic acid. It. crystallises in large concentrically grouped needles and is readily soluble in water and hot alcohol. The m r o - chloride separates from an aqueous solutioii of the hydrobromide in flat needles when auric chloride is added to an aqueous solution of the hydrobromide. Buty ZbromaZZy Zamine C4HgNH*C3H4Br can be prepared by boiling the isobutyldibromo-derivative with dilute alcohol for a long time adding alkali and distilling with steam. It can also be obtained by mixing the hydrobromide with excess of alcoholic potash in the cold keeping the mixture for some time diluting with water and adding potassium carbonate until the alcoholic solution of the base separates A crystalline salt probably118 ABS'I'HAGTS OF CHEMICAL PAPERS.a t the surface of the aqueous solution; the solution of the base is dried over potassium carbonate poured into an alcoholic solution of oxalic acid and the precipitated salt decomposed with alkali. It is a yellowish oil with a camphor-like odoar ; it cannot be obtained in the pure state as it is partially decomposed when distilled. The oxalnte C7HI4BrN,CZH2O4 cr,ystallises in colourless needles melts at 230-231' and is moderately soluble in water. Isoam y ldibromopropy 1 am ine hydrobromide C5Rl,*NH.C,H5Br2,HBr prepared by treating isoamylallylamine with bromine in glacial acetic acid solution and then adding concentrated hydrobromic acid crystallises in plates melts at 230-231" and is sparingly soluble in alcohol and cold water.The free base resembles the corresponding butyl base. The platinochloride is a reddish-yellow oil. Amy l d i bromoprop y lamine hydro b romide prepared by treating am pl- allylamine as described above crystallises in needles melts at 150° and is moderately soluble in cold water and alcohol. Isoamylbronzalll! lamiite C5Hll*NHG3H4Br prepared by treating iso- amyldibromopropylamine hydrobromide w i t h alcoholic potash or hy boiling the free base with dilute alcohol is an oil ; it is insoluble in water and boils a t about 150" with partial decomposition. F. S. K. Synthesis of Hydroxypropylenediisoamylarnine.By E. LOU~SE ( A n n . Ch im. P h ys. 13 433-442 ) .- Hyd~ox!pi*op y 1 e nediisoamy lumine C,,H,,NO is best prepared by heating propplenechlorhydrin (1 mol.) and diisoamylamine (at least 16 mols.) a t 100" in a closed vessel for 30 hours. The product is mixed with concentrated potash to decom- pose the diisoamylamine hydrochloride which is formed in the reaction the mixture is again heated for 10 hours and the oil which separates is dried over potassium carbonate and fractionated. The yield is 70 per cent. of the theoretical quantity but it is impossible to get rid of the whole of the diisoamylamine by fractional distillation. The hydroxypropylene-derivative is obtained in the pure state by agitating the fractionated liquid with a small quantity of dilute warm hydro- chloric acid and decanting the supernatant oil.It is a colourless oil with a somewhat disagreeable smell and boils a t 242-2+b0. It is sparingly soluble in water but readily in alcohol ether and other solvents of the fatty series. All the simple salts with the exception of the picrate which is sparingly soluble are syrupy liquids and very readily soluble in water. The platinochloride ( C,,H,,NO)z,H2PtCl separates from acidified alcohol in orange crystals but the auro- chloride is a yellow sparingly soluble oil. Propy lenediisoamylamine benzoate CIsH2,N*OBz is prepared by gradually adding a slight excess of benzoic chloride to a well-cooled dry ethereal solution of the alcohol and after evaporating the ether heating the mixture a t 100" for six hours in a sealed tube.The product is treated with boiling water the cold mixture shaken with ether to remove benzoic acid and the salt separated by adding potassium cat bonnte. It is a colourless oil readily soluble in alcohol ether chloroform &c. but insoluble in water. It is hydrolysed when boiled with potash or when treated with strong acids and is decom- posed when distilled. This salt still has basic properties ; its oxalate,ORGANIC CHEMISTRY. I1 9 C,,H3,NO2,C2H,O4 crystallises from hot water or alcohol in slender colourless needles and is readily soluble in acetone and chloroform but insoluble in ether. Most of its other salts do not crystallise and are very readily soluble excepting the platinochloride and the auro- chloride which are only sparingly soluble.Propy lenediiaoamylamine acetate prepared in like manner is a colourless oil readily soluble in alcohol ether &c. b u t only sparingly in water. Its oxalate crystallises in needles and is very readily soluble in alcohol and chloroform but only moderately in water and sparingly in ether. Its other salts are very readily soluble in water and do not crystallise. F. S. K. Glyoxalbutyline and Glyoxalisobutyline. By J. RIXGER (Monatsh. 9 603-612 ; compare Radzissewski Abstr. 1883 308 728 1086 ; 1884 986) .-Glyoxalhufyline prepared according to the directions given by Radziszewski from glyoxal ammonia and normal botaldehyde is a viscid hygroscopic oil having a sp. gr. of 1.0125 at 20" and boiling under a pressure of 738 mm. a t 266-268".It is fairly soluble in water and when an aqueous solution is treated with oxalic acid the compound (C6HloNz)z,CzH,04 + 2H20 is formed ; this crystallises in rhombic plates or long needles and melts at 159-161". The anhydrous oxalate ( C&I,,N2),,C,HzOa is precipitated as an amor- phous white powder on mixing alcoholic solutions of the acid and base. It partly sublimes a t 170° and melts with decomposition a t 290-195". The platinochloride 2C,HloN2,H~PtC16 crystallises in orange-red prisms and on treatment with iodoparaffins gives the following bases :- Omdviethylbutyline C6HgMeN2 is a colourless viscid liquid having a sp. gr. of 0.9850 at 19.8" and boils at 214-216" under a pressorc of 722 mm. It dissolves readily in cold water alcohol ether and chloroforrn.The platinochloride 2C,H,MeNz,HzPtC;16 crystallises in orange-red rhonibic prisms. Oaalethylbutyline C6H9EtNz has a sp. gr. of 0.9593 a t 16.5" and boils at 218-222" under a pressure of 736 mm. The platinochloride is a yellow amorphous powder. Oxalpropylbutyline C6HgPrN2 is a liquid of sp. gr. 0.9393 at 18.9". It boils at 226-228" under 8 pressure of 726 mm. and forms a platinochloride insoluble in alcohol and ether but readily s o h ble in hot water. OxalbzLtylbutyline C4Hg.C6HgN2 has a sp. gr. of 0.9379 at 18.9" and boils a t 242-245" under a pressure of 728 mm. It forms double salts with the chlorides of zinc cadmium. and platinum and on oxidation with hydrogen peroxide gives butyloaamide CzH,0LN2*C4H9 crystallising in lustrous needles which sublime at 130" and melt at Oxa2i.sobutylbutylie has a sp.gr. of 0.9403 at 13*4" and boils at The platinochloride forms Oxalisoamylbutylilze C5Hll*CBH9N2 has a sp. gr. of 0.9197 a t 18*9" The platino- 197-198". 231-233" under a pressure of 736 mm. orange-yellow needles soluble in alcohol. and boils at 250-252" under a pressure of 784 mm. chloride crystallises in rhombic needles.1-20 ABSTUCTS OF CHEMICAL eAems. GlyoxaZisobuty line prepared from isobutnlde hyde ammonia and glyoxal is a crystalline solid melting at 125-126" and boiling a t 256-260'. It readily dissolves in hot water alcohol chloroform and ether and forms the salts C6HJ!Tq,HCl melting a t 205" C6H,,N,,HBr melting a t 22Z0 and C,H,,N,,C,H,O melting at 194-195". By treatment with iodoparaffins it furnishes the follow- ing bases:- Oxalmethyl~sob~tz~lilzP C6H,MeN ; this is a colourless viscid oil of sp.gr. 0.9576 at 16.6" and boils a t 205-206". The platinochloride crys- tallises from water in orange-red plates the compound CsH,MeN2,MeI in colourless rhombic prisms melting a t 245-246". Oaalpropylisobufyline C6H9PrN2 which has a sp. gr. of 0.9299 and boils at 225-227'. The platinochloride crystallises in orange-red needles. Oxalisoamylisob~~tyline; this has a sp. gr. of 0.9281 a t 17*3" and boils at 246-248" under a pressure of 738 mm. The platinochloride is scarcely soluble in alcohol but dissolves readily in water. All the oxalines described above turn yellow on exposure to the air are miscible with alcohol ether and chloroform and have charac- teristic unpleasant odours.G. T. M. Action of Sulphur on Paraisobutaldehyde. By G. A. BARBAGL14 (Gazzettn 18 85-88).-Unlike isobutaldehyde sulphur has no action on the paraldehyde a t 150" but when heated with it for a long time (100 hours or more) at 180" it becomes reddish-brown and on opening the tube abundance of gas escapes containing much hydrogen sul- phide. The liquid has an acid reaction and if left for a time sepa- rates into two layers. On submitting it to distillation a liquid i q obtained which by means of fractional distillation c m be separated into three portions ; the first distilling between 70" and go" was found on analysis to be isothiobutaldehyde ; the second distilling between 90" and 140" has not yet been examined ; whilst the third 140-160" is isobutyric acid.The reaction is probably in the first place- 4CHMe2GOH + S2 = 2CHMe2*CSH + 2CHMe2.COOH but a t the high temperature necessary for the reaction the excess of sulphur acts on the isothiobutaldehyde converting i t into polgsulphide with evolution of hydrogen sulphide- CH3 CH3>HC*CHS + S2 = S<gz>HC*CHS + H,S. In all probability this product exists in the intermediate portion of the distillate. C. E. G. Action of Ammonia on Methylethylacraldehyde. By E. HOPPE (Monatsh. 9 634-657 ; compare Waage Abser. 1884 172).-On passing ammonia into an ethereal solation of methylethylacraldehyde a t O" a substance separates in white flakes but is of so unstable a nature that it is impossible to isolate it. When heated in sealed tubes at 100" with excess of alcoholic ammonia methylethylacraldehpde yields aORGANIC CHEMISTRY. 121 viscid liquid which has a bitter taste and an odour resembling parroline. No definite compound can be isolated from it but its solution in hydrochloric acid gives white or yellow precipitates with most of the salts of the heavy metals. When heated in sealed tubes at 200" for 12 hours the substoance decomposes and on opening the tube much ammonia is evolved.After several heatings in sealed tubes no more ammonia is produced and the following bases can be isolated from the residue :-(1) Picoline ; (2) parvoliiie identical with that G b - tained by Waage and yielding on oxidation a-p-pyridinedicarboxylic acid; ( 3 ) a new base C12H19N which forms a clear mobile liquid having a pale blue fluorescence a bitter taste and a smell resembliug parvoline but less intense.It dissolves readily in alcohol and ether hut is only slightly soluble in water. The platinochloride crystallises in orange-red monoclinic prisms is very soluble in alcohol but only slightly so in water. G. T. M. Action of Sulphurous Acid on Methylethylacraldehyde. By E. LUDVIG (Monmtsh. 9 658-674).-The author has further investi- gated the compound obtained by Lieben and Zeisel from sodium hydrogen sulphite and methylethylacraldehyde (Abstr. 1883 570) and finds that it is most conveniently prepared by the direct addition of sulphurous acid to the unsaturated aldehyde. 10 grams of the aldehyde and 30 C.C. of water were introduced into a tube and saturated with sulphurous acid at 0"; after sealing the tube was heated at 80" for four hours and the contents then neutralised with barium carbonate.The filtered solution on concentration in a vacuum at 30" gave barium hTdroxyhexanedisulphonate C6H1,0 (SO,) Ha + 'LH,O. The salt dissolves readily in water is only slightly soluble in alcohol and is very unstable. On heating with baryta-water methyl- ethylacraldehyde and barium snlphite are formed. If the contents of the tube after heating are diluted with an equal volume of water and three-quarters of the liquid distilled off the residue on neutrali- sation with barium carbonate and concentration in a vacuum over snlphuric acid gives the barium salt of capraldehydesulphonic acid ( C,Hl1O*SO3),Ra as an amorphous mass. Capraldehydesulphonic acid can also be prepared by allowing aqueous sulphurous acid to react with niethylethylacraldehyde at ordinary temperatures for several clays when all the oil disappears.From the solution after saturation with barium carbonate and oxidation with bromine-water barium sulphocaproate C6HloS05Ba crystalhing in hexagonal plates may be isolated. Si~Zp7~ocaproic acid may also be prepared from barium hydroxyhexanedisulphonate. The silver salt C6HloS0,Ag crystal- liees i n small plates the calcium salt C6H,,,So5Ca + l+H,O in scales. On reduction with sodium amalgam in solutions containing free sulphuric acid both hydroxyhexanedisulphonic acid and cap'. aldehydesulphonic acid yield a siilphonic acid of hexyl alcohol the sodium salt of which C6Hl3So4Na) obtained in a slightly impure condition forms an amorphous hSgroscopic mass and yields on distillation with lime a mixture of hexyl and hexenyl alcohols boiling at 149*6-151*6".G. T. &I. VOL. LVI. k122 ABSTRACTS OF CHEBIICAL PAPERS. Action of Potassium Cyanide on Ethyl a-Bromopropionate. Freparation of the Isomeric Symmetrical Dime thylsuccinic Acids. By N. ZELINSKY (Ber. 21 3160-3172).-Ethyl a-cyano- propionate and ethyl dimethylsuccinate are obtained when ethyl a-bromopropionate (250 grams) is boiled for about six hours with finely divided potassium cyanide (96 grams) in alcoholic solution (130 grams) the whole beinq constantly shaken. The yield is greater when the mixture is heated by a stream of hot air. The product is washed with water dried and fractionated. A small quantity of a crystalline substance is also formed i% this reaction.Efhyl a-cyclnopropionate CN.CHMe*COOEt is a colourless liquid boils at 197-198' is not miscible with water and yields a very hygroscopic sodium-derivat ive. E thy1 dimethyls~iccinate (compare Scherks Abstr. 1882 38) can be prepared by gradually adding ethyl a-bromopropionate (56 grams) to a mixture of sodium (0.72 gram) and ethyl a-cyanopropionate (4 grams) in alcoholic solution. It boils at 272-273" (compare Scherks Zoc. c i t . ) and yields dimethylsuccinic acid melting at 192" and the isomeric acid melting at 123-124" when heated for 6-8 hours with hydrochloric acid (compare Otto and Beckurts Abstr. 1885 753 ; Otto and Rossing Abstr. 1888 45 ; also Bischoff and Hjelt Abstr. 1888 1057). Both acids yield the same anhydride when distilled.The anhydride crystallises in small plates melting at 87". When the anhydride is boiled for a short time with a small auantitv of water. it is almost entirelv converted into the acid of 1 d " lower melting point but a small quantity of the isomeric acid is also formed. F. S. I(. Solubility of the Silver Calcium and Barium Salts of Normal Caproic and Diethylacetic Acids. By P. KEPPICH (Monatsh. 9 589-602 ; compare ibid. 6 565).-The solubilities of the different salts were determined by Raupenstrauch's method. Tho formula? deduced from these determinations are as follows :- Silver normal caproate.. . . Calcium normal capoate.. Barium normal caproate . . Silver diethylacetate . . . . . Calcium diethylacetate . . . Barium diethylacetate is so intensely soluble in water that the S = 0.07768 + 0.0008268S + S = 2.727 - 0*01475(t - 0.7) + S = 9.47 - 0 08975 ( t - 0.S) + S = 0.402 + 0.000847 ( t - 0.7) + S = 30.119 - 0.2617 ( t - 0.7) + 0 000031213t2.0.0002203 ( t - 0.7)'. 0.0014983 ( t - 0.5)' 0.000038 ( t - 0.7)2 0.001498 ( t - C.7)'. author did not succeed in obtaining any analytical results. G. T. M. Chlorine-derivatives of Ethyl Acetoacetate. By P. GENVRESSE (Corryt. rend. 107 687-689).-When chlarine is passed into ethylORGANIC CHEMISTRT. 123 acetoacetate the temperature rises to 265" but afterwards falls and the chief products are the di- and tri-chlorinated derivatives together with small quantities of higher substitution products. When the dichloro-derivative is heated in sealed tubes with dilute hydrochloric acid it yields unsymmetrical dichloracetone water and alcohol and hence it has the constitution CHC1,.CO.CXL.COOEt. When treated with chlorine at l i O " it yields the tri-derivative together with small quantities of the tetra- and penta-derivatives.The trichloro-derivative when heated with dilute hydrochloric acid in sealed tubes a t 170" yields trichloracetone CCl,*COMe alcohol and carbonic anhydride so that its constitution is CCI,*CO-CH,.COOEt and not CHCl,.C(OH):CClGOOEt as supposed by Mew-. Efhy Z tetrachZorcLcetoacetate boils with partial decomposition a t 229-231" under ordinary pressure and with less decomposition a t 153-157" under a pressure of 40 mm. It is colourless and heavier than water; when heated with dilute hydrochloric acid under pressure it yields carbonic anhydride alcohol and unsymmetrical tetrachloracetone so that its constitution is CCI,*CO*CHCl-COOEt. Ethyl pentachloi*ncetoac~tate boils a t 240-244" under ordinary pressure or at 164-168" under a pressure of 35 mm.and is a colourless liquid heavier than water. When heated at 160" with dilute hydrochloric acid it yields carbonic anhydride alcohol aiid pentachloracetone so that its constitution is CC13*CO*CC1,.COOEt. If ethyl acetoacetate is subjected to the action of chlorine a t 150" to 220" for 10 days derivatives containing 7 and 9 atoms of chlorine are obtained. The former CC13*CO*CCl,~COOC,H3Clz is a qvupy almost colourless liquid which boils a t 270-272" with much decomposition under ordinary pressure or with slight decomposition at 220-225" under a pressure of 110 mm.The derivative with 9 atoms of chlorine CC13.C0.CC1,*COOC,HC1 is a syrupy liquid which does not solidify a t -23" and boils at 225-230" under a pressure of 40 inm. Methyl acetoacetate yields similar derivatives. C. EL. B. Dihydroxystearic Acid obtained by the Oxidation of Oleic Acid with Potassium Permanganate in Alkaline Solution. By N. SPIRIDONOFF ( J . Russ. Chent. SOC. 1887 19 646-654).-The dihydroxystearic acid was prepared by Syrneff and Snytzeff's method from ordinary oleic acid and the present paper contains a determitia- tion of its constants. Solubility in ethyl alcohol of 99.5 per cent,. a t 19" 100 pts. of solution contain 0.59 pt. of the acid dry ethyl ether a t 18" = 0.19 pt. The ethyl salt (m. p. 9.3 8-100°) was obtained by the action of hydrogen chloride on an alcoholic solution of the acid.Solubility in alcohol of 91.5 per cent. 100 pts. of the solution at 16" contain &*58 pts. ; a t 18" = 4.72 pts. ; ethyl ether at 18" = 1-75 pts. The methyl salt (m. p. 105-106.5") 1 0 pts. of the alcoholic solu- tion a t 18.5" contain 3.34 pts.; dry ether at 19" = 1.03 pts. The acetyl-derivative was obtained by the action of acetic anhydride at 150" on the acid. It is a colourless viscid liquid and its composition is Cl8H34Ac204. Oxidation with potassium permanganate in alkaline 1; 2124 ARSTRACTS OF CHEMICAL PAPERS. soIution yielded as the chief products caprylic suberic and azelai'c acids together with some unchanged dihydroxyst,earic acid. This was proved by t'he analysis of the free acids and their salts.The same acids are found among the products of oxidation of oleic acid and are therefore only products of the oxidation of dihydroxg stenric acid. B. B. Action of Ally1 Iodide and Zinc on Ethyl Malonate. By V. MATV~EFF ( J . Rum. Cl~em. SW. 1887 19 643-646).-Following the method by which Schukoffsky prepared the ethyl salt of diethyl- malonic acid (Abstr. 1888 1179) the aiithor by the mutual action of ally1 iodide zinc and ethyl malonate has obtained ethyl dially Zmalonate C(C,H,),(COOEt) together with free propylene. The ethyl salt is an oily liquid boiling a t 239-241" and having the sp. gr. 0.99181 at 20" 0.98707 a t 30° and 3.98085 at 35". The free acid obtained by hydrolysis of the ethyl salt is described and also the corresponding sodium calcium and silver salts.B. B. Action of Malei'c Acid on Aniline. By I. OSSIPOFF (J. BUSS. Cltenz. Soc. 1888 20 85-97).-Referring to the work done by Perkin Michael Wing and Palmer and especialIy by Anschutz and Wirtz on the constitution of male'ic acid the author tried to solve the problem in the following manner :-Hydrogen sodium maleate was dissolved i n water and boiled with aniline in a flask furnished with a reflux condenser when crystals were formed which were greenish- yeilow melted a t 141- 143" and left no ash on incineration. They are only sparingly soluble in ether chloroform benzene and light petro- leum but easily i n alcohol. After purification they become white and the melting point rises to 144 -145". Elementary analysis however proved that the substance is not homogeneous; the principal con- stituent is the aniline salt of phenylaspartic acid or its isomeride.The product was treated with baryta-water and the barium lend and silver salts prepared. With acetic anhydride i t yields acetanilide. With diphenylamine it gives a substance melting a t 207-208" pro- bably phenylaspartanil. The liquid from which the crystals have sepa- rated contains a mixture of sodium salts. The author concludes that mnle'inanil is the anil of male'ic acid and phenylaspartanil the anil of a lactone isomeric with phenylaspartic acid. B. B. Isomerism of Fumaric and Malei'c Acids. By I. OSSIPOFF (J. Buss. Chem. Soc. 1888 20 97-lW).-A purely theoretical p.iper based on the results described above. B. B.Methyl and Ethyl Salts of Ethylenediamidoformic Acid and their Nitro-derivatives. By A. P. N. FRANCHIMONT atld E. A. KLOBBIE (Rec. Trav. Chim. 7 258-262).-The methyl salt C,K4(N H-COOMe)2 is easily obtained in almost theoretical quantity on mixing methyl carbonate (2 mols.) with ethylenediamine (1 mol.). It is very soluble in boiling water alcohol and chloroform but less soluble in ether and benzene and melts a t 138-133". It dissolyes inORGANIC CHEMISTRY. 125 concentrated nitric acid with development of heat and on adding water to this solution a white powder is precipitated having the melting point of the original compound but containing 21-23 per oeiit. N the original compound having only 16.41 per cent. It is nearly insoluble in cold but more soluble in hot water very soluble in chloroform and benzene but only slightly in ether and alcohol.From ail solvents it separates in slender needles. The ethyl salt bas already been described by Fischer and Koch under the name ethylenediurethane. The authors have obtained it along with various bye-products by heating a mixture of ethyl carbo- nate and ethylenediatnine at about 200" for 16 hours as a colourle+~ substance soluble in ether. The nitro-derivative is obtained in like manner to that of the methyl salt. It is a compound of very similar properties melting at 83-84'. Analysis shows that it is a dinitro- derivative. Distilled with aqueous poIabh i t gives a distillate which on the addition of potassium carLonate separates into two layers. The upper contains ethyl alconol and the lower ethjlme dinitratnine.'This nitro-derivative therefore has the constitnlion CzHk [ N( NO,) *COOE t]z. H. C. Ureides and their Nitro-derivatives. By A. P. N. FRANCHIMONT and E. A. KLOBBIE (Rec. Trav. Cltim. 7 236-257).-The authors diy- tinguish-(1.) Ureides of bibasic acids in which each of the tMo NH-groups is between two CO-groups; these do not yield nitro- deriiatives. (2.) Ureides of monobasic acids i u which one of the NH-groups is betweeu two CO-groups and the other between a CO-group and the hydrocarbon residue these give mononitro-deriva- tives. (3.) Ureides in uhich each NH-group is attached to a hydro- carbon residue and neither lies between two GO-groups. These last compounds yield dinitro-dei-ivatives and the name " ureinrs " is proposed for them.A number of the nitro-derivatives of (2) and ( 3 ) have been considered i n a former paper (Abstr. 1888 llSO) and the present is a continuation of this work. Nitrohydantoin when boiled with 25 times its weight of water loses 1 mol. of carbonic anhydride and takes up 1 niol. of water being converted into nitramidoacetamide which on further evapora- tion of the aqueous solution yields glycolamide. Nitro-lactylcarb- amide treated in the same manner loses carbonic anhydride and nitrous oxide and yields an acid solution which gives with cobalt acetate the reaction for lactic acid. Nit?.oacetonllZcarEar,zide is prepared by evaporating acetonylcarb- amide with five times its weight of nitric acid and recrystallising the residue from absolute alcohol or benzene.It forms Flender colourless needles melting at 140-141". Its probable constitution is When boiled with 25 times its weight of water it loses carbonic anhydride and nitrous oxide and appears to yield a-hydroxybutyr- amide and pc- hydroxy butyric acid.126 ABSTRACTS OF CHEMICAL PAPERS. Ethylenedinitrureine ~etkyEenedinitrocarbalnide) N(N02)-CHz co<N(NOz)-CH2>9 gives a compound with 4 mols. NaOH soluhle in water and insoluble in alcohol and with 4 mols. AgNO a white compound which detonates violently on heating. On boiling with water it yields ethylenedi- nitramine; this compound forms salts containing 2 mols. of the metal. Heated with dilate sulphuric acid it loses nitrous oxide and gives aldehyde and glycol. Reduction experiments have up to the present led to no definite results.A cety ZerLetetramet liy2diureine (t et rame th ylgl ycolnril e) co/NMe*CH*NMe \co \NMe*AH*NMe/ is prepared by evaporating on a water-bath aqueous solutions of glyoxal and dimethylcarbamide to which a few drops of hydrochloric acid have been added. It crystallises in long colourleas brittle needles of bitter taste melting a t 217” very soluble in water alcohol and chloroform and slightly soluble in ether and benzene. On treatment with strong nitric acid it is converted into acetylene- trimethylmononifvodiureine by the displacement of one of the methyl- groups by the nitro-group. The nitro-derivative crystallises in fine colourless needles melting at 225-226” not very soluble in water or alcohol and still less so in ether and benzene.Dinietliy ZocztyZePcediurein~ (tlimethylglycoluiile) NH-CMe-NH ‘NH-CMe-NH’ separatcs as a white powder when a mixture of 20 parts of diacetyl 50 parts of water and 35 parts of carbamide is left for 24 hours. It is slightly soluble in water from which it crystallises i n slender needles or small prisms ; it is very slightly soluble in alcohol and not a t all in ether chloroform or benzene. With nihic acid it yields a dinitro- derirative which on boiling with water loses carbonic anhydride and nitrous oxide and gives diacetyl and carbamide. This nitro-deriva- co’ I b o NH - Chile-N (NO,) ‘XH*CMe*N( NOz) tive probably has the constitution GO’ ] )CO. From the above and the authors’ former experiments it appears that the action of nitric acid on the ureides (2) and (3) results in the displacement of one or more of the hydrogen-atoms of the NH-groups by NOz and the formation of nitramides.H. c. Identity of Methronic Acid and Sylvanecarboxyacetic Acid. By R. FITTIG and A. HANTZSCH (Ber. 21. 3189-3190; compare Fittig and Schloesser Ahstr. 1888 1089 Polonowsky ibid. 1175).- The acid obtained from glyoxal and ethyl acetoacetate (compareORGANIC CHEMISTRY. 127 Polonowsky Abstr. 1888 1067) is identical with methronic acid pre- pared from ethyl acetoacetate and sodium succinate. The Rame mono- basic acid is obtained by the distillation of carbopyrotritaric acid methronic acid and sylvanecarboxyacetic acid. Isomeric Changes on Synthesising Aromatic Compounds by means of Aluminium Chloride. By J. SCHRAMM (Monatsh. 9 613-625).-When isobutyl bromide (300 grams) is allowed to drop very slowly into a mixture of benzene (900 grams) and alumi- nium chloride (300 grams) kept cool with ice a butylbenzene (yield 60 per cent.) having a sp.gr. of 0.8718 at 15" and boiling at 167-167-5" under a pressure of 736 mm. is formed. It does not agree in its properties with the isobutylbenzene boiling at 170-170*5" sp. gr. 0.8578 at 15" formed by Fittig's method (Gossin Abstr. 1884 MU) for the product on treatment with 1 mol. of bromine in presence of iodine gives a monobromobutylbenzene boiling a t 230-231*5" under a pressure of 736 mm. readily solidifying on cool- ing and melting at 13-14" whilst the monobromobutylbenxene froin the butylbenzene prepared by Fittig's method boils at 232-233*5" and does not solidify a t -20".The product of the synthesis is there- fore trimethylphenylmethane (tertiary butylbenzerze) CMejPh. Gossin's butylbenzene boiling a t 152-155" was not formed. Tertiary butyl chloride (50 grams) benzene (150 grams) and aluminium chloride (50 grams) under similar conditions give tertiary butylbenzene (yield 60 per cent.). In t h i s case no isomeric change takes place but normal butyl chloride (75 grams) benzene (300 grams) and aluminium chloride (80 prams) give secondary butylbenzene CHMeEtPh boiling at 173-5-1 74*5" under a pressure of 735 mm.) and having a sp. gr. of 0,8669 at 13" ; it is identical with the butylbenzene which Radziszewski prepared from a-p henylethyl bromide and zinc ethyl. Isoamyl chloride (170 grams) benzene (360 grams) and aluminium chloride (170 grams) give an amylbenzene (20 per cent.yield) which boils a t 187.5-188.5 under a pressure of 757 mm. aiid has a sp. gr. of 0.8683 at 15'. It therefore does not correspond with the isoamylbenzene which Essner (Abstr. 1862 46) prepared from isoamyl bromide and bromobenzene and must cuiise- qnently be represented by one of the formula CHMePh-CEIMe or CMe2EtPh isomeric change having taken place. It follows from the above that when the primary monochloro- derivatives of the fatty series act on benzene in presence of aluminium chloride the phenyl-group does not take up the position of the halogen but links itscblf to another carbon-atom thereby forming a secondary or tertiary hydrocarbon. The isomeric change is not walogous to t h a t of normal- into iso-propyl bromide in presence of aliiminium chloride as observed by Kekule' and Schrotter (Bw.12 2280) moreover Essner has shown that isoamyl chloride does not behave similarly. On the contrarF the author finds that ihobutyl ehloride in presence of aluminium chloride splits up into hydrogen chloride and butylcne and holds the opinion that the isomeric changes depend on a reaction similar to that observed by Bahlsohn (AbBtr. 1879 78S) who found that ethylbenzene could Le prepared from F. S . I(.188 ABSTRACTS OF CHEMICAL PAPERS. benzene and ethylene in presence of aluminium chloride. He there- fore concludes that the chloroparaffin splits up into hydrogen chloride and the corresponding olefine which reacts with the benzene in the following way :-PhH + Me,C:CH2 = CPhRle3 the phenyl-group attaching itself to the carbon-atom which is directly united to the smallest number of hydrogen-atoms.G. T. &l. Orthocresol. By A. CLAIJS and U. A. JACKSON (J. pr. Chem. [Z] 38 321-336).-Wroblewsky is mistaken in regarding the golden-yellow needles obtained by the action of nitrous acid on bromorthotoluidine as bromocresol for they are really nitrobromorthocresol. During the action parabromorthocresol is formed as well as the nitro- compound; to separate them the acid liquid is distilled with steam and the yellow oil thus obtained which partially solidifies on cooling treated with weak sodium carbonate solution; the red solution thus formed is shaken with ether which dissolves the bromocresol ; the alkaline solution is then precipitated with weak hydrochloric acid and the precipitate sublimed when nitrobrontortho- cresol [OH Me Br NO = 1 2 4 61 is obtained forming beautiful golden-yellow needles melting at 88" (uncorr.) and having all the properties of Wroblemsky's bromorthocresol.The sodiunh salt crystal- Iises in red prisms having a green lustre. Amidobromorthocresol [OH Me Br NH = 1 2 4 61 is formed when the nitro-compound is reduced with stannous chloride and strong hydrochloric acid in alcoholic solution ; it crystallises from ether as a white mass which rapidly becomes brown and sublimes in colourless needles melting at 110" (nncorr.) ; its hydrochloride is described. ParabromorthocresoE [OH Me Br = 1 2 41 may be prepared from bromorthotoluidine as above or by dropping a chloroform solution of bromine into a similar solution of orthocresol containing one-tenth of its weight of iron wire.It crystallises from hot water and from alcohol in colourless needles which sublime unchanged ; it melts at 64" (uncorr.) and boils at 235" (uncorr.). When oi-thoparadibrorno- cresol (Werner Abstr. 1886 1015) is oxidised by chromic acid in an acetic acid solution,rnetabromofoluquiwne [Me Br 0 0 = 1 3 2 53 is precipitated in yellow flocks which crystallises from ether in yellow prisms subliming as needles which melt at 93" (uncorr.) and are sparingly soluble in water freely so in other solvents; when an ethereal solution of it is shaken with it hydrochloric acid solution of stannous chloride until it is decolorised the corresponding quinoE is obtained; this forms white laminae which melt at 112" (uncorr.) and dissolve easily in the usual solrents ; the acetyl-derivative melts at 57" (uncorr.).By chlorinating a glacial acetic acid solution of parabromorthocresol chZorobromorthocresoZ [OH Me Br CI = 1 2 4 67 is obtained ; it crystallises i n colourless needles melt- ing a t 48" (uncorr.) and yields chlorotoluquinone on oxidation (comp. Abstr. 1886 614). PLcrachZmorthocresoZ [OH Me CI = 1 2 41 is obhined by chlorinating a glacial acetic acid solution of orthocresol coiitaining some iron ; the oil crystallises with difficulty,ORQANIO CHEMISTRY. 129 and by sublimation yields crystals melting a t 33" (uncorr.) and boiling at 220" (uiicorr.). The authors describe orthocresolparasulphonic acid and its potas- sium (2 mols.H,O) and barium salts ; orthocresolorthosu1phon;c acid and its putassium salt ( 1 mol. H,O) ; orthocresolorthoparadisul- phonic acid and its potassium (2 mols. H20) barium copper and lead salts ; but these acids have been described before. Bromocresolpura- sulphoizic acid [OH Me Br S03H = 1 2 4 61 is obtained as its potassium salt (1 mol. H20) by brominating potassium orthocresol- parasulphonate and as its barium salt by treating t h i s with barium chloride; the free acid melts in its water of crystallisation at '3.5" (uncorr.). ; the caEcium (3 mols. H20) copper lead (3 mols. H,O) and silver salts are described. The parabromorthocresolorthosulphonic acid is obtained from orthocrcsolorthosulphonic acid in a similar way.A. G. B. Dinitrortho-xylenols. By E. NOLTING and B. PICK (Rw. 21,3158 -3160).-Dinitrortho-~yleno1 [OH Me (NO,) = 1 3 4 2 61 is obtained when the yellow ammonium salt formed in the prepara- tion of nitro-xylene (compare Jacobsen Abstr. 1884 737) is de- composed with acids; it can also be prepared by nitrating 1 . 2 . 4 - ortbo-xylidine and diazotising the product. It crystallises in yellow needles melts a t 127" and is readily soluble in boiling alcohol hut only sparingly in water and cold alcohol. The ammonium salt is sparingly soluble in cold but more readily in hot water. The iso- meric compound [OH Me (NO,) = 1 2 3 4 61 is obtained in like manner from 1 .2.3-ortho-xylidine. It crystallises from alcohol in small yellow needles melts at 82" and forms an ammonium salt which crystallises in needles and is moderately soluble in water.Con- centrated aqueous s o h tions of the ammonium saits described above give orange or yellow cr~stallirie precipitates with barium or calcium chloride and other inorganic salts. Benzene-derivatives of High Molecular Weight. By I?. KRAFFT and J. GOTTIG (Ber. 21 3180-3188 ; compare Krafft Abstr. 1887 252 ; 1888 1087).-~exadecyZlplrenetoZl C&.3,*C,H4*OEt is pre- pared by heating hexadecplphenol with ethyl iodide and alcoholic potash. It crystallises from alcohol in plates and melts a t 43-44" It yields parethoxybenzoic acid melting at 195" when heated a t about 120" with nitric acid of sp. gr. 1.12. Acethexudecylaniiide C16H33*C6H4mRHAc prepared by treating ami- dohexadecylbenzene wikh acetic chloride melts a t 104-104*5" and boils a t about 295" ( 2 5 mm.).Orthomethy Zhexadecylbensene C16H33*C6H4n/Ie is obtained by heating a mixture of sodium (10 grams) orthobromotoluene (34 grams) and cetyl iodide (48 grams) at about 140". It crystallises from a well- cooled mixture of ether and alcohol melts at 8-Y0 and boils a t 238.5-235" (15 mm.). It resembles hexadecylbenxene in its be- haviour towards solvents and the melted substance is fluorescent. The corresponding meta-derivative prepared in like manner melts at 11-12" boils a t 236.5-237" (15 mm.) and resembles hexadecyl- F. S . I(.130 ABSTRACTS OF (3HEMICAL PAPERS. benzene in its behsvioui* towards solvents. The para-derivative melts at 27.5" and boils a t 239-5-240" (15 mm.).The melted substance solidifies to a mass of crystals but doe8 not melt again a t 27.5" until i t has been either well cooled or brought into contact with a crystal of the original substance. It yields toluylic acid when heated a t 120-130" with nitric acid of sp. gr. 1.12. Sodium para met hy 1 hexndPcyl b enzenesulp hoii d e C 16H3'J*C6H3Me*S 03Na is obtained in nacreous plates when the preceding compound is dis- solved in fuming sulphuric acid the product poured into ice-cold wHter the acid extracted with ether and treated with sodium chloride. Yaramefhy Zh exadecylpheitol C c6H3Me*OH prepared by melt- i n g the preceding compound with potash and a little water a t 150" crystallises from alcohol melts a t 6 2 O and boils a t 267-268" (15 mm.). Yaratnethylhexndecylphenetozl obtained by healing the phenol with ethyl iodide and alcoholic potash melts a t 26.5." Amidoparanj eth!/lheradecylbenzene C ,H,,* C6EIIMe*NH2 is obtained when paramethyltiexadecylbenzene is dropped into cool.fuming nitric acid and the resulting nitro-compound melting at about 40" reduced with stannous chloride. It melts at about 54" and boils at 264-265" (15 mm.). Dirnetlylhexadecylbenzene [Me c,,H = 1 3 41 prepared by heat- ing bromometaxylene and cetyl iodide with sodium crystallises from z i well-cooled mixture of ether and alcohol melts at 33.5" and boils at Z'rimet~~yZhexu~ecyZbenzene [Me3 C1,H = 1 3 5 61 prepared in like manner from bromomesitylene seems to melt a t about 40" and boils a t 258-258.5" (15 mm.). 249 5-250".F. S. I(. Constitution of Styphnic Acid. By S. KOSTANECKI and B. F E i s s r E r N (Ber. 21 3119-3123).- Consecutive dinitroresorcinol is best prepared by the method Stenhouse and Groves employed in the case of dinitroorcinol. S typhnic acid is obtained by boiling consecutive dinitroresorcinol with dilute nitric acid and by the action of very strong nitric and sulphuric acids on the symmetrical dinitro-derivative in the cold. The acid has therefore the constitution [(OH) (NO,) = 1 3 2 4 61 ascribed to it by Nolting and Collin (Abstr. 1883 1004). (This Journal 1877 i 545.) N. H. M. Action of Carbon Bisulphide on Dimethylaniline in Pre- sence of Nascent Hydrogen-By J. WIERNIK (Ber. 21 3206- 3207).-When dimethylmiline and carbon bisulphide are treated with zinc-dus t and hydrochloric acid tetrame thyldiamidophen-yl- methane melting at YO" and thioformaldehyde are formed.The former compound is identical with that obtained by Troger (Abstr. 1888 287) who took it for the ethane-derivative. This however crzstalliseJ in slender needles and melts a t 50" (Schoop Abstr. 1881 169). N. H. 31.ORQANIC CHEMISTRY. 131 1 . 2 . 3-Metaxylidine and its Identity with Wroblewsky's Orthoxylidine. By E. NOLTING and B. PICK (Ber. 21 3150-3154 ; compare Grevingk Abstr. 1885 144 and Nolting and Forel Abstr. 1 886 58).-Metaxylidine can be obtained from commercial xylidine as follows :-The bases are converted into the sulphates the solution is allowed to crystallise and the mixture of bases obtained from the mother-liquor from the last crop of crystals is fractionated.The portion distilling at 212-216" is treated with acetic anhydride and the mixture of acetyl-derivatives boiled for a few hours with four times its weight of 25 per cent. sulphuric acid. On cooling the greater part of the metaceto-xylide separates unchanged and the remainder can be obtained by extracting the dilated mother-liquor with ether. The acetyl-derivative is then decomposed by heating at 150" with concentrated hydrochloric acid or at 200" with three times its weight of 70-75 per cent. sulphuric acid. Metaxylidene can also be prepared from commercial xylidine by heating the mixture of bases obtained from the mother-liquor from the sulphates (see above) for 24 hours with an equal weight of glacial acetic acid and distilling the product.The portion passing below 300" is then treated with acetic anhydride and the acetyl-derivative boiled with 25 per cent. sulphuric acid and isolated as described above. The fraction passing above 300" contains a small quantity of metaceto-xylide which can be separated by heating with 25 per cent. sulphuric acid as already described. The sulphate ( C8HgNH2),,H2SO4 crystallises in needles and is decomposed into hydrogen xylidiue s u b h a t e C8H9NH2,H2S04 + 2&H20 when the aqueous solution is evaporated. 1 .Z.%Metaxylidine is only with difficulty converted into the acetyl-derivative ; the latter melts at a comparatively high tempera- ture and is hydrolysed only with difficulty. The sulphate is very readily soluble. In these respects this base differs from all the isomeric compounds. 'l'he compounds described by Wroblen sky (Bey.18 2304 3106 ; 19 235) as srtho-xylidine is idenhical with 1 . 2 .3-metaxylidine. F. S. I(. Metaxylylamidornethane. By W. HIKXICHSEN (Rer. 21 3082- 3086) .-&letaxylonitrile prepared from metaxylidine by Sandmeyer's reaction melts at 23- 25". Met m y l y lainidomethane ( m e t azy lobenzy 1- anvine) C6H,Me2*CH2.NH2 prepared by treating a hot alcoholic solution of metaxylonitrile (10 grams) with sodium (16 grams) boils at 218-219" is readily soluble in alcohol and ether sparingly in water and absorbs carbonic anhydride and water on exposure to the air. The hydrochJoride CgHI3N,HC1 crystallises in needles or plates and melts at 210". The hydriodide is crystalline. The plutinochloride ( GH,,N)2,H2PtC16 crystallises in small yellow needles melting at 226-228" with decomposition.The mercuroclrloride CgH,,N,HHgC1 crystallises in large plate6 or needles melts at 205" and is very sparingly soluhle i n water. The sulphate crystallises from water in needles melting at 254". The picrate C9Hl?N,C6H3N30 crystallises in yellow plates and melts at 22.3" with decomposition. The nitrate crystallises132 ABSTRACTS OF CHEMICAL PAPERS. in slender needles melting at 157-158'. The salt C9H,,N,CdI? pre- pared by adding a solation of potassium cadmium iodide to a solutwn of the bfise is crystalliw and moderately soluble in water. The cndmioiodide (C9H13N)2,2HI,Ccl12 prepared by adding a solution of potassium cadmium iodide to an aqueous solution of the hydro- chloride is only moderately soluble in alcohol and very sparingly so in water.Metaxylyl carbinol (mefaxylobenzyl alcohol) C6H3Mea*CH2*OH is prepared by treating. the preceding compound with nitrous acid and distillirig the product with steam. I t is a colourless aromatic-smelling liquid boils a t about 232" solidifies when cooled in a freezing mixture and melts a t 22". Dimethylbewzaldehyde (metcrx~ilobenzaldehyde) C6H3Me2.CH0 is formed when the alcohol is oxidised with sulphuric acid and potas- sium dichromate. The product is distilled with steam and purified by means of the crystalline sodium hydrogen sulphite compound. It is a colourless oil boils a t 223-225' smells like benzaldehyde and turns yellowish on exposure to the air. F. S . K. Action of Amines on Nitrogenous Organic Compounds.By B. LACHUWICZ (MovLatsh. 9 695-70O).-When hydrobenzamide is gently warmed with the amines decompositions occur which may be represented by the general equation N,(CHPh) + 3RNH = 2NH3 + 3CHPh:NR. By means of this reaction the author has formed the following derivatives of benzylidene :- C7H6:NPh prepared from aniline agrees with the description given of it by Cedi (Abstr. 1878 408) except that its melting point is 49" whereas Cech gives it as 42'. C7H6:N*C6H1Cl prepared from metachloraniline is a viscid liquid which boils at 338". C7K6:NC6H3Cl2 prepared from paradichloraniline (m. p. 63") crystallises from alcohol in thin plates melting a t 84". C7H6:N.C6H4*N02,. prepared from paranitraniline crystallises in yellow needles melting a t 115" ; the compound prepared from meta- nitraniline crystallises in yellow needles melting at 73".C7H6:N.C7H7 prepared from orthotoluidine forms an oil boiling a t 309-310" (745 mm.). C7H6:N*CloH7 prepared from a-naphthylamine crystallises from alcohol in yellow needles melting a t 7:+". The compound from /3-naphthylamine forms yellow needles melting at 101". CHPh(C,NHE,,)2 prepared from piperidine melts at 81". The amides of the acids react with hydrobenxamide with erolution of ammonia strong bases such as piperidine and formamide being similarly decomposed. G. T. M. Condensation Products from Bases of the Para-series with Para- and Meta-nitrobenzaldehyde. By A. BISCELER (Rer. 21 3207-3219 ; compare Abstr. 1888 287).- Diacefyl-/3-parar~itropherLyl- diparmnidotolylmef hane NO2*C,H,*CH( C,H,*NHAc) prepared bg boiling the base with a slight excess of acetic anhydride for one or twoORGANIC CHEWSTRT.133 hours crystallises from dilute alcohol in light yellow grains melting a t 136". It is readily soluble in cold alcohol and ether. The henzoyl-deriz~ative C,H,NO,( C,H,-NHBz) is obtained by heating the base with benzoic anhydride a t 120-1 30" ; i t forms yellow needles melts a t 152" and is readily soluble in warm alcohol and ether. p-Metanitrophenyldiparamidotolylmethane is prepared by adding strong sulphuric acid to an intimate mixture of metanitrobenzaldehyde and paratoluidine sulphate ; after three to four days it is treated with much water and heated ; i t is then filtered made alkaline and steam distilled. The oily residue which solidifies when cold is crystallised from hot alcohol.It crystallises in yellowish needles melts a t 85-86' dissolves very readily in chloroform readily irl hot alcohol rather 1.eadi1-y in etber and benzene. The hydrochloride forms voluminous yellowish needles readily soluble in hot alcoho! ; hot water decomposes it. The pZatirmchZoride CI~Hz,N,02,HzPtCl crystallises in yellow voluminous needles sparingly soluble in a1 co hol. The acet y I - conip ouizd N 0 z*C6H** C H ( C,H,*NH Ac) % separates froin the aqueous alcoholic solutim in pale yellow needles melts at 103-104" and dissolves readily in warm alcohol and benzene. The benzoyl-compound C35H?9N304 forms groups of yellowish needles melts at 1$6" and is readily soluble in alcohol less 80 in ether.Mef~xmid~lienyldipai-amidoto7ylnzet~~ane C2,RL,N obtained by reducing the nitro-compound with tin and hydrochloric acid cr) stnl- lises in white plates readily soluble in alcohol and ether. The hydro- c,hloride forms white plates the p1at;nocliloride crjstallises in small yellow plates sparingly soluble in hot water. a-1Metanitrophenilldiparamidotolylmetha e Ca,H2,N ?02 is prepared by the action of hydrochloric acid on metani trobenzaldehydr and para- toluidine. It melts at 125-128". The salts are decomposed by water. Pnranitrop heny Zdiparanaidophenylisobutyln Lethane NO,.C,H,*CH( C,H,Bu*NH,) prepared from paranitrobenzald ehy d e parami doi sobn t y I ben zene sulpl~ate and strong sulphuric acid crystallises in Iustroi~s yellow needles melts a t 125-126" and is readily soluble in chloroform benzene and hot alcohol.The h y d r o c h b i d e forms light yellow plates readily soluble in hot alcohol ; the platinochloride crypt al~i'es in yellow plates. The acetyl-compound crystallises in yellow grains melts at 114' and dissolves readily in benzene and in warm alcohol and ether. The benznyl-derivative forms long yellowish needles melts at 185-126" and is readily soluble in ether benzene chloroform and boiling alcohol. Meta?iitr~henyldz.yfrram idop herby lisobu fy Zmethaw e CnHJ3N302 forms light yellow plates melts a t 64-65' and resembles the para- compound in solubility. The benzoyl-derivative cr-y stalliseq from hot aqueous alcohol in yellowish plates melts a t 113-114" and is readily soluble in hot alcohol.134 ABSTRACTS OF CHEMICAL PAPERS.Paranitropheny Wianiidoni etaxyly hethane NOz'C,H,.C H (CsH8.N Hz) prepared from paranitrobenzaldehyde (10 grams) unsymmetrical metaxylidine (10 grams) and sulphuric acid crystslliseN in light yellow lustrous hair-like needles melts at 89-90' and dissolves wadily in hot alcohol in ether benzene and chloroform. The hydro- chloride forms pale yellow flat needles dissolves readily in hot alcohol and is decomposed by water. The platinochloride separates in yellow crusts. The acetyl-derivative forms small light yellow grains melting a t 88" ; the benzoyl-dwivative cpystallises in voluminous lustrous pale yellow needles melting at 191-192" ; both compounds dissolve easily in hot alcohol less readily in ether. Netunitrophenyldiamidomefaxylylwiethane C2,H2,N302 crystallises from alcohol in pale yellow sleuder plates melts at 91-92" and resembles the para-compound in solubility.The hydrochloride crys- tallises from alcoholic hydrochloric acid in pale yellow plates ; the plntinochlorid e forms a greyish- yellow crystalline precipitate. The acetyl-compound separates from ether in small light grey needles melting at 131-132" ; the benzoyl-compound forms voluminous yellowish needles and melts at 185-186". N. H. M. Halogen-substituted Acetamido-derivatives of the Aromatic Series and their derived Piazines. By P. W. ABENIUS and 0. WIDMAN (J. pr. Chem. [2] 38 296-312).-The substance of the formula C9H,Br2N0 formed by digesting alcoholic potash (1 mol.) and bromacetodibromorthotoluidide (1 mol.) (see next Abstract) ; is very sparingly soluble in hot alcohol but may be recrystallised from glacial acetic acid in colonrless hexagonal lamina melting at 277'.It is an indifferent Substance soluble in neither alkalis nor strong mineral acids. I t s constitution is most probably CO-CH C6H2Br2Me*N<CH 6>N*C6H,BrzMe. 2 A. G. B. Action of Bromine on Orthacetotoluidide at a High Tem- perature. By P. W. ABENIUS and 0. WIDMAN (J. pr. Chew. [2] 38 285-295) .-Brow acetodibromort ho toluid ide C8HzBr2Me.NH*CO*C H,Br is obtained when orthacetotoluidide (10 grams) is heated a t 160" and bromine (32 grams) added drop by drop; the product solidifies on cooling to a hard brittle black resin which when treated with chloro- form yields besides an oil the bromo-compound as white prismatic needles ; the needles recrystallised from glacial acetic acid melt a t 807" ; they are sparingly soluble in hot alcohol more so in benzene.As this compound can be synthesised from bromacetic chloride and dibroinorthotoluidine its constitution is as expressed by the above formula. If it is digested for an hour with alcoholic potash (in mol. proportion) it loses a molecule of hydrogen bromide and a sparingly soluble substance of the formula C,H,13r2N0 separates ; but when heated with a considerable excess of alcoholic potash in a reflux apparatus i t is decomposed with formation of dibromorthotoluidineORGANIC CH E MISTR P. 135 and potassium bromacetate. DibronaorthotoEuidi1le platinochloride cryvstallises in sparingly soluble yellow needles.Diacetyldibrornort hotoluid ide C6Hi,BrzMe.NAc2 prepared by heating dibromorthotoluidine for several hours with an excess of acetic anhgdride forms white needles very soluble in alcohol and melting at 88". When only gently warmed wihh acetic anhydride a substance melting at 200" is obtained and is doubtless acetyldibromortho- toluidide but has not yet been malysed. dcet~~lgl,ycolyldibromorthotoZuidicZe C6H~Br2Meo~H.CO*CH~*OAc.- Perfectly pure bromacetyldibromorthotoluide (2 grams) is heated with acetamide (6 grams) at 150-170" until blackening begins ; the mass is washed with water to remove excess of acetamide and hydrobromic acid and the residual acetyl compound recrpstallised from alcohol ; it forms white needles melting at 172". This substance was also obtained by heating bromacetodibromo~*thotoluidide with silver acetate.When heated wihh weak aqueous potash i t i s dissolved and con- verted into gZ~col~/ldl:bromorthotoZuidit€e C6H,Br2Me*NH*CO*CH,-OH which crystallises as the solution cools in colourless laminae having curved edges; with a stronger solution of potash the acetyl com- pound is converted into the laminae without being dissolved. The laminm crystallise from alcohol in slender colourless needles which melt at 182" and are more easily soluble in weak alkali than in water ; they are precipitated from the alkaline solution on neutrnlising it with hydrochloric acid. This compound is also obtained when the acetyl-derivative is heated with aqueous soda or with weak hydro- chloric acid. A. G. B. Phenylenediazosulphide.By P. JACOBSEN (Ber. 21 3104- 3107).-Orthophenylenedinzosulphihide C6H4<z>N is formed when the diazo-compound of diamidophenyl disulphide is boiled with water (AEstr. 1887 961) and in much larger amount hy the action of nitrous acid on amidophenyl mercaptan. It crystallises in plates melts a t 36-37' has an agreeable aromatic odour and distils readily with stcam ; it is soluble in strong hydrochloric acid. N. H. M. Azo-xylenes Diamido-dixylyls and Colouring Matters derived therefrom By E. N~LTING and T. STRICKER (Ber. 21,3138 -3149).-Consecz~tive nzortho-zylene C6H,Me2*N:N*C6HI,Me2 [Me2 N = 1 2 31 is obtained when zinc-dust (20 grams) is gradually added to a boiling alcoholic solution (100 c.c.) of orthonitro-xylene (20 grams) and 32 per cent.soda (20 grams). After filtering and concentrating the solution the product is washed with dilute hydro- chloric acid and recrystallised several times from alcohol. It can also be obtained by oxidising the hydrazo-compound (see below) with ferric chloride or hydrogen peroxide in alcoholic solution. It crys- tallises in orange-yellow needles melts at 110-lll" and is readily soluble in alcohol ether. and benzene. The hydrazo-componnd can be prepared by treating the azo-derivative with hydrogen sulphide or by reducing orthonitro-xylene as described above employing 25 grams of136 ABSTRACTS OF CHE?vIICAL PAPERS. zinc-dust. It crystallises from alcohol in colourless needles melts at 139-141" quickly oxidises on exposure to the air aiid is soluble in the ordinary solvents-although not so readily as the azo-compound.Unsymmetrical azortho-zylene [Me N = 1 2 41 is prepared as described in the case of the isomeric compound except that much more alcohol and very little soda must be employed otherwise a red condensation product is formed (see below). It can also be obtained by reducing nitrortho-xjlene with the theoretical quantity of sodium amalgam. It crystallises from alcohol in which it is more sparingly soluble than the 1 2 3 compound in red needles and melts at The hydmzo-compound prepared by reducing an alcoholic solution of nitro-xylene with sodiiim amalgam or by treating the azo-compound with zinc-dust and soda ammonium sulphide or sodium amalgam crystallises from alcoliol in yellowish needles melts a t 106-107° and is tolerably stable in the air.Unsymmetrical azomotaxylene [Me2 N = 1 3 41 melting at 129" can be obtained by reducing an alcoholic solution (300 c.c.) of the nitro-compound (25 grams) with zinc-dust (25-30 grams) and 32 per cent. soda (15 grams). (Compare Schultz Abstr. 1884 902.) The hydrazo-compound is obtained by boiling a mixture of alcohol (250 grams) nitro-xylene (30 grams) 32 per cent. soda (30 grams) and zinc-dust (40 grams) until the solution becomes almost colourless and treating the crnde product with hydrogen sulphide in alcoholio ammonia solution. I t crystallises from alcohol in colourless needles and melts a t 120-122". X!ynzmetricnl azornrtaxylene [Me N = 1 3 51 prepared by re- ducing an alcoholic solution (GO c.c.) of nitrometaxylene (10 grams) with zinc-dust (10 grams) and 32 per cent.soda (10 grams) crystal- lises in orange needles is readily soluble in the usual solvents and melts at 136-137". The hydrazo-compound is prepared by treating nitrometaxylene (10 pams) with soda (3 grams) and zinc-dust (15 grams) in alcoholic solution (50 c.c.). It crystallises from alcohol in colourless needles melts a t 124-125" and quickly osidises on expo- sure to the air. It cam also be obtained by reducing the azo-compound with ammonium sulphide. Azopnraxylene [Me N = 1 4 21 obtained by treating nitro- paraxylene (20 grams) with zinc-dust (16-20 grams) and 32 per cent soda (16 grams) in alcoholic solution (200 c.c.) crystallises in yellow needles and melts at 119". The azo-xyleoe prepared by Werigo (Zeit.f. Chem. [ a ] 1 312) is probably identical with this compound. The hydrazo-compound prepared by reducing nitroparaxylene (30 grams) with 32 per cent. soda (25 grams) and zinc-dust (45 grams) i n alcoholic solution (250 c.c.) crystallises from alcohol in colourless needles melts a t 14.5" and is moderately stable in the air. The hydrochlorides of the corresponding diamidodixylyls were prepared by heating the hydi azo-xylencs with moderately dilute hydro- cllloric acid either alone or in alcoholic solution adding excess of soda extracting the base with ether and saturating the dried ethereal solution with hydrogen chloride. Hydrazometaxylene [Me2 N = 1 3 41 by this treatment yields 140-141".ORGANIC CHEMISTRY. 137 chiefly azo-xylene and xylidine ; the last-named compound is separated from the dislmidodixylyl by distilling with steam.Hydrazortho- xylene [Me2 N = 1 2 41 is hardly acted on a t all when boiled w i t h acids and the hydrochloride of the corresponding di- amidodixylyl was obtained by boiling an alcoholic solution of the azo-compnund with hydrochloric acid and stannous chloride separat- i n g the xylidine by distilling with steam and saturating an ethereal solution of the base with hydrogen chloride. Nitrortho-xylene [Mez NO,= 1 2 41 yields a red and nitrometn- xylene [Me. NO = 1 3 41 a brownish-red condensation product when treated with alcoholic soda. The red compound is almost in- soluble in ordinary solvents and when reduced with stannous chloride and hydrochloric acid is converted into dimethyldiamidostilbene.(Compare Bender and Schultz Absty. 1887 268.) All the bases obtained from the nitro-xylenes after diazotising yield with naphthionic acid a-naphthol-a-sulphonic acid and P-naphthol- disulphonic acid R compounds which dye unmordanted vegetable fibres. The diphenyl-derivatives are reddish dyes with a more or less blue or yellowish shade whereas the stilbene-derivative yields a bluish-violet dye with a-naphthol-a-sulphonic acid. The toluidines from meta- and para-nitrotoluene were also prepared ; these bases yield red dyes with the above-named sulphonic acids. F. S. K. Nitroso-derivatives of Resorcinol Azo-dyes. By S. V. KOSTA- NECKI (Eer. 21 3109-3 114).-NitrosophenyZazoresorcinoZ CI2H9N3OS is readily obtained by adding a mixture of phenylazoresorcinol (1 mol.) dissolved in dilute alkali and sodium nitrite (1 mol.) to cooled dilute sulphuric acid.The product is filtered washed and crystallised from alcohol. It separates in lustrous brownish-red plates which when heated at 168" detonate ; it dissolves sparingly in hot water readily in benzene and still more readily in chloroform ; ether dissolves i t sparingly. I t dissolves in alkalis with yellowish-brown and in strong sulphuric acid with olive-green colour and yields an intense olive-green colour with iron mordants. Similar dyes were prepared from ortho- and para-toluidine xylidine pseudocumidine meta- and para-nitraniline amidoazobenzene and nnphthionic acid. Nitrosopseudocum?/Z~xoresorcinoZ Cl5HI5NJO3 crystallises from chloro- form in brown plates decomposes when heated above 190" and dissolves in alkalis and in strong sulphuric acid yielding brownish- yellow and brownish-red soliltions respectively.When nitrosophenylazoresorcinol is reduced with tin and hydro- chloric acid diamidoresorcinol is formed. P h m y lazonitrosoresorcirLoZ C1,H9N303 isomeric with nitrosophenyl- azoresorcinol is obtained by adding nitrosoresorcinol dissolved in aqueous sodium carbonate to a solution of diazobenzene chloride cooled wihh ice. It crystallises from alcohol in golden plates which decompose at 225". The solution in dilute soda is reddish-yellow ; the sulphuric acid solution is olive-brown. When reduced it yields the same diamidoresorcinol as that obtained from nitrosophenylazo- resorcinol. N. H. M. VOL. LVI. 1138 ABSTRACTS OF CHEMICAL PAPERS.Isomeric Phenyldiazoresorcinols. By S. V. KOSTANFCKI ( Rer. 21 3114-3119).-Syn~metrical diamidoresorcinol C6H2(mH2),( OH) is isolated in a manner similar to the consecutive derivative (pre- ceding Abstract) ; it is identical with Typke's isodiamidoresorcinol (Abstr. 1883 917). The szdphrtic! (with 2 mols. H,O) crystallises from very dilute alcohol in needles. Symmetrical phenyldiazoresorcinol is formed when resorcinol (1 mol.) is added to a diazotised solution of aniline (2 mols.) and the whole poured into an excess of dilute alkali. Consecutive phenyldiazoresorcinol is obtained by adding a mixture of diazoben- zene chloride (2 mols.) and resorcinol (1 mol.) to aqueous sodium acetate or sodium carbonate. Thc consecutive compound is best pre- pared as follows :-Aniline (2 mols.) is dissolved in dilute hydrochloric acid (5 mols.) and diazotised with sodium nitrite. When an excess of nitrous acid is no longer present resorcinol (1 mol.) is added the whole added to a dilute solution of sodium acetate or carbonate and after being kept for some time filtered dried and crystallised from a mixture of chloroform and alcohol.The isomerides have the proper- ties already ascribed to them (Liebermann and v. Kostanecki Abstr. 1884 1146). Phenylazoresorcinol is best prepared by adding resorcinol (1 mol.) to the diazotised solution of aniline hydrochloride (1 mol. ) pouring the mixture in a thin stream into an excess of dilute alkali precipi- t,ating the phenylazoresorcinol with acid and crystallising it from dilute alcohol.oc-Ethylenephenylhydrazine. By 0. BURCHARD and A. M~CHAELIS (Rer. 21,3202-3204) .-a-~'tlLylenc!phen~jlhydrazine C2H4 NPh-N H,) is prepared by adding the calculated amount of ethylene bromide to finely powdered sodium phenylhydrazine covered with benzene. After 10 minutes the mixture becomes warm and in a short time the reaction becomes so violent that the flask has to be cooled with ice water. The product is treated with water and the benzene separated and extracted first with very dilute hydrochloric acid to remove any phenylhydrazine which is present. and then with strong hydrochlorie acid. The base is precipitated from the aqueous solution with soda and crystallised twice from alcohol. It forms colourless prisms or plates melts a t go" and is readily soluble in hot alcohol and ether and in dilute acids. It gradually reduces Fehling's solution when heated.The hydyoch Zoride ClaH18N6,2HCl crystallises in needles of a silky lustre When the base is treated with alcohol and then with acetaldehyde heat is developed and the condensation product C,H,(NPh*N:CHMe) separates in long white needles which melt at 82". The corresponding benzyzidene-derivative crystallises from hot glacial acet'ic acid in slender needles melts a t 193O and is very sparingly soluble in ether and alcohol. The theoretical yield is readily obtained. N. H. M. N. H. M. Di-phenylmethyltriazole. By J. A. BLADIN (Ber. 21 3063- 3065) .-Di-phenylmethyltriazole <cMe.N>CG<N.cMe> is ob- N-NPh NPh-N tained when cyanophenylhydrazine (Senf Abstr.1887 929) isORGANIC CHEMISTRY. 139 heated for a few minutes with excess of acetic anhydride. It crystal- lises from alcohol in colourless prisms melts at 222-223" and is readily soluble in chloroform moderately so in alcohol but only sparingly in benzene and ether and insoluble in water. It is very stable and is not decomposed when boiled with alcoholic potash or strong acids. The hydrochloride CI8Hl6N6,2HC1 separates as a crys- talline powder when concentrated hydrochloric acid is added to a boiling alcoholic solution of the base. It is almost insoluble in fuming hydrochloric acid and is decomposed by water. The platino- chloride C,8H,6N6,H2PtC16 + 4H20 crystallises in orange-yellow plates becomes anhydrous at 125" and is d&omposed by water F.S. K. Action of Sodium Hypobromite on Nitrogen-derivatives in the Benzene Series. By G. DEN~GBS (Compt. rend. 107 662).- When an alkaline solution of sodium hypobromite is boiled for a few minutes with a solution of hippuric acid or R hippurate gas is evolved and a reddish-yellow precipitate is formed. Benzoic acid gives no reaction and glycocine decolorises the hypobromite with evolution of nitrogen. With sodium hypobromite benzamide and benzonitrile give no reaction in the cold but a kermes-red precipitate on heating. Aniline gives an orange precipitate and the reaction is almost as delicate as that with hypochlorites. Methylaniline and dimethylaniline give a greenish-yellow precipitate in the cold and a red precipitate on heating. Toluidine behaves like aniline but the precipitate is darker in colour.Anilides give no reaction in the cold but a reddish pre- cipitate is formed on boiling and an odour of methyl cyanide can be perceived. Metaphenylenediamine diamidobenzoic acid and toluylene- diamine yield maroon-red precipitates in both cold and hot solutions. Ferrocyanides ferricyanides and nitroprussides yield a precipitate of ferric hydroxide. Pyridine gives no reaction and pure quinoline also gives no reaction but if as is frequently the case it contains aniline an orange precipitate is formed. C. H. B. Aromatic Derivatives of Oxamide and Oxamic Acid. By J. MAUTHNER 2nd W. SUIDA (Illonatsh. 9 736-750 ; compare Abstr. 1886 886 ; Ber. 3 227)-When ethyl oxalate and orthotoluidine are heated together in molecular proportions ethyl oxalorthotoluidate is formed together with a little oxaltoluidide the latter remaining undissolved on treatment with alcohol.On heating either alone or with acetic chloride the free acid is converted into oxalorthotoluidide which can also be obtained by heating together orthotoluidine (1 mol.) and anhydrous oxalic acid (2 mols.) at 220". Oxalortho- toluidide melts at 207-208" and appears to be identical with the polyformotoluide described by Ladenburg. Oxanilidediorthocarboxy lie acid C2O,(NH*C6H4*COOH) may be obtained by the oxidation of oxalorthotoluidide with permanganate as well as by heating a mixture of anthranilic acid (2 mds.) and ethyl oxalate (1 mol.) at 140-150". When sulphuric acid is added E 2140 ABSTK-ACTS OF CEEMICAL PAPERS.to an ammoniacal solution the acid is thrown out in the form of a pulverulent precipitate. The copper salt C,6HloN,06Cu + CuO has a bright green colour ; the silver salt C1,HI,,N2O6Ag forms an in- soluble white precipitate. Oxalxylidic acid C8Hg*NH*CO*COOH is formed by heating a t 180-190" a mixture of a-amidometaxylene (1 rriol.) and ethyl potas- sium oxalate (1 mol.). It crystallises in needles containing 1 mol. H,O and melts at 128-129". The silver salt CloHloAgN03 and the calcium salt are both soluble in water and crystallise in needles. On heating the free acid it is converted into oxdxylidide C,oH20N?02 which crystallises from acetic acid and benzene in flat needles melting at 210". OxaZ-+-czLmidic acid C9H:Il*NH*CO*COOH is prepared by heftting at BOO" a mixture of Feumidine melting a t 63" (1 mol.) and ethyl oxalnte (1 mol.).It crystallises in needles containing 1 mol. H,O and melting at 167". The sodium salt CIlH,,N03Na + 3H10 crys- tallises in scales ; the potassium salt CllH12N03K,CllH13N03 in needles; the calcium salt (C,1H,,N03)2Ca + H,O is a crystalline powder ; the acid silver salt C11H1~NOSAg,CIlH18N03 forms bundles of needles and the normal salt C1,H12N03Ag is a crystalline powder. On heating the free acid it is converted into oxal-y-cumidide which can be directly prepared by the action of anhydrous oxalic acid on the base and crystallises from acetic acid in needles melting a t 230". Phthalimidine. By C. GRAEBE (Awnalert 247 288-301).- Phthalimidine is prepared by the reduction of phthalimide by tin and hydrochloric acid.The tin is precipitated from the crude product by strips of zinc and the phthalimidine is deposited as the nitroso- compound on the addition of a concentrated solution of sodium nitrite Nitrosophthdimidine is decomposed by strong hydrochloric acid yielding a mixture of phtlalimidine and its hydrochloride. The conversion of the nitroso-compound into phthalide and the pro- perties of some of the phthalimidine-derivatives have already been described (Abstr. 1885 167 and 979). Phthalimidine melts a t 150" and boils a t 336-337" under 730 mm. pressure. It is freely soluble in alcohol ether and chloroform. On the addition of bromine to the solution in chloroform the tribromide ( C,H4N0)2Br3 is deposited ; it melts a t 150" with decomposition. The hydrochloride C,H,ON,HC'l picrate (m.p. 140°) and aurochlorids (C8H,0N)2,HAuC14 are crystnl- line. Phthalimidine silver CsH60NAg is deposited from ammoniacal solutions in crystals. Acety Zphthalintidine C8H60NAc melts at 151" and does not yield a nitroso-derivative. Nitrosophthdimidine is decomposed by sodium hydrogen sulphide yielding thiophthazide C8H60S ; this is freely soluble in alcohol and ether melts a t 60" and is converted into a thio-derivative of hydr- oxymethylbenzoic acid by solution in alkalis and reprecipitation by acids. Nitrophtha!irnidine melts a t 210" and is deposited from alcoholic solution in pale yellow scales. It is soluble in alkalis acids p&cipit;tte from the alkaline solution the compound C,H,O4N ; this is freely soluble in alcuhol ether and in hot water.Dinitrophthal- imidine melts a t 195". w. c. w. G. T. M.ORGANIC CHEMISTRY. 141 Substituted Phthalimidines. By C. GRAEBE and A. P I c T h T (Anr/wZerz 247 302-306) .-Methylphthalimide C8H402NMe and methylphthaliniidine C8H6O4NMe have been previously described by the authors (Abstr. 1884 lolH). Methylphthalimide melts at 132" arid boils at 28.5-286". Ethyl phthalimide melts at 79" and boils a t 282.5" under 726 mm. pressure. Ethyl phthalimidine melts at 45". The aurochloride ( C,oHloON)2,HAuC14 forms golden prisms melting a t 145". Phenyl phtha.limidine C,&ONPh prepared by reducing an alcoholic solution of phthalanil with tin and hydrochloric acid is identical with Hessert's phthalidanil obtained by the action of By J . VILLE (Compt.rend. 107 659-661) .-Dihydro.cyheiizylene~ho.~hznzc acid PO( CHPh*OH),*OH is obtained by the action of hypophosphorous acid on benzaldehyde and crystallises in white radiating lamellae which can be purified by solution i n potassium hydroxide and repre- cipitation by hydrochloric acid. It is only slightly soluble in water chloroform or benzene but dissolves readily in ethyl alcohol or ether and is still more soluble in methyl alcohol. With acids it forms crystallisable salts and its solution has no reducing action on copper sulphate or amrnoniacal silver solutions. It begins to melt at 165" and forms a yellowish liquid which if more strongly heated gives off hydrogen phosphide and leaves a bulky carbonaceous residue. When heated in sealed tubes a t 130" for several hours with dilute sulphuric acid it jields benzaldehyde and phosphoric acid.The silver salt forms a white crystalline precipitate which blackens when exposed to light and is inscluble in water and nitric acid but dissolves readily in ammonia. The ethy7 salt is almost insoluble in water and is only slightly soluble in ether or chloroform but i t dissolves readily in ethyl alcoliol from which it cryhtallises in brilliant prisms. It is slowly saponified by cold solutions of potassium hydroxide and if the liquid is acidified the free acid separates in crystals. With hot potassium hydroxide the yeaction is more complex and benzaldehyde and phosphoric acid are obtained. When the ethyl salt is treated with acetic chloride it yields the compound PO( CHPh*OAc),*OEt a viscous transparent substance soluble in alcohol or ether from which it separates in very white ci-ystals.The acetyl-derivative is slowly saponified by potash in the cold and if the product is acidified dihydroxybenzylenephosphinic acid separates and the solution contains acetic acid. With hot potash the products are benzaldehyde phosphates and acetates. aniline on phthalide. w. c. w. Action of Hypophosphorous Acid on Benzaldehyde. Dihydroxybenzylenephosphinic acid is monobasic. C. H. B. On Mono- and Di-nitroparazobenzoic Acids. By Madame A. RODSIANKO (J. Rum. Chem. Soc. 1888 20 18-29).-The action of nitric acid on parazobenzoic acid was studied and the product compared with the nitro-compound obtained from azobenzoic acid by Zinin. Solid nitrotoluene is oxidised by chromic mixture to paranitrobenzoic acid and this on treatment with sodium amalgam142 ABSTRACTS OF CHEMICAL PAPERS.yields parazobenzoic acid ; the latter after having been dried between blotting paper still contains 30-35 per cent. of water. It is treated with 16 times its weight of nitric acid of sp. gr. 1.535 gradually warming the mixture until the temperature reaches 79' and all the acid is dissolved On adding water 90-94 per cent. of a solid product is precipitated. This is washed with water and recrystallised silccessively from glacial acetic acid and several times from alcohol. The product consists of nitrazobennoic acid ClaHE,(N02) N204 and forms a pale yellow crystalline powder consisting of rhombic scales. It is highly electric. It is insoluble in water ether and benzene soluble in acetic acid and in 26.2 parts of hot and 280.4 parts of cold alcohol.It forms two series of salts; the acid salts are stable but the normal salts are decom- posed by water with formation of acid salts. The normal potassium salt Ki,C,aH,(N0,)N204 + 3H20 loses its water at U O " and is decomposed by carbonic acid yielding the acid salt. The calcium salt CaC14H,(Pu'02)N,04 and the barium and silver salts have an analogous composition. The ethyl salt obtained from the silver salt and ethyl iodide forms pale yellow rhombic scales melting at 98". Dinitroparazobenzoic acid is obtained when 30 parts of nitric acid. of sp. gr. 1.555 is employed for 1 part of azobenzoic acid and the mixture heated nearly to the boiling point. It is purified like the mononitro-acid and forms tufts of slender yellow needles.It decom- poses at 257" without melting. Like the mononitro-compound it IS soluble only in acetic acid and in 16.5 parts of hot and 160.3 parts of cold alcohol. Its stable normal salts have a composition corre- sponding with that of the potassium salt K2C14H,(N02),N,04 + 4H20. The calcium and barium salts contain 5 mols. H,O ; the silver salt is anhydrous. The ethyl salt) forms slender yellow silky needles melting at 128". Finally azobenzoic acid obtained by the decomposition of nitrobenzil (Zinin) was treated with nitric acid and a product obtained which proved to be identical with the mononitroparazo- benzoic acid described above. The two azobenzoic acids are there- fore identical. B.B. It does not melt but decomposes at 270". Reissert's Pyranilpyrok Acid. By R. ANSCH~TZ (Bey. 21 3252-3256) ; A. REISSERT (Bey. 21 3257).-Anschutz's paper is a reply to one of Reissert's (Abstr. 1888 954). Reissert mentions that the most important evidence in favour of his views depends on the knowledge of the constitution of anilsuccinic and P-milpropionic acids and that this point is not discussed by Anschutz. Nitro-derivatives of Isophthalic Acid. By A. CLAUS and S. WYNDHAM ( J . pr. Chem. [ 2 1 38 313-320).-Dinitroisophtkalic acid is formed when isophthalic acid (5 parts) is heated with fuming nitric acid (1 part) in a sealed tube for six hours at 150-180". It is but little soluble in cold water more freely in hot water and in alcohol and ether ; it forms colourless needles or short prisms arranged in papillary aggregates and containing 5 mols.H20 half of which is lost over sulphuric acid ; the anhydrous acid melts at 215" (uncorr.). The sodizcrn and potassium salts (2 mols. H20) the barium salt N. H. M.ORQANIC CHEMISTRY. 143 (7 mols. H,O) the calcium and ?nagnesium salts (4 mols. H,O) and the lead and silver salts are described. As the same dinitro-compound can be obtained by nitrating symmetrical nitroisophthalic acid one of the nitro-groups is in the position 5 but the position of the other remains an open question. Diarnidoisuphthalic acid C6H,(N~,),(COOH) obtained by reduc- ing the above acid crystallises with 1% mol. H,O in shining flat needles of a very light-brown tint becoming darker on exposure to light and not melting below 300"; its aqueous solution deposits a black tarry matter when incautiously evaporated and acquires a musliroom-like odour after a time.Dibromisuphthalic acid obtained when symmetrical nitroisoplithalic acid is heated with bromine €or several hours at 300" in a sealed tube crystallises in colourless needles melting at 155" (uncorr.) sparingly soluble in water freely in alcohol and ether and subliming with the same crystalliue form. The calcium and silver salts form anhydrous crystals. Nitroisophthalic acid (NO COOH COOH = 4 1 31 may be obtained by oxidising 4-nitrometatoluic acid with potassium per- manganate ; it crystallises with 3 mols. H,O in small white needles easily soluble in hot water in alcohol and ether. The anhydrous acid melts at 246" (uncorr.) ; its sodium potassium (1 mol.H20) barium (4 mols. H,O) calcium (i mol. H20) and magnesium (6 mols. H20) lead and silver (7+ mols. H,O) salts are all described. A. G. B. Phenylglycinorthocarboxylic Acid Glycocine-derivatives. By J. MAUTHNER and W-. SUIDA (Monatsh. 9 727-735).-Instead of employing 2 mols. of the base to one of chlomcetic acid in the pre- paration of glycocine-derivatives as in the ordinary method the authors replace the second molecule of the base which is needed to combine with the hydrochloric acid liberated by an equivalent quantity of a metallic carbonate whereby not only is material saved but the reaction is hastened. Phmy Zg lycinorthocarbox!/lic acid CO OH*C6H4*NH* CH,*C 0 OH is prepared by boiling a mixture of anthranilic acid (25 grams) chlor- acetic acid (20.6 grams) sodium carbonate (32.8 grams) and water (1 litre) for several holm the water as it evaporates being replaced.After cooling the product is supersaturated with hydrogen chloride acid and allowed to remain for one day when the acid separates as a bright-yellow crystalline powder which melts with frothing a t 207". It dissolves readily in alcohol acetic acid and ether but is insoluble in benzene and chloroform. The acid potassium salt C9H,N04K crystallises from dilute alcohol in microscopic scales. The calcium salt is anhydrous and furnishes aniline on distillation. The barium salt CgH,NOaBa 4- 2H20 crystallises in needles ; the silver salt C9H,N04Ag4 is insoluble in water and the ethyl salt CgH,N04Et forms an oil which crystallises on standing.If chloracetic acid (50 grams) soda (53 grams) and excess of ammonia are boiled for 7-8 hours glycocine is formed (16 to 18 per cent. of theory). If the ammonia be omitted glycollic acid (yield 75 per cent. of theory) is the product. G. T. M.144 ABSTRAOTS OF CHEMICAL PAPERS. Orthonitranilinesulphonic Acid and some of its Derivatives. By R. KIETZKI and Z. LERCH (Her. 21 3220-Y223).-Orthonitrani- linesulphonic acid (Goslich Abstr. 1876 i 929) is prepared by treating acetanilidt? (1 part) with fuming sulphuric acid containing 18 to 'LO per cent. of anhydride (3 parts) and ordinary sulphuric acid (2 parts). The calculated amount of nitric acid previously mixed with an equal volume of sulphuric acid is then gradually added the whole being kept at 0".The product is poured on to a little ice when it solidifies to a mass of yellow needles. It is ex- tremely soluble in water less so in alcohol or i n dilute sulphuric or hydrochloric acid. When the potassium salt is boiled with an excess of potash for a long time ammonia is evolved and the potassium salt OK.C6H3(N02)-S031( (Kolbe and Graebe AnnaZen 147 76) is obtained. Nitrodiazobenzenesu~ponic acid NOz*C6H3<S63 N'N > obtained by treating the aqueous solution of the amido-acid with hydrochloric acid and potassium nitrite cry stallises in slender light-yellow needles dissolves sparingly in water and detonates rather violently when heated. Orthop lzeny lenediam inesulp h onic acid C6H,( NH2),*S 03H is formed when the nitranilinesulphonic acid is rediiced with tin and hydro- cliloric acid.When exposed to air it becomes greenish-blue and gives a reddish-brown colour with ferric chloride. The acid is not identical with Sachsse's acid (this Journal 1877 ii 7511 but possibly is with the one prepared by Post and Hartung (Abstr. 1880,394). Ortho?iitrophenylh?jdruzineparasulphonic acid is obtained by adding orthonitrodiaaobenzenesulphonic acid to a well- cooled strongly acid stannous chloride solution. It dissolves in water and in aqueous alkalis and alkaline carbonates. TVhen reduced with hot acid stannous chloride solution the corresponding urnidoh ydrazine- sulyhonic acid is formed. The hydrochloride crptallises in plates and dissolves readily in water but only sparingly in strong hydro- chloric acid.N. H. M. The Sulphonic Acid of Methyl Phenylcarbamate. Bg E. NOLTING (Ber. 21 3154-3155).-The compound obtained by Hentschel (Abstr. 1885 792) by treating methyl phenylcarbamate with fuming sulphuric acid is probably the acid COOMe*NH.C6H4*S 03H. This substance can also be obtained by adding soda (1 mol.) to a warm aqueous solution of sodium sulphanilate (1 mol.) and methyl chloroformate (1 mol.). The amidosulphobenzoic acid prepared by Hentschel (Abstr. 1884 1016) is probably sulphophenylcarbamic acid SO3H.C6H4*NH*COOH. When methyl phenylcarbamate is heated at about 260" with lime aniline monomethylaniline dimethyl- aniline and carbanilide are formed. F. S. K.ORGANIC CHEMISTRY. 145 Diphenic Anhydride and Orthodiphenyleneketonecarb- oxylic Acid. By C. GRAEBE and C.AUBIN (Aniialen 247 257-%8). -Diphenic acid is convered into diphenic anhydride <c,H:.co>O by the action of acetic chloride or acetic anhydride (Abstr. 1887 589) also by boiling with stannic chloride or phosphorus trichloride or by the action of phosphorus pentachloride containing oxychlorjde at 120". Concentrated sulphuric acid zinc chloride and an excess of boiling phosphorus oxychloride convert dipheni c acid into ortho- C H C O diphenyleneketonecarboxylic acid <C6HI>C6H3.COOH. CO- Monomethyl and ethyl diphenates are prepared by boiling diphenic anhydride with methyl or ethyl alcohol. They crystallise in colourless plates dissolve freely in alcohol and distil without decomposition. The ethyl salt melts at 88" and the methyl salt at 110".Dipherzio chloride ClrE16C1 prepared by the action of phosphorus pentachloride on the anhydride a t 180" is a crystalline substance soluble in benzene ether and acetic acid. It melts a t 93-94" and distils without decomposition. On reduction dipbenic chloride yields phenanthra- quinol which changes into phenanthraquirione by oxidation. Diphenic anhydride is converted into the anzinic acid COOH.C6H~.CsH~.CONHz by boiling it with ammonia. This substance melts at 193" and decom- poses on distillation yielding diphenirnide < c6H4*C0>NH. C6Ha'CO The imide is deposited from hot alcohol in colourless needles soluble in chloroform. It melts a t 219-220". Warm strong ammonia converts the imide into diphenamide NH2.CO*C6H4*C6HI.C0.~H2. The amide nielts at 208-d09" and is insoluble in sodium hydroxide.Phenylhydrazine unites with diphenic anhydride forming ani&do- diphenccmic acid C20H1603N2 molting at 174". ,4t 'LOC)" the acid begins to lose water and slowly changes into anilidodiphenimide C6H4'Co>N-NHPh. This substance melts a t 150" and is insoluble in alkaline carbonates. The salts of orthodiphenylcarboxylic acid have been previously described (Abstr. 1887 589). The acid yields a mono- and n tri- chloride on treatment with phosphorus pentachloride. The mono- chloride C1,H,OZC1 melts a t 128O and the trichloride a t 95". The trichloride dissolves in alcohol and the solution depo,sit,s crystals of the composition <g$>c6Hs*CoOEt. Reduction with zinc and acetic acid converts the trichloride into fluorenecarboxylic acid.The acetoxime melts at8 263" and decomposes at a high temperature. The <CeH4*CO hydrazone <C(N,HPh)>C6H~'COOH C6H4- crystallises in yellow needles or prisms and is soluble i n alcohol and ether decomposes at 210". It melts at 205" and r)rtho~zlorenecal.boxylic acid <c6HI>C6H3*COOH CH2 melts a t 175",146 ABSTRACTS OF CHEMICAL PAPERS. and dissolves freely in ether alcohol and acetic acid. salt melts at 64". The methylic Hydroxyfluorenecarboxylic acid < zf/oE> C6H3.C0 OH prepared by the action of zinc-dust on an amuonLicaf solution of diphenylene- ketonecarboxylic acid is soluble in alcohol ether benzene chloroform and in'hot water. The substance which Graebe and Mensching (Abstr. 1880 8 1 2 ) described as a phthalejin of diphenic acid is a condensation product of phenol and diphenylene- ketonecarboxylic acid and is probably represented by the formula It melts at 203".C(CsH4QH),> C,H,.CO OH. On heating a mixture of resorcinol and stannic chloride at 115* a yellowish-brown crystalline powder is produced. The solution in alkali8 has a yellowish-red colour and exhibits an intense green fluorescence. w. c. w. 'C6Hp - Nitro-derivatives of Tetramethyldiamidodiphenylmethane. By P. VAN ROMBURGB (Rec. Trav. Chim. 7 226-235).-TetramethyZ- diamitiodi~henylmsthane was prepared by heatirig methylal and dimethylaniline with zinc chloride. It melt8 a t 9Uo gives a violet compound with trinitrobenzene melting a t 114" and a dark red compound with metadinitrobenzene melting a t 74" the first con- taining equal molecular proportions the second 2 mols.of the amine to one of dinitrobenzene. Added in acetic acid solution to nitric acid (sp. gr. 1*48-1-5) it is converted into tetranitrodimethyl- danitrumidodiyheny h e t h a n e OHz[ CGH,(NOz)z.NMe*N0z]2. This nitr- amine is a yellow crystalline substance which darkens in colour at 210" and decomposes a t 217-2.?0". I t is nearly insoluble in alcohol ether petroleum carbon bisulphide and chloroform dissolves readily in acetic acid and acetone but is best recrystallised from nitric acid. Precipitated as a white powder from the nitric acid solution by the addition of water and boiled with 12.5 per cent. aqueous potash it gives a brown solution which on evaporation was found to give off methylamine. When boiled with phenol i t gives tetranitrodiriiethyl- dinmidodiphenylmethane an orange-coloured compound melting with decomposition a t 250".It is slightly soluble in alcohol petroleum and benzene but more soluble in acetone acetic acid chloroform and ethyl acetate. When treated with nitric acid it is reconverted into ths nitramine. The latter when oxidised with chromic anhydride y.ields a com- pound exactly resembling that obtained by the nitration of tetra- methyldiamidobenzophenone ; on treatment with phenol this gives a teti*anitrodimethyldiamidobenzophenone melting a t 225". Admitting the formula which the author proposed for the nitramine derived from benzophenone that of the one now in question will be ~02.~Me*C6H,(N02),*CHz*C,H2(N02)2~NMe*~o~. The compound obtaiiied from this by boiling with pheaol was also oxidised in acetic acid solution with chromic anhydride and gave a 4 3,5 1 2,6 4ORGANIC UHERlTSTRP.147 tetranitroaiamidobertznp7renone crystallising in small yellow needles from acetic or phenol and melting with decomposition at 250-260". H. C. Action of Primary Aromatic Amines on Benzil. By F. X. BANDROWSKI (Monatsh. 9 685-694 ; compare Voigt Abstr. 1885 1067).-Benzil forms condensation products with the amines when they are heated together in open vessels at 100-150". With aniline and orthotoluidine only monosubstituted but with paratoluidine and a-naphthylamine a mixture of both mono- aud di-substituted com- pounds were obtained. All the compounds of benzil described below are characterised by not forming salts with dilute acids and by the ease with which they are reconverted into their generators.Anilbenzil COPh.CPh:NPh melts at 105" and gives characteristic colours with alcohohic potash (violet) and with cold concentrated sulphuric acid (blood-red turning to green). OrthotoliZbewziZ COPh.CPh:Pu'*C7H crystallises from alcohol in yellow plates which melt at 104" and readily dissolve in ether and benzerie. Paratolilbenzil crystallises in yellow prisms melting at 116-11 7". ParaditoZiZbenziZ C,H,.N:CPh.CPh:N.C,H is a bright yellow crys- talline powder melting at ltjl" and more soluble in alcohol than para tolilbenzil. a-Naphthilbenzil COPh*CPh:N*CloH7 crystallises from alcohol in golden-yellow needles melting at 1313-139". It dissolves readily in benzene less readily in ether and with difficulty in light petroleum.Di-oc-naplit~ilbe~~z~l CloH,*N:CPh*CPh:N*CloH is insoluble in alcohol but crystallises from a mixture of benzene and light petroleum in dark yellow needles melting at 218-219". Orthotolilbenzoin OH*CHPh-CPh:N*C,H is obtained by heating together equal quantities of benzo'in and orthotoluidine for three- quarters of an hour at 150". It crystallises from alcohol in light yellow needles readily soluble in ether and melts at 141". G. T. M. Derivatives of Ethyl Phenacylbenzoylacetate. By S. KAPF and C. PAAL (Ber. 21 3053-3063). The compound melting a t 142-145" obtained together with benzoic and benzylpropionic acid by hydrolysing ethyl phenacylbenzoylacetate (compare Abstr. 1888 839) is diphenacyl (diphenyl ethylene diketone) (compare Bolting and Kohn Abstr.1886 349 ; &,us and Werner Abstr. 1887 827 ; and Hollemann Abstr. 1888 275). It can be obtained by mixing ethyl phenacylbenzoylacetate (1 mol.) with a small quantity of alcohol adding an 8 per cent. aqueous solution of potash (li mol.) and keeping the mixture for 8 to 10 days at the ordinary tempera- ture ; the whole is then filtered the residue extracted with cold ethyl acetate to remove the unchanged ethereal salt and recrystallised from alcohol or from a mixture of benzeue and light petroleum. The yield is 20-25 per cent. of the ethereal salt employed. Diphenacy Zdihydruzone C2H4( CPh:N,HPh) prepared by boiling the diketone with phenylhydrazine crystallises from alcohol in slender colourless needles melts at 180" with decomposition and is readily soluble in ether benzene and hot glacial acetic acid.The impure148 ABSTRACTS OF CHEMICAL PAPERS. compound is unstable especially in the light. The dioxime C2H4( CPh:N*OH),? prepared by boiling a dilute alcoholic solution of the diketone with hydroxylamine crystallises from dilute alcohol in colourless needles or plates melts at 203-204" and is readily soluble in glacial acetic acid alcohol ether alkalis and mineral acids but sparingly in benzene and light petroleum. aa'-Diphenylfurfuran (Zoc. cit.) is obtained when the diketone is heated a t 130-150" with Concentrated hydrochloric acid. It gives a dark grey coloration with isatin and sulphuric acid and dissolves in concentrated sulphuric acid forming a green solution which on heating changes to reddish-brown with a bluish-green fluorescence.Diphenacyl gives the same reaction with concentrated sulphuric acid. Dipk enyltetrahydrofurfuran O<CIIPh.CH2> C HP h*CH prepared by treating a hot alcoholic solution of diphenylfurfuran with sodium is a colour- less viscid oil boiling a t 230-232". It is insoluble in water but mixes with most of the ordinary solvents in all proportions. 2 5 Diplzenylthiophen CaSH2Ph2 obtained by heating diphenacyl (1 part) with phosphoric sulphide (14. parts) at 160-186" crystallises from alcohol or acetic acid in yellowish or colourless plates melts a t 152-153" is readily soluble in most of the ordinary solvents and distils unchanged. When ethyl phenacylbenzoylacetate is heated at 150-2W0 with glacial acetic acid and excess of phosphoric sulphide an acid melting at 216" probably diphenylthiophenuarboxylic acid is obtained.E t h y l aa-di,~henylficrfura.n-/J-carboxylate C1HPh20*COOEt is ob- tained when finely-divided ethyl phenacylbenzoylacetate is boiled with alcohol and excess of moderately concentrated hydrochloric acid. It separates from dilute alcohol in large crystals. Phenylacetylenebenzoylacetic acid (Zoc. cit.) yields a monobromo- substitution product which crystallises in colourless needles melting at 200". When the acid is treated with phosphoric chloride in chloro- form or carbon bisulphide solution and the product poured into well- cooled methyl alcohol it yields a methyl salt which crystallises in orange needles and contains chlorine. A yellow crystalline htydr- azone Cz9H4,N40 is formed when the acid is warmed with phenj-1- hydrazine ; it melts a t about loo" is insoluble in water and resinifies when treated with most ordinary solvents.The acid also combines with hydroxylamine. It shows the indophenin and Laubenheimer's reaction. E t h y l di~henyl~moline-~-carboxylate C4NH,Ph,*COOEt [= 2 5 31 is obtained when ethyl phenacylbenzoylacetate is heated with ammo- nium acetate and glacial acetic acid. It crystallises from acetic acid in colourless needles melts a t 159" and dist'ils unchanged when heated in small quantities. It is readily soluble in alcohol ether benzene and glacial acetic acid sparingly in light petroleum and insoluble in water. It dissolves in warm concentrated sulphuric acid with a reddish-brown coloration which changes to reddish-violet with a blue fluorescence when the solution is heated more strongly.ORGANIC CHEMISTRY.149 2 5-Diphenylpyrrolinecarboxylic acid (Zoc. cit.) melts at 216". The compound described as ethyl ocz-diphenylpyrroline-b-caaboxylate (Zoc. cit.) is the amide <Cph:CH NH'CPh>C*CONH2. aa-Diphenylpyrroline can be obtained by boiling ethyl diphenylpyrrolinecarboxylate with alcoholic potash by boiling diphenacyl with ammonium acetate and glacial acetic acid and by heating the diketone at 150-160" with alcoholic ammonia. It is also obtained by distilling diphenylpyrrole- carboxylic acid over heated lime but considerable decomposition takes place (compare Baumann Abstr. 1887 735 and Holleman Eoc. cit.). I t gives the same coloration with concentrated sulphuric acid as the ethereal salt described above.Et hy 1 trip h my@ yrrolinecarbox y late C,NHPh,*CO@Et [Ph, COOEt = 1 2 5 31 prepared by boiling ethyl phenacylbenzoylacetnte with aniline and glacial acetic acid crystallises from glacial acetic acid in yellowish slender needles melts at 169-170"? and is only sparingly soluble in most ordinary solvents. CJTHPh3*C OOH prepared by boiling the ethereal salt with alcoholic potash crystallises from glacial acetic acid in needles melts at 273" and is rather sparingly soluble in most of the ordinary solvents. It sublimes with only slight decomposition and gives a reddish-brown solution when heated with concentrated sulphuric acid. 2 5-Triphenylpyrroline (compare Baumann Zoc. cit.) and a com- pound melting at 140-142" are obtained when the preceding com- pound is distilled over heated lime.The substaiice melting at 140-142" crystallises in colourless needles or plates and has the same composition as triphenylpyrroline. Trip heny Zpyr~o Zinecarbox y Zic acid F. S. K. Derivatives of a-p-Dichloronaphthalene. By P. HELLSTR~M (Ber. 21 3267-3271).-DinitrodichEoronaphthalene C,oH,CI,(NO,)I is prepared by the action of a mixture of fuming nitric and strong sulphuric acids (equal parts) on dichloronaphthalene. It crystallisev in spherical aggregates of bright yellow slender flat needles melts at 169*5" and dissolves very sparingly in ether very readily in boiling glacial acetic acid. When distilled with phosphorus pentachloride a compound possibly hexachloronaphthalene is obtained which crystal- lises in long bright yellow needles melting at 135-136".a-P-Dic~~lorona~hthaq~~~none CloH402C12 obtained by adding a solution of a-P-dichloronxphthalene in glacial acetic acid to a solution of chromic acid i n glaciaJ acetic acid (Guareschi Ber. 19 1154) melts at Nl" sublimes in long yellow needles and is rather sparingly soluble in alcohol. It yields with hydroxylamine a com- pound which crystallises in reddish-brown needles and carbonises at 215". When a solution of the quinone is treatled with aniline dichlor- anilidonaphtliapuinone CloH302Cl,~~ HPh is formed. It is a red crystalline substauce melts at 254-255" and is very sparingly soluble i n glacial acetic acid less soluble in alcohol ; it sublimes in carmine-red needles with a greenish- bronze lustre.150 ABSTRACTS OF CHEMICAL PAPERS.The above results show that a-/I-dichloronaphthalene is not identical with the so-called a-dichloronaphthalene. N. H. M. Disubstituted Naphthalenes from the Isomeric Chloro- phenylparaconic Acids. By H. ERDMANN and R. KIRCHHOFF (Annalm 247 366-3SO).-The isomeric chlorophenylparaconic acids yield chlor-a-naphthols on distillation just as phenylparaconic acid yields a-naphthol (Abstr. 1884 906). The naphthols are con- verted into the corresponding dichloronaphthalenes by the action of phosphorus pentachloride. Metachlorophenylparaconic acid yields the 1 1'-chloronaphthol. Ortho- and para-chlorobenzaldeb ydes are prepared- by converting the chlorotoluenes into chlo~obenzal chlorides and decomposing the product by the action of anhydrous oxalic acid at 160".The meta- chlorobenzaldehyde is obtained from metamidobenzaldehyde. When the chlorobenzaldehydes are heated at 120-140" with succinic anhydride and potassium acetate in molecular proportion chloro- phenylparaconic acids are produced. The ortho-acid C,,H&lO + lQHzO crystallises in needles and melts at 146-147". 100 parts of boiling water dissolve 1.4 parts of the acid. The para-acid crystallises with Q mol. H,O. 1 part by weight of the acid dissolves in 100 parts of water at loo" and in 500 at 16". The acid melts at 119-120". The meta-acid forms prisms and melts at 160-161". Chloronaphthol [Cl OH = 4 1'3 crystallises in plates and melts at 131.5". Both salts are crystalline. The 2 1'-chloronaphthol melts at 123" and the picrate at 139".The acetate is an uncrystallisable oil. R y the action of ammonium calcium chloride at '260" the chloronaphthol is converted into chloro- naphthylamine. The hydrochloride melts a t 235-239" and yields a crystalline precipitate with platinum chloride. 3 1'-chloronaphthol crystallises in prisms and melts at 94". The acetate forms rhombic plates and melts at 47". The picrate crystallises in needles and melts at 165". The three dichloronaph thalenes obtained by the action of phos- phorus pentachloride on the chloronaphthols have the following melting points :- C1 C1 = 4 1' melts at 107" and is identical with 1 4' dichloro- naphthalene ; 2 1' dichloronaphthalene melts at 61.5" ; and 3 1' at 48". The two last compounds have been previously described by Cleve and others.w. c. w. The acetate melts at 53" and the picrate at 160". Dimethylea-Naphthylamine and DiethyL-Naphthylamine. By P. FRIEDLANDER and P. WELMANS (Ber. 21 3123-3130).-Di- methyl-a-naphthylamine (Hantzsch Abstr. 1880 813) boils at 272-274" (uncorr.) and is very strongly refractive. Amidodimeth y lnaphthylamine NH2*CIoH6*NMez is prepared by reducing the nitroso-compound or from the azo-derivative. It dis- solves readily in the usual solvents and in dilute mineral acids andORGANIC CHEMISTRY. 151 separates from the aqueous solution as an oil; it quickly becomes resinous when exposed to air. The acefyl-derivative crystallises in pointed plates melts at 194-195" and dissolves readily in alcohol and glacial acetic acid sparingly in ether.Nitrosodimethyl-a-nuphthylnmine NO*C,,H6.N1\fe2 is obtained by adding a strong solution of sodium nitrite (7 grams) to dimethyl- naphthylamine (17 grams) dissolved in hydrochloric acid (30 c.c.) in presence of ice. The solid product is freed from adhering liquid by suction dissolved in cold alcohol and precipitated with ether. The substance which is probably the hydrochloride of the base is readily soluble in a little water but is decomposed when the solution is diluted. The free base is precipitated as an oily precipitate which gradually solidifies when sodium carbonate is added to the solution of the hydrochloride. It quickly decomposes into dimethylamine and nitrosonaphthol. Dimeth y lnap ht h!y lam inecarboxyl ic acid COOH-CInH6-NMe2 prepared by heating the base (2 rnols.) with carbonyl chloride (1 mol.) at 60-70" for three to four hours crystallises from alcohol in white pointed needles melting at 163-165".(COOH~CloH,yNMe2),,H,PtC1 The ylatinochloride crystallises in yellow needles. The salts of the alkalis are readily soluble and do not crystallise well. Brornodimet h y lnaphthy larnine h ydrobromid e cryst allises from water in presence of hydrogen bromide in quadratic plates of a silvery lustre. The free base is a strongly refractive oil which boils at 260" with decomposition. Dimethy1naphthylaminesulp;ho.nic acid SO3H-CloH6*NMe2 prepared by heating the base with sulyhuric acid (4 parts) at 150" crystallises in lustrous plates dissolves sparinqly in water readily in ether and alcohol.The sodium potassium calcium and barium salts form orys- talline precipitates. Diniethylnaphthylamine is readily attacked by nitric acid yieldinq two nitro-componnds melting respectively at 87-88" and 126-128". Tetmrnethyldiarnidodinaphthylphenylmethane CHPh(CloH6*NMea)2 is obtained by heating dimethylnnphthylamine (2 rnols.) benzaldehyde (1 mol.) and zinc chloride at 110-120" dissolving the product in the smallest possible amount of benzene and adding ether. It separates in lustrous crystals melts at 188-189" dissolves sparingly in alcohol and ether readily in glacial acetic acid benzene carbon bisulphide and in dilute mineral acids. The platinochZm*de is sparingly soluble. Heaanzethyltriarnidodinaphthylp henylmethane NMe2*C6H4*CH( C10H6*NMe2)2 prepared by the action of dimethylparamidobenzaldehyde on dimethyl- naphthylamine forms white needles melting at 178-179".Diethyl-a-napht hylamine is readily obtained by heating naphthyl- amine with aqueous soda and ethyl bromide or iodide at 110-120" and is purified in a manner similar to dimethylnaphthylamine. It forms a clear oil which gradually becomes brown and boils at152 ABSTRACTS OF CHEIlICAL PAPERS. 283-28.5" (uncorr.). Sp. gr. = 1.005. The subhate crystallises in thick prisrns readily soluble in water. The carbozylic acid prepared by the action of carbonyl chloride on the base Iorms white plates melting at 3 66". When naphthylamine is heated with ethyl bromide (1.5 part) and alcohol a t 120" (Smith Trans. 1882 180) a product; consisting essentially of monethylnaphthylamine is formed. N.H. M. a-Naphtholbidiazobenzene and a-Naphthylaminebidiazo- benzene. By C. KROHN (Rer. 21 3240-3242).-a-Naphtholbi- dinsobensene OH*CIoH5(N2*Ph)z [OH N2Ph N2Ph = 1 2 41 is readily obtained by adding a solution of diazobenzene chloride (2 mols.) to a slightly alkaline solution of a-naphthol (1 mol.). After 12 hours the compound separates as a brown powder and is extracted with boiling dilute alkali. It is purified by crystallisa- tion from aniline and will then crystallise well from any solvent. It melts at 183" and dissolves very readily in chloroform readily in ether benzene. and in boiling aniline sparingly in light petroleum alcohol and glacial acetic acid ; the solution in strong sulphuric nuid is dark-green. When reduced with tin and hydrochloric acid aniline and diamido-2-naphthol are formed.a-Naphthylanzinebidiazobenzene [NH NzPh N2Ph = 1 2 41 is prepared by adding a strong aqueous solution of diazobenzene chloride (1 mol.) to an alcoholic solution of naphthylazobenzene (1 mol.) con- taining sodium acetate; in 12 hours the reaction is finished. It crystallises from aniline in red needles melts at 189" and dissolve8 readily in chloroform sparingly in most other solvents. The acetyl- derivative is yellow arid melts a t 265" ; the solution in sulphuric acid is brown. When a-naphthylaminebidiazobenzene is reduced with tin and hydrochloric acid aniline and a triamidonaphthalens are formed ; the latter reacts with phenanthraqninone in presence of glacial acetic acid yielding an azine which dissolves in Rtrong sulphuric acid forming a green solution.The azo-group is therefore in the ortho- position to the amido-group. N. H. M. Naphthoic Acids. By A. G. EKSTRAND ( J . p r . Chem. [2] 38 241-285 ; compare this vol. p. 52).-The acetyl-derivative of amido- a-naphthoic acid (m. p. 2 11') forms microscopic needles melting above 280"; the calcium salt crystallises with 3 mols. HzO in very soluble violet needles ; the hydrochloride forms anhydrous violet needles soluble in warm water and alcohol melting above 290" ; the sulphate and nitrate are also described. When the acetyl-derivative is treated with nitric acid (sp. gr. 1-42) nitrncetylamido-a-naphthoic; acid is produced ; it melts a t 259" and is easily soluble i n alcohol. When chlorine is passed through R glacial acetic solution of the Same amido-a-naphthoic acid containing some iodine a mixture of amm oniurn chloride and dichloroii ap ht haquinonecar box y Zic acid CloH30aC1,*COOH is obtained. This acid crystallises in violet needles melting at 255" ; when treated with a,mmonia it is converted into red needles of o diammonium salt ONHI.CloH3O2Cl*C0ONH~,ORGhSlC CHEMISTRY.153 of ch 101.hyaro~yna~hthaquinonRcarboxylic acid. From this the acid is obtained by heating with sodium hydroxide solution until all aniuionia is expelled and then adding hydrochloric acid ; i t crystal- lises in orange-yellow rhombic tables melting a t 246"; the acid t~mmo7~iui1 salt is obtained by the action of mineral acids on the diamni oniu m salt. Ck lo?-rnr tm- a-nap hthoic acid obtained f i-om chlor-a-na pht hoic acid (1 l ' ) crystallises i n broad prisms melting at 227" ; its ethyl salt melts a t 84".By reduction this acid yields chloramido-z-.ncxphthoic acid which crystallises i n needles beginning to melt at 210" but not fully melted until 285" ; its hydrochloride is described. Dichloronifro-~-na~~~t720iC acid is obtained from dicliloro-a-naphthoic acid (COOH C1 C1 = 1 1' 47 and melts a t 165"; it has a very bitter taste. The sodium salt of dinitro-a-naphthoic acid of melting point 265" (Abstr. 1884 1361) crystallises with 6 mols. H20 arid the barium salt with 2$ mols. H20 ; the calcium salt is soluble 111 138 parts of water at the ordinal y temperature. The compound formed when this acid is reduced with hydrogen sulphide in a n ammoniscal solution (Abstr.1886 949 ; 1887 373) contains sulphur as part of the mole- cule ; i t would thus appear to be a sulphide of dicxzinerqhthoic acid S[ <$>CI,H,.COOH],. When th6 dinitro-acid is reduced with tin and hydrocl~loric acid dianiidonaphthalene is formed and at the same time if the acid is first dissolved in glacial acetic acid a black powder which appears t o be di-imido-a-naphthoic acid COOH.C,,H,< NH The ethyl salt of trinitro-a-naphthoic acid (m. p. 283") crystallises from alcohol in small brown prisms which melt at 131"; the calciim salt crystallises in brown laminzt or needles with 5 mols. H,O. When nitro-a-naphthamide (Abstr. 1886 948) i s reduced with t i n and h j drochloric acid chZoronaphthostyvi1 is produced ; it crystallises in green or yellowish-green needles which melt a t 265" and sublime.ChZoronaphthoZacfone ClaH,CIOCO (compare Abstr. 1886 716) is formed when chloimine is passed through a carbon bisulphide solution of naphtholactone containing some iodine ; it melts a t 184-185" ; when it is dissolwd in weak soda solution and hydrochloric acid added slender needles melt'ing a t 190-191" are obtained ; these arc c h l o r h y d r o z y - a - r ~ ~ ~ l ~ t h o i ~ acid. The rulciurn salt is anhydrous. If the naphtholactone is dissolved in nitric acid (sp. gr. 1.42) and SotUe fuming acid added rzitrona~htholacto?re is formed ; i t cryst:illiqes from glacial acetic acid in slender yellow needles melting at 242" aud sparingly soluble in alcohol ; by treating it like t h e chloronaph tho- lactone a nitrohydvoxytIaphthoic acid is obtained in rhombic tables melting a t 242" ; its calcizcm salt contains 5+ mols.H,O. By m ~ . PALMAER (Ber. 21 3260-3664) .-Nitronaph thalene is heated ou a water-bath n i t h ordinary sulphuric acid (2 parts) and fuming acid (1 p a r t ) ; after 10 hours the pi*oduct is pourvd into water when the a-sulphonic acid separates. The filtrate is neutralised with chalk . NH> A. G. B. Action of Sulphuric Acid on a-Nitronaphthalene. FOL. Lvr. m131 ,4BSTRACTS OF CHEJIICAL PAPERS. and evaporated down; on cooling the calcium salts of the a- and &acids separate. The mother-liquor from the calcium salts is treated with potassium carbonate and the potassium salts converted into chlorides. On crystallising from various solcen ts two chlorides N02*CloH6*S02CI melting respectively at 167" and 126" were separated.The chloride of higher me1 ting point forms slender ye1lowic;h needles sparingly soluble in glacial acetic acid; when heated with water in closed tubes the acid is obtained in readily soluble needles. The ethyl salt NO,.C1,H,*SO,E t forms thin yellow needles melting at 106-107". The amide NOz*CIoH6*S020NH2 crgstallises in small yellowish-white needles melting at 228". When the chloride is dis- tilled with phosphorus pentachloride dichloronaphthalene melting at 62' is formed. The chloride is therefore a derivative of the &acid (a-nitro-&sulphonic acid). The potassium salt NO2.C1,,H6*SO3R -t 4H20 fornis very readily soluble yellow needles ; the sodium salt cyystallises in spherical aggregates of needles ; the silver salt crystal- lises in readily soluble well-formed needles ; the barium salt (with 31 mols.H,O) forms groups of needles ; the anhydrous barium salt dissolves in 9.1 parts of boiling water and in 377 parts of water at 17". The calcium salt forms long soft needles very soluble; the lead (with 3 mols. H20) naagnpsium (with 9 mols. H,O) rrnanga*nese (with 10 mols. H,O) copper (with 8 mols. H,O) and zinc (with 10 11101s. H,O) saZts were also prepared. The sulphochloride me1 ting at 126" forms monoclinic crystals iden tical with the chloride of /3-nitronaphthalenesulphonic acid ; a b c = 0.9956 1 0.8308 ; ,@ = 81" 28'. N. H. M. 6,-Amidonaphthalenesulphonic Acid. By P. T. CLEVE (Ber. 21 NH2*CIoH6*8 03K and the amnioniisn salt are very readily soluble ; the sodium salt forms readily soluble scales; the silver salt with 1 mol.H,O separates in white microscopic needles ; the calcium and barium (with 1 mol. H,O) salts are readily soluble and crystallise respectively in needles and thin plates ; the lead scrlt forms very lustrous prisms. in rather large yellow crystals. SO,.NH + H20 p'e- pared by reducing the nitrosulphonamide with hydriodic acid crystallises in small groups of lustrous needles melts at 131" and dissolves readilg in dilute hydrochloric acid. The hydrochloride forms sparingly soluble yellow prisms. 3271-3276). Potassium r-amidoiia~htltalenesulp~~t~ate 7- Uiazonaphthal enesulphonic acid CloH,< N:N > cry stalli ses y- Arnidon aphtli aleuesulp honamide NH2* C so3 The acetyl-derivative NH2.S 02*CloH,.NHAc crystallises from boiling water in tufts of needles which melt a t 220-221".The c a r b a d d e NH2*CO*NH.Cl,H,.S0,*NH.C0.NH is formed by the action of potassium cyanide on the hydrochloride of the ttmide. It is amorphous melts at 273O is readily soluble in aqueous soda almost insoluble in water.ORUANIO CHEMISTRY. 155 r-Chloronaphthaleiae sulphochloride c ~ c 1 ~ s 0 c ~ is prepared by heating the diazosulphonic acid with hydrochloric acid neutinalising the product with potassium caxbonate and treating the potassium salt with phosphorus pentachloride. It is crystallised from light petroleum. I t melts at 106". Potassium chloronaphthalenesulphonate crystallises in thin lustrous scales rather soluble in boiling water ; the silver salt forms small stellate gronps of needles ; the barium salt with 3 mols.HzO forms very sparingly soluble microscopic needles. The ethyl salt crgstallises from alcohol in long needles melting at 76-79". The amide forms small triangular scales melts at 168' and is very sparingly soluble in water. N. H. 1111. 6.Amidonaphthalenesulphonic Acid. By P. T. CLEVE (Ber. 21 3264-3267) .-Yotassiuw 6-a~~zidonu~hthnlenesulphonate) NH2.C ,OH,* S O,K forms very soluble thin scales the sodium salt (with + mol. H,O) forms readily soluble thin needles ; the nmmonizcrn salt crystallises in very soluble thin plates ; the calcium salt (with 2 mols. HzO) is a readily soluble powder and becomes quickly coloured when exposed to air; the barium salt crystallises in rather sparingly soluble flat needles.The zinc salt (with 4 mols. HzO) forms lustrous yellow rather sparingly soluble well-formed needles ; the naqnesium lead and silver salts are also described. The diazo-acid C10H6N2803 prf- pared by the action of nitrogen trioxide on the anhydrous acid suspended in absolute alcohol is a powder. When aqueous alcohol is used an intensely violet dye of the formula + 2+Hz0 is obtained ; this is soluble in water and becomes brown when treated with alkali. The sulphonamide NH,.C,oH,.SOz*NHz is prepared by boiling the nitrosulphonamide dissolved in glacial acetic acid with hFdriodic acid ; i t crystallises in slender yellowish needles and melts at 181". The hydvochloride NB z*S02*CloH6*NH2,HC1 + H,O forms slender needles ; the hydriodide forms lustrous yellowish needles soluble in water and alcohol ; the acetyl-derivative NHAc*C,oH,j*SO2*NHZ crystallises from boiling water in slender white needles melting at 213".The carbamide NHa*CO-NH*CloH6*SO2*NH*CO*NH2 is pre- pared by the action of potassium cyanate on the sulphate of the amide ; it is an amorphous powder melts at 225" and dissolves very sparingly in water alcohol glacial acetic acid &c. readily in aqueous soda. Amidothionaphthol 2CloH6*NHz*SH + EtOH is obtained by heating the amide with hydriodic acid and phosphorus; the thin lustrous plates of amidothionaphthol hydriodide are treated with ammonia arid the oil dissolved in alcohol. It separates in sparingly soluble needles melting at 127". N. H. M. m a156 ABSTRACTS OF CHEMICAL PAPERS.Constitution of Isomeric Naphthalene-derivatives. Part 3. ag-Disubstituted Compounds. By H. ERDMANN (Annalen 247 306-3661) .-The naph tliylaminesulphonic acids yield a- or /3-naphthyl- arnine on the elimination of the sulphonic groups and a- or /%naphtha- lenesulphonic acids on the elimination of the aniide-groups. The disubstitution products of naphthalene are divided into four classes for the purpose of clnssifica tion namely 3-o~~-na~hthylaminesulphonic acids ; S-PP- ; 4-a-j!- ; and 4-/3-a-naphthylaminesulphonic acids. I n the preparation of ar-nitronnphthalenesulphonic acid [I 4'1 from a-nitronaphthalene by Cleve's process the more soluble isomeride [l 1'1 is obtained as a bye-pi*oduct. The properties of [ 1 41 az-naphthylaminesulphonic acid have beeh described by Pirin (as naphthiorzic acid) (Annalen 78 31) and by Witt (Abstr.1586 364). The author has previously shown (Abstr. 1888 %90) that the acid which Wit+ (Abstr. 1886 554) obtained by the action of fuming sulphuric acid on a-nnphthylamine- hydrochloride is the [ 1 4'1 nnphthylaminesulphoniu acid. The [l 1'1 acid is obtained from SchBllkopf's patent iiaphthylaminesul- phonic acid S which consists chiefly of the sparingly soluble sodium salt of this acid. 238 parts of boiling water or 4800 parts of water at 21" dissolve 1 part by weight of the acid. The cold aqueous solution produces a violet coloration in solutions of auric or ferric chloride. The sodium salt crystallises in compact tables or plates and the potassium salt crystnllises in plates.One litre of water dissolves 26.7 grams of the sodium salt a t 100" and 11.3 at 24"; also 149 grams of the potassium salt a t 100" and 35.6 at 19". The lead salt chrystallises in plates and the silver salt in feathery crystals. Benzaldehjde unites with the sodium salts of the aa-naphthylaminesulphoiiic acids forming sodium benzal- naphthylaniinesulphonate. The sodium salt of the [l 41 acid crystal- lises with 1 mol. H20 in golden plates the [l 4'1 salt is whitre cont'ains 2 mols. H20 and is distinguished from the preceding salt by its ready solubility in water. An analogous [l 1'1 compound is n d formed. Dilute sulphuric acid a t 180" converts each of the three isomeric roc-naphthylaminesulphonic acids into a-naphthylamine. I n preparing the diazo-compounds the sulphonic acids must be in a finely divided state the solutions must be cold and strongly acid and during the operation the nitrous acid must be present in slight excess.The [l 41 diazonaphthalenesulphonic acid is jellow the [I 4'1 is grey and the [l 1'1 forms greenish-yellow prisms. The latter compound is distinguished from the others by melting without detonation. Reduction with tin and hydrochloric acid converts the diazo-com- pounds into a%-naphthyl hydrazinesulphonic acids. The [ 1 41 acid forms white needles soluble in hot water but more freely soluble in hot hydrochloric acid. The sodium salt C,,,H6(N2H,)*SO3Na + 4H10 crystallises in plates. The [l 4 ' j acid forms plates or groups of needles. Its sodium salt crystallises with 39 mols.H20. The [l 1'1 acid is deposited in slender plates. The potassium arid sodium salts are anhydrous. The latter is chnracterised by its sparing solubility in water. The ammonium salt is freely soluble. The pure acid forms white needles.ORQSNIC CHEMISTRY. 157 The three isomeric acids yield a-naphthalenesulphonic acid on boiling with an acid solution of cupric chloride. The 1 4- and 1 4'-nLcphtholszclp7ionic acids are prepared by dis- solviiig the corresponding diazonaphthaleiiesulphonic acids in boiling sulphuric acid diluted with four times its weight of water. The former has been described by Neville and W inther (Trans. 1880 632). The latter is a deliquescent crystalline substance and melts between 110' and 120". Under similar conditions [l 1'1 diazonaphthalene- sulphonic acid yields an anhydride naphtkosultons C1,H6<-'->. The sultones bear the same relation to yhydroxysulphonic acids that the lactones do to y-hydroxycarboxylic acids.Naphthosultone crystallises in prisms melts at 154" and boils above 360" with partial decompo- sition. It is soluble in chloroform and in warm benzene. A t the ordinary temperature alkalis do not act on the sultone but at 130" alcoholic ammonia converts it into the ammonium salt of [l 1'3 naphtholsulphonic acid OH*C,oH6*SOsNH,. The ammonium salt is freely soluble in water and the solution gives a precipitate with lead salts and also on boiling with an excess of scdium hydroxide the basic sodium salt C,,H,SO,Na + l&H,O. The free acid crystallises with 1 mol.HzO and produces with ferric chloride a deep green color- ation changing to red. The conversion of [ 1 41- and [I 4'1-naphthylaminesulphonic acids into the corresponditig dichloronaphthalenes has been previously described by the author (Abstr. 1838 290) but the [l 1'1-diazosul- phonic acid on treatmenl with phosphorns pentachloride yields chZoroiinphthosuZto~~e Cl0H5C1SOs. This compound forms yellow needles and melts a t 174-175". It is not attacked by alkaline solutions a t the ordinai-y temperature. [ 1 41-Dihydroxynaphthalene is identical with a-naphthahydro- quinol ; [ 1 4'1-dihydroxynaphthalene has been described by Bernthsen and Semper (hbstr. 1887 674). The [l 1'1-dihydr- oxynaplithalene is obtained from nnphthosultone by fusion with potassium hydroxide.I t crystallises in needles or plates and melts at 157-138" and dissolves freely in ether benzene and toluene. The dincetute C,H,( Ohc) melts a t 147-148". Two au-dinitronaphthalenes are known; [l 4'1 melts at 218" and [I 1'3 a t 170". Aguiar (Ber. 7 309) has described the preparation and properties of [l 4'1- and [l 1'1-diamidonaphthalenes from the corresponding S 0 2 dinitronaph t halenes. w. c. w. The Dextrorotatory Terebenthene. By L. PESCI (Chem. Centr. 1888 1097-1098 fi-om Ann. Chirn. Fawn. 7 353-358) .-The terebenthene was obtained from American turpentine by fractionat- ing in a vaciium and was found to be the principal product; sp. gr. = 0.8641 boiling point 156-157'. Specific rotation [a]= = + 1394.5". The American turpentine contains also 1aevorotatoi.y sub- stances.Nitroterebenthene was prepared by treating the terebenthene wit11 potassium nitrite and dilute sulphuric acid the green oily product158 ABSTRACTS OF CHEMICAL PAPERS. was shaken with ammonia washed with dilute hydrocliloric acid and distilled twice in a current of steam. I t is a yellow liquid having the odour of peppermint oil. Sp. gr. 1.0499 ; specific rotation [z]D = +2*984. By reduction with zinc and acetic acid the same amidoterebenthene C10H,5NH3 was obtained as the author prepared from the I~evorotatory terebenthene. The hydrochlorides of both show the same specific rotation [a] = -48.508" and - 48.629". The hydrochloride of lceuoterehenthene possesses the specific rotation [a]D = -30*687" melting point 125". Lcevoterebenthene hydrobroinide specific rotation [ a ] = -27.802" and melting point 87".Dextroterebenthene hydrochloride and hydrobronaide are optically in- active. Their melting points are 125" and 91" respectively. These facts go to prove the non-identity of the two terebenthenes. Hydroxycamphoronic Acids. By J. KACHLER and F. V. SPITZER (Monatsh . 9 7O8-726) .-The two isomeric hyclroxycamphoronic acids formed by the action of aqua regia on camphoronic acid car- respond in their crystalline form with the two modifications which Kachler obtained by heating camphoronic acid with bromine and sub- sequent treatment with water. Further investigations of the com- pounds obtained by the action of bromine show that they are not chemically identical as previously suggested. I n order to isolate the isomerides the mixture of acids dissolved in a small quantity of warm water is treated with aqueous baryta until the solution gives only a feebly acid reaction.Ammonia is added until the solution is distinctly alkaline and the mixture shaken for some time when bibasic barium a-hydroxycamphoronate separates out the /3-salt remaining in solution. ac-Hydro.cZ/cam~horonic acid C9H1407 crystallises in monoclinic plates or prisms. It is only slightly soluble in ether dissolvesreadily in cold water a n d alcohol softelis a t loo" and melts a t 216.5" (corr.). On long exposure to air or more quickly over sulphuric acid the crystals lose water and are converted into the anhydride CgH,,O which on heating loses more water forming the anhydride CgHlo05.This is a crystalline powder which dissolves readily in alcohol and water and melts a t 135-137'. Botjh anhydrides are reconverted into the acid by boiling with water.. The salts of the a-acid are mostly easily soluble in water. The acid potassium salt CgH,,K07 crys- talliscs in stout needles the dipotassium salt C9H1,K3O7 + +H,O in scales; when heated a t loo" the latter yields the compound cgH&06. The calcium salt C~RRII",CRO~ + 4&0 crystallises in bundles of needles ; the barium salt CgH1,BaO7 in thin plates only slightly soluble in water ; the silver salt CgH,,Ag207 + H,O forms minute crystals ; the copper and lead salts are anhydrous. All the above-mentioned salts in the anhydrous condition lose the elements of a molecule of water when heated. The ethyl compound CgHllEt06 crystallises in rbombic plates melting a t 158" (corr.).I f heated it gives the anhydride of a-hydroxycamphoronic acid and alcohol and on passing ammonia through the ethereal solution the salt C6HloEt06.NHI crystallising in needles melting a i 168-170" is formed. /3-Hypoxycamphoronic crcid is not so soluble as its isomeride. When air-dried it has the formula C9H1107 melts a t 250.9" (corr.) J. W. L.ORGANIC CHEMISTRY. 159 but loses water on heating forming an anhydride and furnishes mono- di- and tri-basic salts of which the tribasic salts of lead and barium are insoluble. The potassium salt CgH,,K,07 + +H20 is hygroscopic. The barium salt C9H12Ba07 + 4H20 crystallises in needles. The ethyl-derivative C,H,,F to forms needles melting at 158.5-159.5" (cow.) and resembles its isomeride forming with ammonia the com- pound C,H,,EtO,*NH melting a t 165".The authors find that when camyhoronic acid is heated with bromine no bromo-derivative is produced but the above-mentioned anhvclrides which on treatment with water yield a mixture of a- and /3-hydroxycamphoronic acid. G. T. &I. Syringin. By G. KORNER (Chenz. Cenfr. 1888 1098-1099 from Rend. R. Inst. Loinbardo [2] 21 563-572).-The author finds that syringin formerly considered as a glucoside is hydroxymethylconi- ferin C17H2107. He prepares it according t o Kromaycr's method ( D i e Bztterstofe 1861 56). It crystallises from water in long slender white needles which are only sparingly soluble in cold water but readily in hot. It contains water of crystallisation which is given off :rt 100".Melting point 191-192". It does not form insoluble corn- pounds with solutions of metallic salts ; it reacts with mineral acids similar17 to coniferin. By the action of emulsin syringin is split up into dextrose and syringenin OH*C,H,( OMe,)2*C,H4*OH ( h y d r o q - nzethylconiferyt dcohol) ; the latler resembles- coniferyl alcohol. By oxidising syringin with potassium permanganate g Zucosyringic acid C15HL0010 is formed crystallising from water in slender colour- less needles with 2 mols. H,O. It is sparingly soluble in cold water readily in hot. Melting point about 208". When crystallised from alcohol it melts a t 214". Thus prepared it contains no combined water. The lead salt is but little soluble ; the salts of potassium and barium crystallise in needles.By heating glucosyringic acid with dilute sull'huric acid it splits up into dextrose and s!/ringic acid CgHl,05. This decomposition is also effected by the action of ePrmlsin at SO". By the oxidation of sgringin with cold very dilute chromic acid ~ZucosyringinnIdeh~jcle is formed; it is soluble in water but only sparingly in alcohol and insoluble in ether. It combines with phenyl- Iiydrazine the compound crystallising in needles and melting a t 156'. The aldoxinie is decomposed by emulsin or dilute sulphuric acid into glucose and syri7igi.riaL~eJzytde C9H1004 which has the smell of vanilla. It reacts readily with phenylhydrazine and hydrogen sulphites forming soluble compounds. Syringic acid is sparingly soluble in cold water more readily in hot water soluble in alcohol.I t is monobasic and melts a t 202". The barium salt crystallises with 3 mols. B,O. The methy1 salt CgH,05Me + H20 is soluble in hot water and melts a t 83.5". Syringic acid when heated with hydrogen iodide a little above loo" decomposes with liberation of methyl iodide. With sodium methyl oxide and methyl iodide it forms methyl nzethzJlsyrin!iate C,,H1,05 melting at 82.5". Methylsyringic acid CI0Hl9O5 melts a t 168" and is somewhat soluble in hot water. Dis- till ation with calcium hydroxide produces trime thylpyrognllol. By heating syringic acid above kLo dimethglpyrogallol 0H*C6H,( OMe),,160 ABSTRACTS OF CHEMICAL PAPERS. is formed ; with ferric chloride it gives a t first a blood-red coloration which changes into copper-red needles.Cedriret was observed in the solution. Methylsyringic acid was identified as trimethylgallic acid. J. W. L. Arganin. By S. COTTON (J. Pharm. [ 5 ] 18 298-302).-This bitter principle is extracted from the kernel of the nut borne by the argan tree of the order Sayotacew growing in Morocco and Mada- gascar. Tho almond itself is bitter but contains over. 66 per cent. of a sweet fixed oil which congeals a t O" and has a density of 0.914. The bitter principle insoluble in oil ether chloroform cai*bon bisul- phide and light petrc)leum is easily soluble in water and 90" alcohol ; and somewhat less soluble in absolute alcohol. It is ext,racted by treating the crushed kerne!s with ether or some other solvent to remove the oil then extracting with 99" alcohol with the aid of heat.The alcoholic solution is then treated fractionally with ether a t intervals so as to obtain the arganin in crystals. After some days the liquid is decanted and the crystals are dissolved in boiling absolute alcohol from which they recrytallise on cooling. Very short bril- liant prisms are thus ohtained which become gummy on the filter from exposure to the moisture of the air. J. T. Homopterocarpin and Pterocarpin from Red Sandal Wood. Bv P. CAZENEUVE and L. HUGOUNENQ (Con@. rend. 107 737-740).- When homopterocarpin is heated just to the point a t which dccompo- sition begins i t yields creosote and a small quantity of catechol and when distilled with zinc powder it yields a small quantity of a volatile oil with an odour OF cournarin together with benzene toluene methane ethylene.and carbonic oxide. The principal product of the action of hydrochloric acid on homopterocarpin (Abstr. 1887 972) is a black uncrj stallisable resin which dissolves in alkalis and forms fluorescent solutions ; the hydrochloric acid retains in solution a small quantity of an amorphous red colouring matter which dis- solves in alkalis with fluorescence and probably belongs to the fliiorescein-group. Hydrioclic acid produces similar results. When heated in sealed tubes with 10 per cent. sulphuric acid Iiomoptero- carpin undergoes an isomeric change and is converted into an opaline yellowish non-crystallisable resin similar in appearance to amber whilst the sulphuric acid remains unaltered. Homopterocarpin is not affected by aqueous potash at 200" hut is attacked hy fused potash at 250-300" and yields a small quantity of a volatile oil with an odour of conmarin and phloroglucinol but no acid.Ordinary nitric acid att:icks homopterocarpin in the cold with formation of an amorphous green unstable nitroso-derivative which contains 5.5 per cent,. of nitrogen. Fuming nitric acid acts with considerable energy and on tlie addition of water an insoluble red resin separates. The nqneous solution when evaporated yields a crystalline product from which cold water extracts oxalic acid whilst hot water dissolves a substance which crystallises in yellow needles melting at lRcLo and has all tite properties of trinitro-orcinol. It yields a barium salt C',H,( N02)302Ba + 3H20 which cryshllises in yellow needles,ORGANIC CHEJIISTRI' a 161 and explodes above 150".The product of the action of nitric acid also coil tains a non-crystallisable isomeric trinitro-orcinol. If homopterocarpin is treated with excess of bromine the compound C2,H,,Br60 is obtained; it dissolves i n benzene and separates in crystalline plates melting a t 270" when the benzene is mixed with an equal volume of ether. The interaction of equal molecular pro- portions of homopterocarpin and bromine in Rollition in chloroform yields a mono-derivative C,,H,,Br06 which separates from boiling alcohol in white crystals. Phenylhydrazine and ace tic anhydride have no action on homopterocarpin. Prom these results it follows that the formula originally ascribed to homopterocarpin must be doubled and it would seem to be a condensed poly-orcinol but its con- stitution is not yet definitely determined.Pterocarpin yields similar results but the action of nitric acid is more energetic. It yields a crystalline monohomo-derivative CzoH15BrOs and hence its true formula is C,oH:,606. Pterocarpin is in all probability a lower homologue of homopterocarpin. C. H. B. Dipicolylmethane. By A . LADENBURG (Ber. 21 3099-3104) .- DipicolyZmethn~/e CH,(CH*C,NH,) is obtained by heating a mixture of picoline (from the mercury salt) with methylal in molecular propor- tion in presence of zinc chloride for 10 hours at 280-290'. The product is treated with dilute hydrochloric acid heated on a water-bath for some time made alkaline and distilled. The residue is extracted repeatedly with ether and the base extracted from the ethereal solu- tion with dilute hjdrochloric acid.The solution is treated with mer- curic chloride as long as any resin is precipitated filtered freed from mercury by means of hydrogen sulphide made alkaline with soda and extracted with ether. The base is distilled under reduced pressure. It is a light-yellow oil insolnhle in water readily soluble in alcohol and ether and boils at 319-323" under 760 mm. pressure. Sp. gr. = 1.0381 at 0". The hydmchloritie forms deliqumcent needles ; the platinochlnride C13H14N2,H2PtC16 crystdlises from water in sparingly soluble lustrous plates which melt at 215" with decomposition ; the ciurochloride (C,,H I,N,)2,HiA~iC119 + 1+H,O separates as an oil which solidifies to small needles ; the mercurochloride 13H14N1 H2HgAC110 crystallises like ammonium chloride or in large plates and melts a t 161" ; the picrate cadmioiodide periodide aiid bismuthoiodide were prepared.Dipipecolinem ethane C17H?BN2 prepared by reducing the above com- pound with sodium and alcohol forms a white crystalline mass melts at 52-51" and boils a t 195" under 26 mm. pressure. It dissolves readily in benzene and ether very readily in alcohol and is rather sparingly soluble in water. It is a strong base bnt yields mostly oily salts. The hydrochloricle Cl3Hz6N,,2HC1 is crystalline. Tetramethyl- dipipecolyl methiodide C,,H241LIe,N,,2MeI forms white crystals very readily soluble in water ; the aurochloride C1 K24Me2N2,H2Au2C Is,168 ABSTRACTS OF CHEMICAL PAPERS.crystallises in needles melting at 170-1 71" with decomposition. The constitution of the base is probably CHz(CHz-C5NMeH,)2. N. H. M. The Two Bidesyls. By J. C. GARRET (Ber. 21 3107-3l.08).- Both bidesyls (Knoevenagel Abstr. 1888 706) yield tetrapheny2- pyrroZine C2eH21N when heated with alcoholic ammonia a t 150". 'I'his crystallises in large needles melts at 211-212" and is almost insoluble in alcohol. On one occasion the preparation from iso- bidesyl melted at 234-235" but was otherwise identical with the other preparations. N. H. M. Methylstilbazole and its Reduction-products. By F. BACH~R (Ber. 21 3071-3082) .-~~eth~ilstilbazole C,,H,,N is formed when a-ylutidine is heated a t 215" with benzaldehyde (1 mol.) and anhy- drous zinc chloride. The product is mixed with alcohol acidified with hydrochloric acid distilled with steam to free it from benzalde- hyde and hydrocarbons and the residual oily liquid separated.After adding excess of soda the mixture is distilled with superheated steam ; the unchanged lutidine which passes over first is collected separately and the new base which is very slightly volatile is extracted from the latter portions of the distillate with ether the soiution dried over potash evaporated and the base distilled. The yield is about 15.4 per cent. of the theoretical quantity. It is a -yellow viscid strongly refractive oil boils a t 321-326" with slight decomposition and is readily soluble in alcohol ether chloroform and carbon bisnl- phide but insoluble in water. The hyhochlorids and the hydrobromide cannot be obtained i n crystals but the hydriodide prepared by dissolving the base in fuming h ydriodic acid crystallises from hot alcohol in microscopic yellow iieedles melting a t 210-211".The periodide is crystalline and readily Poluble in alcohol b u t insoluble in water. The picrate Cl4Hl3N,C6H3N3O7 crystallises from hot alcoholic hydrochloric acid in microscopic yellow needles melts a t 192-193" with previous soften- ing and is very sparingly soluble in hot dilute hydrochloric acid. The mercurochloride CliH13N,HHgC13 crystallises in needles has no well-defined melting point and is soluble in dilute hydrochloric acid. The platinochloride C,4H13N,H?PtClGr crystallises in smal? yellow iieedles with 1 inol. H20 melts at 183" decomposes a t 188 and is soluble in hot dilute alcohol but very sparingly soluble in hot hydrochloric acid. The nzLI-ochloride C14Hl,N,HAuC14 prepared by precipitating a boiling solution of the hydrochloride crptallises in golden needles melts a t 141-142" and is sparingly soluble in boiling water.Potassium bismuth iodide potassium cadmium iodide and stannous chloride produce precipitates in a hydrochloric acid solution of the base. The bromide Cl4HI3Br2N prepared by treating the base with bromine (1 mol.) in carbon bisulphide solution sepa- rates from hot alcohol in small nodular crystals and melts at Uih ydromethylstilhazole CIBH15N is prepared by heating methyl- stilbazole (1 part) with fuming hydriodic acid (10 parts) a t lt;O" treating the resulting periodide with sulphurous anhydride decom- 139-1 40".0 RO AS I C C k1 EM1 S T RT .163 posing the iodide with Fola and distilling the base with steam. It is a colourleps oil boiling at 290-295". The picrate CIIHl5N,C,H3N3O crystallises in small citron-yellow needles melts a t 154-156* and is readily soluble in hot alcohol but only sparingly in ether. The p7atino- chloride Cl4HI5N,H2PtCl6 is crystalline melts at 168" with decom- position and is very spaxingly soluble in water but more readily in dilute alcohol. The msrcurochZoride CllHllN H HgC1 + H20 crystallises from hot dilute hydrochloric acid in which i t is readily soluble in large needles and melts a t 93-95'. The remaining salts cannot be obtained in a crystalline condition. Me!hyZstiZbuzoZir~e C,,H,,N is prepared by reducing a boiling alcoholic solution of methylstilbazole with sodium and distilling the product with steam ; it is a colourless oil boils a t 286-291" and becomes yellow on keeping.It is readily soluble i n alcohol and ether hut sparingly in water to which it imparts an alkaline reaction. It yields an oily nitrosamine and all the salts examined were also oily compounds. Meth7;l~13yri~inecurbo~yZic acid C5NH,Me*COOH is obtained in small quantity when a-ylutidine is oxidised with the calculated quantity of a 14 per cent. solution of potassium permanganate but tlie principal product is lutidinic acid. Met hylpyridinecarboxylic acid crystallises from hot alcohol in which it is only moderately soluble in small plates decomposes at about 260" and is very readily soluble in watcr.It gives no reaction with ferrous salts and yields picoline when heated with lime. When a-y-lutidine is heated at about 225" with benzaldehyde (2 mols.) and anhydrous zinc chloride an oily seemingly neutral compound is obtained. p-Ethyl-a-stilbazole and its Derivatives. By G. PLATH (Ber. 21 3986-3099).-P-~ElthyI-a-sti2bazoZe C5NH,EtCH:CHPh [ = 3 61 is formed when collidine (10 grams) prepared from paraldehyde and aldehyde-ammoriia (compare Durkopf Abstr. 1887 499) is heated at 220-222" with benzaldehyde (9 grams) and zinc chloride. The pro- duct is acidified and distilled with superheated steam to free it from benzaldehyde and hydrocarbons. Excess of alkali is then added the unchanged collidine distilled with steam and as soon as tbe dis- tillate commences to become turbid the stenni is superheated and the distillate containing the new base which is only very slightly volatile is collected separately.The yield is about 37 per cent. of the theoretical quantity. It crystallises from dilute alcohol in colourless plates melts a t 58*5O boils a t 344" and is readily soluble in alcohol ether benzene acetone and chloroform but insoluble in water. The hydrochZoride C15H,,N,HCI separates from hot benzene in an oily condition but solidifies on cooling; it crptallises in needles and melts a t 193". The platinochloride (C15H15N),,H2PtC16 + 2H20 crystallises in needles melts a t 188" with decomposifion and is soluble in dilute hydrochloric acid but insoluble i n cold water. The auro- chloride C15H15N,HA~C14 crystallises in long needles melts a t 1 6 8 O and is insolnble in water.The stannochloride Cl5Hl5N,HSnCl3 + 3H20 crystallises from hot dilute hydrochloric acid in white needles F. S. I(.164 ABST RA CTS OF CHEMICAL PAPERS. melting at 245.5 -246 ". The mecrurochloride CI5Hl5N H AgC I crys- tnllises from hot dilute hgdrochloric acid in long needles melting a t 196". The picrate Cl5HI5N,C6H3N3O7 crystalliPes from alcohol or hot water in long yellow needles melting at 203". An aqueous solution of the hydrochloride gives precipitates with ammonium molybdate potassium dichromate and potassium cadmium iodide. The per- iodide is crystalline but unstable. The bromide C,,Hl5Br,N pre- pared by treating the base with bromine (1 mol.) in carbon bisul- phide solution crystallises from alcohol in small needles melts a t 127*5-128" and is very readily soluble in chloroform carbon bisul- phide benzene alcohol and ether but insolnble in water.Diht/droethylstilha,ole C,NLT3Et*CH,-CH2P h [ = 3 61 is obtained when ethylstilbazole is heated a t 160-165" with concentrated hydr- iodic acid. The product is treaked with sulphurous anhydride the resulting iodide diwolved in water and the solution shaken with ether ; excess of soda is then added the base extracted with ether and distilled. It is a colourless oil boils a t 316.3S" (cow.) and is readily soluble in alcohol and ether but insoluble in water. The aurechloride C,,H,,N.HAuCI + HzO and the hydrochloride are with difficulty obtained in a crystalline state. Tlteplatinochlorids ( C15H,,N),,H,PtCI crystallises from dilute hydrochloric acid in long needles melting a t 168".The mercurochloride C15H17N,HHgC13 crystallises from very dilute hydrochloric acid in long needles and melts at 136.5". The picrate is sparingly soluble in water from which it crystallises in yellow needles. OctohydroethyZstilbazole C,NH,F,t*CH2*CH2Ph prepared by treating a boiling alcoliolic solution of ethylstilbazole with sodium and purify- ing the product by mean? of the nitroso-derivative is a colourless oil boiling a t 303" (uncorr.). It lias a strong piperidine-like odour an alkaline reaction and is volatile with steam. It is soluble in chloro- form benzene ether and alcohol but only sparingly in water. No crystalline salts were obtained. I?. s. K. Paraxyloquinolinesulphonic Acids. By E.NOLTING and J. FR~~HLING (Ber. 2 1 :-I1 56-31 58) .-XylopuinolinesuIp hoiLic cicid [Me2 SO,H = 1 4 21 (compare Nolting and Kohn Abstr. 1886 355) crystallises in prisms and is very readily soluble in hot water and dilute acetic acid but only spariiigly in cold water. The bnriunh salt (CI,NHlo.SO,),Ba + H20 crystallibes in needles loses its water a t 150" and is readily soluble in hot water. The potassium salt crys- tallises with 1 mol. HzO and is readily soluble. XzJ1oqui)ioliiaesuIphonic acid [Me S0,H = 1 4 31 can be pre- pared from parasylidineparasulphonic acid by S kraup's reaction or by heating paraxyloquinoline with fuming sulphuric acid for 36 hours. It resembles the preceding compound but is more sparingly soluble. The barium salt crystallises in plates with 1 or 2 mols.H20. The potasciunz salt cryI;tallises in anhydrous needles or plates. Paraxyloquinoline is obtained when either of the above acids or any of their salts is distilled with ammonium chloride but it is more easily prepared from paraxylidine. F. S. I(.ORGANIC CHEMISTRP. 165 Isoquinoline. By G. GOLDSCHMIEDT (21Znnatsh . 9 675-684).- The author has previously shown (Abstr. 1888 306) that papaverine and its compounds with methyl iodide and ethyl iodide yield imides of hemipinic acid when oxidised witjh permanganate. This property of forming imides on oxidation with permanganate appears to be common to all isoquinoline-derivatives the base itself giving phthal- imide. I s o q i i i n o l i n e ethobromide on oxidation appears to give ethylphthal- imide but the quantity obtained was insufficient for analysis.Isoquinoliize benzyl chkiride is formed on mixing its constituents in molecular proportion. It crystallises although not easily in prisms dissolves readily in water and alcohol but is only slightly soluble in ether and benzene. When oxidised with permanganate it gives benzylph t halimide melting a t 11 5-1 16". Isoquinoliwe phenncy 1 brmnide is most conveniently prepared by mixing moleciilar proportions of itq constituents dissolved in benzene. It crjstallises from alcohol in prisms which melt a t 205" to a golden- red liquid and furnishes a nitro-compound which in its toxicological action resembles the corresponding quinoline-derivative. On oxidation with permanganate a nearly pure phenacylphthalimide me1 ting a t 156-155" was formed.G. '1'. M. Creatinines. By G. S. JOHNSON (Proc. Roy. Xoc. 43 493-534). -Normal urine when boiled with picric acid in alkaline solution causes a reduction to picramate. About one-fourth of the cupric oxide reducing power of normal urine is due to uric acid whilst the remaining three-fourths has been variously accounted for. The author finds that it is due t o a creatiiiine which can be best precipitated by adding sodium Rcetate and mercuric chloride to normal urine. A flocculent precipitate is first produced which is succeeded by one which is apparenhly crystalline but which under the microscope is found to consist of globules. It has a constitution 4(C1H,HgN,0,HC1),3HgCl + 2H20. The hydrochloride of the base C4H7N30,H Cl is prepared by decomposing the mercury salt with hydrogen sulphide.It is soluble in water and alcohol. No precipi- tate is produced with mercuric chloride until sodium acetate has been added. With platinum chloride in alcoholic solution it gives an anhydrous salt' ( C,H,N,0),,H2PtCI ; in aqueous solution a salt (C4HiN30),,H2PtCI + 'LH,O is formed. The free base is obtained by treating the hydrochloride wi-ch lead hydroxide ; i t can be obtained in three forms according to the temperature at which the solution is evaporated. If the crystals are dissolved in a small quantity of cold water and evaporated in a vacuiim. efflorescent creatinine is obtained in syuare prisms which acquii-e a porcelain-like appearance as the water of crystallisation evaporates. Rut if the evaporation is coiiducted a t 60° anhydrous crystals of tabular p-creatinine of urine are obtained. which when dissolved and again evaporated in the coid give efflor- escent creatinine. Finally if effloresced creatinine is dissolved at lOO" t,abular a-creatinine of urine is obtained and this M hen dissolved and evapoiaated in the cold recrystalliLes unchanged ; 2 mols of creatinine of urine are equivalent in reducing power to 1 mol.of glucose whilstl6G ABSTRACTS OF CHEMICAL PAPERS. 3 mols. of flesh creatinine are required to effect the same amount of reduction. The efflorescent oreatinine has tbe same solubility in water as the tabular a-salt. Urine creatinine differs from flesh creatinine in its power of reduction in the composition of its platinochloride and in its solubility in water and alcohol.Boiled with watev the creati- nine is converted into urinary creatine CdH,N,O + H20. It can be converted by Liebig's process into a creatinine hydrochloride which is identical with that obtained from flesh creatine by the same proce-s. Prom this hydrochloride four different creatinines are obtained which are not identical with the above creatinines directly prepared. C i y - tnllographic measurements of the natural creatinines are given. The creatinines from urinary creatine have less reducing powers than the natural creatinines bu't greater than that of creatinine from flesh crea t ine. Measurements by Hartley of the absorption-spectra of creatinine from flesh creatine (Liebig's process) and of the new base from nrine are given.The spectra are similar the bands being caused by condensation of numerous oxygen- and nitrogen-atoms as in uric acid. The actinic absorption is greater for the urine creatinine than for creatinine from flesh. H. K. T. Bases formed by the Action of Potash on Additive Pro- ducts of Papaverine. By A. STRANSKY (Monutsh. 9 751-761 ; compare Claus and Ritzfeld Abstr. 1886 996).-On boiling papa- verine ethobromide with aqueous potash for several hours a brown resinous substance is formed. I t may be crystallised from water and alcohol and forms prismatic plates which have the formula O(C,H,,NO,Et) and melt at 72". From this oxide the following compounds may be obtained :-The chloride C20H21N04EtC1 which crystallises from alcohol in rhombic needles melting at 80"; the platinochloride ( C,H2,N0,EtCl)2,PtC14 ; the picrate crystallising in light yellow plates ; and the chromate ( CmH21N04Et)2Cr,07 crystal- lising in yellow needles or plates and melting at 78".Papaverine benzyl chloride under the same conditions gives the oxide (C,H2,NOaC7H7)20 which crystallises in needles melting at 165". The chromate (C20H21N04C7H7),Cr207 forms yellow plates which melt with decomposition at 85" and the picrate (C2JLN04C7H7) CJ%N&& crystallises in plates melting at 185". Pavaverine methiodide (30 grams) potash (60 grams) and water (300 grams) when boiled together for 20 minutes give a product crystallising in greenish-yellow needles melting at 215" efflorescing 011 exposure to air and giving the hydroxide C20H,,N0,Me.0H when heated at 100".The corresponding picrate crystallises in plates melting at 205" and the chromate in small needles melting at 8.5". G. T. M. Papaverine-derivatives. By G. GOLDSCHMIEDT and C. OSTER- SETZER (Monut~h. 9 762-777 ; compare Abstr. 1886 83 478 ; 1887 163 ; 1888 302 1116 lll8).-The authoi-s find that the two acids ofORGAXIC CHEMISTRY. 167 the formula CloH,oOs obtained by the oxidation of narcotiiio and papaverine respectively are not identical as was previously suppose(]. The acid from narcotine (hemipinic acid) forms crystals belonging to the inonoclinic system commences to fuse in open tubes at 160-161" in closed tubes a t 156-158" and gives an orange-red precipitate with ferric chloride but no precipitate with silver nitrate. The cor- responding anhydride melts a t 166-167" the ethylimide at 96".The acid from papaverine (metahemzpinic acid) crystallises in the rhornbic system commences to fuse in open tubes a t 17&175" in closed tubes a t 172-1 73" gives a deep orange-red precipitate with ferric chloride and a crvstalline precipitate (needles) with silver nitrate. The corre- spondini anhyd&k milts at 175" the ethylimide a t 230". G. T. M. Constitution of Papaverine. By G. GOLDSCHBIIEDT (Monatsh. 9 778-781 ; compare preceding Abstracts).-Metahemipinic acid ob- tained by the oxidation of papaverine is dimethoxy-orthophthalic acid C,H,(OMe)2(COOHj [(OMe) (COOH) = 1 2 4 51,and differs from hemipinic acid by giving protocatechuic acid [COOH (OH) = 1 3 41 on fusion with potash. The cunstitution of papaverine must therefore be represented by the formula- Strychnine.By W. F. LOEBISCH and H. MALFATTI (Monatsh. 9 626-633 ; compare Abstr. 1887 282) .-Stoehr on distilling strych- nine with quicklime obtained a mixture of scatole and /%methyl- pyridiue. The authors find that when the alkalo'id is distilled with soda-lime in addition to the above-mentioned compounds. carbazole is formed; in quantitr equal to 0.5 per cent. of the shychn&e used. G. T. M. Relations between Atropine and Hyoscyamine. By A. LADENBURG (Bey. 21 3065-3070).-The author is of the opinion that atropine is an inactive base and that it stands in the same relation to hyoscyamine as racemic acid to lavotartaric acid ; moreover that the supposed conversion of atropine into hyoscyamine although possible has not hitherto been accomplished and that all observations to the contrary result from the employment of impure atropine.(Compare Will and Bredig Abstr. 1888 1316.) This view is supported by the following experiments :-20 grams of atropine aurochloride prepared from " pure " atropine was recrydallised 14 times and yielded 1 gram of hyoscyamine aurochloride. Another sample of atropine aurochloride prepared from the purest commercial atropine which had been further purified by recrystallising many times and then melted at 114" was recrystallised 14 times. 1 gram of atropine aurochloride was obtained; it melted a t about 140" and an 18 per cent. solution of the free base prepared from this sample of salt was optically inactive.168 ABSTRACTS OF CHEMICAL PAPERS.Atropine cadniioiodide crystallises from alcohol in needles and is almost insoluble in water. F. S. K. Constitution of Berberine. By S. HOOGEWERFF and W. A. VAN DORP (Rec. I’rav. Chiin. 7 206-209).-The view is expressed hat berberine is a derivative of isoquinoline and the authors are engaged on experiments with the object of proving this. Commercial Preparation and Partial Synthesis of Cocaine. By C. LIKB~~KMAKN and F. GIESEL (BPT. 21 3196-3202).-Most of the amorphous alkaloids obtained in the preparation of coca’ine yield ecgonine whcn boiled for about a n hour with hydrochloric acid (compare Liebermann Abstr. 1888 1210). The ecgoiiine can be isolated by evaporating the filtcrrd solution to d r p e s s boiling the residue with a small quantity of alcoliol to remove impurities decom- posing the salt with sodium carbonate and recrjstallising the base from alcohol.Benzojlecgonine can be easily obtained by treating ecgonine wit)h benzoic chloride or benzoic anhydride but the yield is not good in either case. The following method however gives rery good results :-Benzoic anhydride (a little more than 1 mol.) is gradually added to a hot saturated aqueous solution of ecgonine (1 mol.) and the mixture is heated on the water-bath for about an hour. The cold product is shaken with ether t o remove benzoic acid and anhydride arid the residue is rubbed and washed u ith a small quantity of water on the filter-pump. The yield is about 80 per cent. of the ecgonine employed. Small quantities of benzoylecgoiiiiie can be obtained by evaporating the mother-liquor and if the filtrate is again treated with benzoic anhydride the greater part of the unchanged ecgonine is converted into the benzoyl-derivative.The whole of the excess of benzoic acid (anhydride) employed can be obtained from the ethereal extract. Anhydroecgonine melts a t 235” is far less readily soluble in alcohol than ecgonine and the crystals effloresce when kept in a partial vacuum. The hydrochloride is horn ever far more readily soiuble in alcohol than ecponine hydrochloride. CocaYne was prepared by Einliorn’s method from the benzoyl- ecgoiiine obtained as described above and the preparation was found t o be identical with the natuml alkaloi’d in every respect. It has been observed by Lossen that when a solution of coca‘ine hydrochloride is precipitated with ammonia the precipitate is redis- solved on adding more ammonia.The authors find that this pheno- menon is simply due to the additional quantity of water and not to any solvent action of the alkali. F. S. I(. Cocaine. By A. EIR’HOXN (Eev. 21 3029-3044) .-Cocay?benzoyl- hydyoxyacetic acid C5NHiMe.CBz(OH)-COOH is obtained when a 3 per cent. solution of potassium permangaiiate (230 c.c.) is gradually added with consta1,t stirring to an aqueous (1 litre of TT ater) solution of benzoylecgonine ( e 5 grams) and sodium carbonate. The excess of potassium permanpinate is reduced with alcohol in the cold the Gltcred solutioii c a ~ e f u l l ~ acidified with h) drochloric acidORGANIC CHEMISTRY. 169 and evaporated ; the crystalline residue is extracted with and recrjs- talli~ed from alcohol and the resulting hydrochloride decomposed by boiling with ammonia.The acid which separates from the ammoni- ncal solution crystallisa from alcohol or hot water in large prisms melts a t 230" with decomposition and yields benzoic acid and cocayl- hydroxyacetic acid (see below) when heated with concentrated hydro- chloric acid. The hydrochloride CI5Hl7N04,HC1 crystallises from zdcohol in plates with 2 mols. H20 and melts at 217-218". The I/,umchioride C15H17N04,HAuC14 crystallises from dilute hydrochlorio :icid in yellow needles melting at 228" with decomposition. The ylatilzochloride C,5H17N04,H2PtC16 separates from water in jellowish- red nodular crystals containing water and melting a t 233'.The inethyl salt prepared by passing hydrogen chloride into a methyl :ilcohol solution of the acid was obtained in an oily condition; it is readily soluble in water and the solution in hydrochloric acid yields an aurochloride CI6Hl9NO4,HAuCI4 which crystallises in long needles melts a t 181-182" and is sparingly soluble in water. The ethyZ Ealt prepared in like manner is also an oil ; the aurochloride separates from acidified alcohol in yellow crystals melts a t 160.5" and is very sparingly soluble in water. Cocay Zhydroxyacetic acid C5NH7Me*CH( OH)*COOH. is formed in the preparation of the benzoyl-derivative when the oxidation product is evaporated in an acid solution. It can be obtained by gradually adding a 3 per cent. solution of potassium permanganate (900 c.c.) to an aqueous (If litres of water) solution of ecgonine hydrochloride (6 grams) and sodium carhonate.The h y d r o c l h i d e C8HI3NO3,HCl + H,O is isolated as described above. The free base is obtained in the pure state by decomposing the aurochloride with hydrogen sulphide evaporating the filtrate recrystallising the residue from a mixture of methyl alcohol and ether and decomposing an aqueous solution of the resulting hydrochloride with silver oxide. It separates in long needles or in thick prisms when ether is added to am aqueous methyl or ethyl alcohol solution and melts a t 233". The aurochloride CeHl,N03,HAuC14 crystallises from dilute hydrochloric acid in yellow needles containing 2 mols. H,O and melts a t 211". It crystallises from alcohol in short thick well-defined prisms containing alcohol.Anhydroecgonine can be prepared by heating cocai'ne for four hours a t 140" with glacial acetic acid saturated with hjdrochloric acid. When anhydroecgonine is oxidised with dilute potassium permamga- nate a s described above small quantities of ecgonine or cocayl- hydroxyacetic acid are formed according to the conditions of the experiment. A hydrocarbon ammoniiim chloride methyl chloride very small quantities of a secondary base and resinous products are formed when anhydroecgonine hydrochloride is heated at 230" for a long time with glacial acetic acid saturated at 0" with hydrogen chloride. When anhydroecgonine is heated with water a t 150° i t is partially decomposed into an acid and methylamine but all attempts to prepare a simple pyridine-derivative from the base were uusuc- cessful.VOL. LVI. rt170 ABSTRACTS OF CHEMICAL PAPERS. Cocaine methiodide C1,Hz1NO4,Me1 prepared by heating cocaine (1 mol.) with methyl iodide (1 mol.) a t loo" crystallises from absolute alcohol in shining plates melts a t 164" and is sparingly soluble in alcohol . Cocazne rnefhochloride C17H21NOJ,MeCl prepared by treating &he preceding compound with silver chloride crystallises from a mixture of alcohol and ether in small needles or plates melts a t 152*5" and is very readily soluble in water. MethylanhydroPc.go.niiLe methiodide CloH,,NO,,MeI is formed to- gether with benzoic acid when an aqueous solution of cocajine methiodide is heated a t 100". It crystallises from alcohol in slender yellowish needles or in well-defiued prisms and melts a t 195-196'.When cocajine methiodide is heated a t 140" with glacial acttic acid previously saturated with hydrogen chloride benzoic acid and a compound containing both iodine and chlorine are produced. When the last-named sulmhnce is treated with silver oxide a crjstalline hygroscopic base is obtained. Anh!ydroecgorzine methiodide ClnHl6NO2I is formed when an aqueous solution of the base just described is treated with hydriodic acid. It crystallises from alcohol or water in long prisms containing 1 mol. H,O and melts a t 207-208'. The constitution of coca'ine is probably An Acid from Cod-liver Oil. By A. GAUTIER and L. MOURGUES (Compt. rend. 107 740-743).-Cod-liver oil contains an acid in the form of an unstable compound resembling the lecithins which decom- poses in contact with acids or alkalis and yields glycerol phosphoric acid and the new complex acid.Lecithins themselves are present in the oil and add to its value by presenting phosphorus in a readily assimilable form. The oil is systematically extiacted with alcohol of 35 per cent. containing 3 per cent. of hydrochloric acid and the solution is satu- rated with potassium carbonate and distilled in a vacuum at 45". The residue is acidified heated for a moment a t loo" and extracted with alcohol a t 85". The latter dissolves the acid,' which separates as a viscid colourless substance on cooling o r on adding water. The crude product is dissolved in potash neutralised witli nitric acid and lead acetate added so long as the precipitate is not discoloured.The lead precipiiate is washed with water decomposed by hydrogen sul- phide and the solution filtered whilst hot. The lead sulphide is washed with hot alcohol and the washings and the original filtrate are evaporated in a vacuum. The new acid m o r r h u i c acid crystal- lised in soft yellowish square plates of the composition C,Hl,N03 which differs from tyrosine by Hz only. Morrhuic acid has a diRagreeable odour recalling that of kelp ; when freshly precipitated it is oily and viscid bat i t gradually solidifies. It dissolves in hot water but separates on cooling and IS soluble in alcohol but only slightly soluble in ether. It reddens litmus decom- poses carbonates and forms crystallisable salts with the alkalis ; itsORGANIC CHEJIISTRY.lil solutions give precipitates with lead and silver but not with copper salts. Morrhuic acid also combines with acids and forms a crystal- line hydrochlorid<i. which is decomposed by water morrhuic acid separating in the form of an emulsion ; the platinochloride is soluble and crptallises i n very small prisms; the aurochloride forms au amorphous precipitate which readily alters when heated. When distilled with lime morrhuic acid yields a base which gives with methyl iodide and potash the reaction characteristic of the pyridines. When oxidised with potassium permangnnate it yields a monobasic pyridinecarboxylic acid which crystallises in prisms and rhomboidal lamell= and forms a platinochloride and an aurocbloride. The silver salt of morrhuic acid contains 2 atoms of the metal and hence i t is bibasic.The fact that it gives no precipitate with copper acetate indicates that the carboxyl is not in direct union with the pyridine-ring and it probably has the constitution This formula explains the ready reduction of the silver salt even in the cold. De Jongh’s gaduirbe is probably identical with morrhuic acid. C. H. B. Action of Phosphorus Qxychloride on Cholic Acid. By R. CAMPANI (Onzzettu 18 88-89).-The cholic acid employed was prepared from ox-bile by boiling it with dilute hydrochloric acid for 24 hours and then isolating the acid in the usual way. The phosphorus oxychloride (12 grams) is added drop by drop to the cholic acid (5 grams) in fine powder ; a powerful reaction takes place and as soon as it has subsided the product is thoroughly washed with boiling water and allowed to dry a t the ordinary tem- perature.It is a greenish-yellow powder very sparingly soluble in alcohol but easily in ether ; this on evaporation leaves it as a brown amorphous vitreous residue. On analysis it gave numbers corre- sponding with the formula C24HJ603. It is insoluble in aqueous alka- line solutions but ou long boiling with alcoholic potash it dissolves and is reconverted into cholic acid which is precipitated from the rolution on adding hydrochloric acid. The compound therefore is the anhydride of cholic acid. C. E. G. Gelatinous State of Albuminoi’d Substances. By V. MICHAI- LOFF ( J . Russ. Chem. Xoo. 1887 19 666-690; 1888 20 35-72 159-179 274-360 380-388) .-After giving the history of this and similar subjects (collo’idal matters in general) the author shows the conditions under which white of egg from different sources exists in various solutions precipitates and gelatinous coagulates and in coagulates obtained by heat how these different niodifications are formed and transformsd and describes a t some length their properties (chemical and physical) especially those of Tarchanoff’s *‘ tata-albumin ” and its behaviour towards solutions of different salts a t different temperatures as well as the results obtained on dialysis 12 2172 ABSTRACTS OF UHEMICAL PAPERS.(see Abstr. 1887 856). The mutual actions of different kinds of albuminold substances are also studied and it is shown that albumins are acid and globulins basic compounds. Gelatinisation of albumin in the first phase is dne to hydration; in its subsequent phases to dehydration which is more or less complete according to the condi- tions.B. B.I1 2 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Action of Zinc Ethide on Nitroethane. Ry I. BEVAD (J. RUSS.Chem. Soc. 1888 20 125-135). -The object of this investigationwas t,n rlwirle whether " nitroethane " is really a ~ ~ ~ ~ Q - C O L D ~ Q U D ~(V. Meper) a hydroxylamine-derivative CH,.CO.NH,O (Kissel) oran isonitroso-derivative HO.CH,*CH:N*OH (Alexheff). When zinc:ethide ether and nitroethane are mixed i n an atmosphere of carbonicanhydride the mixture becomes red and after some time crystalsare formed which disappear again in about a fortnight.On decompos-ing the product of reaction with water distilling and treating thedistillate with hydrochloric acid a solution is obtained which onevaporation gives crystals of a very hygroscopic salt. On decompos-ing this with alkalis n colourless oil of sp. gr. 0.8935 a t 0" is obtsined,which proTed to be triethylhydrox2/laminc! Et,NO. It is somewhatsoluble in water and soluble in all proportions in ether alcohol andbenzene. Its compounds with hydrochloric snlphuric and acetic acidsare extremely hygroscopic. The oxalate (Et2NO),,H,C,04 was obtainedby mixing ethereal solutions of its constituents. Triethylhydroxyl-amine and its salts have powerful reducing properties as shown bytheir behaviour with silver cupric and mercuric salts.The originalethereal distillate contains in addition some unchanged nitroethaneORGANlC CHEMISTRY. 113but no other product is formed if the substances employed are inmolecular proportion.The author concludes that nitroethane is a true nitro-compound.Ita reaction with zinc ethide takes place in different stages. At firstcrystals are formed of the formula 2EtN0 + 7ZnEt2 (as shown byzinc determinations). When these crystals disappear the compoundEt3N(OZnEt)2 is formed; and this reacts with water as follows:Et,N(OZn*C,H,) + 4H20 = Et,N(OH) + 2C2H6 + 2Zn(OH),. TheEt,N(OH) being unstable however is converted into the free basewith elimination of water.Bitromethane treated in the same way with zinc ethide givesmethyldiethylhydroxylamine. When zinc ethide is added to bromo-nitroethane a violent reaction takes place and when this is over if theproduct is distilied with water secondary nitrobutane CH MeEt-KO,,boiling a t 138" is formed.In this way from lower nitro-compoundsthose of higher homologues may be formed by synthesis. Nitro-benzene with zinc ethide gives no higher nitro-compound reductiontaking place with formation of aniline. If nitroethane were acet-hydroxamic acid it should be formed from hydroxylamine hydro-chloride and acetic anhydride ; the experiments however made bythe author with this object gave a negative result.Action of Chlorine on Isopropylethylene. By I. KONDAKOFF(J. Russ. Chem. See. 1888 20 141-148).-Isopropyiethylene(b. p. 21-22"> was brought in contact with chlorine by passing thegas into the vessel by means of a tube terminating at some distancefrom the surface of the liquid in order to prevent the action frombeing too violent and to keep the course of the reaction as uriiformas possible from the beginning to the end.When no more drops wereformed on the sides of the vessel the process was stopped. Varioustemperatures from -20" to + 16" were employed but in all cases theproducts were the same. After washing and drying the product aliquid was obtained which when submitted to fractional distillation,boiled chiefly between 143" and 145". A small part boiling a t 100-143"was proved to be a monochloride. The principal portion boiling at143-145" was an additive product of isopropylethylene C,H,,CIL.I t s sp.gr. at 0" is 1.1106 and 1.0923 at 17.5". m'hen heated in sealedtubes with fused potassium acetate and acetic acid a t 120" it isconverted into a glycol ; this boils a t 91%-219" ; the quantity ob-tained however was so small that no experiments could be made toprove that it was isopropylethylene glycol. Isopropylethylene whenacted on by alcoholic potash yields a monochloro-derivative boilingbetween 91" and 96". These experiments show that isopropyetbyleneand chlorine yield additive products only as pointed out by Lwoff.B. B.B. B.Polymeride of Methyl Cyanide. By R. HOLTZWART (J. pr.Qhem. [S] 38 343-344).-When an ethereal solution of methylcyanide is acted on by sodium a white powder is formed and methanej evolved ; when treated with water the powder yields a yellow oilwhich can be crystallised in white needles from a mixture of ethe114 ABSTRACTS OF CHEMICAL PAPERS,and light petroleum.A better yield is obtained by digesting thepowder with aqueous ether. The crystals melt at 52-58" aresoluble in ether dcohol benzene and chloroform sparingly so inwater and light petroleum. The molecular formula is C4H6NL.When digested with water ammonia is evolved and a crystallineprecipitate sparingly soluble in cold wat,er is formed having thecomposition C8H8N20 ; and when treated with acetic chloride inethereal solution a yellow amorphous precipitate of the composition2C,H6N,,CO&feCl separates ; this is decomposed by m-ater forming awhite crystalline powder of the formula CsHgN3.The investigationis still in progress.Polymeride of Ethyl Cyanide. By E. v. MEYER (J. pr. Chem. [ 21,38 336-343).-The white powder obtained by the action of sodiumon ethyl cyanide (Abstr. 1888 802) has been proved to be formedas follows :-(1) Na + 2EtCN = NaCN + C2H6 + C,H,Na.CN ;(2) C,H,Na.CN + EtCN = CGH9NaN2. The oil which it yields ontreatment with water cryst allises in tables which melt at 47-48',boil at 257-258" (uncorr.) are little soluble in cold water decomposedby warm water and soluble in ether and alcohol; the molecularformula C,H,,N has been obtained both by Raoult's method and bythe vapour-density determination ; when heated at 330-340" forseveral hours it is converted into ethyl cyanide. Hydrochloric aciddecomposes it half the nitrogen appearing as ammonium chloride andhalf as an oil soluble in ether; the ethereal solution is shaken withsodium hydroxide dried orei- lime and the pure oil precipitated byadding water.This oil has the composition C6HgN0 and is recon-verted into the original substance when heated with strong ammonia.It would thiis appear that the polymeride is a-imidoprojpion2/lethylcyanide NH:CEt*CHiVe*CN and the oil a-propionylethyl cyanide orcyanodiethyl ketone COEt*CHMe*CN. Tbe former is convertedihto ammonia carbonic anhydride and diethyl ketone when heatedwith strong hydrochloric acid at 150° and the latter into propionicacid and ammonia when heated with aqueous Dotash. The imido-A. G. B.compound is converted into propylamine by reduction.A. G.B.Ammeline. By A. SMOLKA and A. FRIEDREICH (Monatsh. 9,701-707) .-When dicyanodiamide (1.5 grams) and carbamide (1.08 grams)are heated at 170-180" for 2+ hours much ammonia is set free andon treating the product with water an inqoluble white residue remains,from which ammeline C,H,N,O (yield 1.57 grams) may be obtainedby dissolving it in alkali and reprecipitating with acetic acid re-peatedly; finally recrystallising it fi-om a hot aqueous solution ofpotash.Ammeline can also be prepared by heating dicyanodinmide withcyanic or cyanuric acid. It may therefore be represented by one ofthe two formulse NiC*NH*C(NH)*NH*CO-NH orC0:N.C (N H)*NH*C (NH)*NH,.The authors consider that the first of these most probably representsthe constitution of the compound since ammeline unlike biguanideORGANIC CHEMISTRY.115derivatives of which the second formula represents a member is nota strong base and does not give coloured compounds with salts ofcobalt and copper.By R. NASINI andA. SCALA (Gazzetta 18 62-72).-The authors have been occupiedfor some time with the examination of organic sulphur compounds,especially with the object of proving the tetravdency of sulphnr andthe appearance of Klinger and Maassen's work (Abstr. 1888 357),whose results are diametrically opposed t o theirs compels them topublish a portion of their researches. Although various sulphurcompounds containing a1 kyl radicles have been obtained of the formSM,A and SM,M,A unfortunately their vapour-density cannot bedetermined and it remains uncertain therefore whether the fourmonad radicles are united to the sulphur or whether the compoundsare molecular compounds.Klinger and Maassen in repeating Kriiger's work found that thesulphine containing one methyl- and two ethyl-groups was the same,whether it was prepared by the action of methyl iodide on ethylsulphide or of ethyl iodide on ethyl methyl sulphide that is theydenied Kriiger's statement that two isomeric compounds of theformula E t,MeS existed capable of yielding distinct platinochloridescrjstallising in different forms.Nasini and Scala state that theyhave prepared the iodides of the sulphine according to Kriiger'sdirections and converted them into the corresponding platino-chlorides one of which crystallises in the cubic system whilst theother is monoclinic.E t h y lrn et hy 1 e thy lsu lp hin e p latinoc hlorid e (E tM eE t S Cl),,P t C14 meltsat 211-212" and fcrms monoclinic crystals,G.T. M.Sulphines and the Valency of Sulphur.a b c = 1.15113 1 0.794745 ; p = 49" 17' 56".Forms observed f l l O ) ( i l l ) (OOl) (010) ; combinations (110) (111)(001) arid (llO)(ill) (001)(010).Diet h y lm eth ylsulishine pl atinoch loride ( EtpLMe S Cl) 2 Pt C14 melts at205" and crystallises in the monometric or cubic system ; combha-tions (100) (1 11). These crystals when auperficially observed mayeasily be taken for monoclinic owing to the development of one face,but their optical properties prove that they belong to the monometricsystem as when examined by polarised light there are no signs ofdouble refraction.This leaves unsettled the question as to whethersulphur is tetravalent or not. C. E. G.Trimethylethyleneglycol from Methyl Isopropenyl Carbinol.By I. KONDAKOFF (J. Busr. Chern. SOC. 1888 20 32-34).-1n a,former paper the author has shown that methyl isopropenyl car-binol when heated with dilute sulpburic acid (1 per cent. H,SO,),becomes converted into trimethylethylene glycol whilst hydrocbloricacid is without action at the ordinary temperature but gives rise toproducts of condensation at a higher temperature. The author nowfinds that chlorine-derivatives of trimethylethylene yield trimethyl116 ABSTRACTS OF CHEMICAL PAPERS.ethylene glycol if left in contact with water in a closed flask a t theordinary temperature for several months.B. B.Combination of Benzaldehyde with Polyhydric Alcohols.By MAQCENNE ( Compt. rend. 107 658-659).-The dibenzoic acetalof perseitol (perseiie) previously described (this vol. p. 32) wasmade with alcohol of 85" to go" without addition of zinc chloride. T tis assumed to be an acetal becausa it resembles the product obtainedby Mennier by the action of benzaldehyde on mannitol and Friedelhas pointed out that in all probability this is an acetal.When a polyhydric alcohol containing an odd number of hydroxyl-groups is converted into an acetal one of the hydroxyl-groups is leftunattacked and since the difference in composition between theacetals of two successive homolopes can be detected by analysis theconversion into acetals affords a convenient method of determiningthe number of hydroxyl-groups in a polyhydric alcohol.I2C. H. B.Constitution of Sorbinose. By H. KILIANI and C. SCHEIBLER(Be?.. 21 3276-3281).-Sorbinose behaves towards bromine andwater similarly to levulose and remains practically unchanged after aweek it contains therefore no aldehyde-group. When heated withnitric acid (sp. gr. = 139 2 parts) for 40 hours at 35O trihydroxy-glutaric acid COOHfCH(OH)]3*COOH (this vol. p. 32) is formed.Potassium trihydroxyglutarate crystallises in monoclinic plates ;a b c = 1.4641 1 0.7094; p = 101" 3'.When sorbinose is reduced with hydriodic acid and amorphoiisphosphorus it is converted almost quantitatively into hexyl iodide.Sorbinose has probably the constitutionOH.CH,.[ C H (OK)],*CO.C E,*OH.N. H. M.Changes suffered by Starch when Dissolved in HotGlycerol. By K. ZULKOWSKI (Ohem. Centr. 1888 1060 from B e y .Oestwr. Gess. Chcm. Ind. 10 2-4).-Starch when heated in glycerolat 200° produces a solution which gives a blue coloration with iodincat first but which gradually changes to red. Addition of alcohol atthis point precipitates erythrodextrin. If the heating is continuedup to 210c until the red coloration gives place to a brown one,glcohol precipitates achroodextrin. Other compounds are formedbesides the t w o above named and were separated by precipitationwith barium hydroxide &c. but were not further characterised.J.W. L.Derivatives of Allylamine. By C. PAAL (Rer. 21 3190-3196 ;compare Gabriel Abstr. 1888 1267) .-Bromallylamine CJH4Br.NH,,1s prepared b,r adding dibromopropylamine hydrochloride to excess ofalcoholic potash diluting the product with water and distilling withstearn. It is a colourless mobile very unstable oil boils a t 125" withpartial decomposition and mixes i n all proportions with all ordinarysolvents. When mixed with potassium carbonate it is decomposeORGANIC CHEMISTRY. 117with separation of potassium bromide. When boiled for a long timewith alcoholic potash i t seems to be for the greater part transformedinto a hydroxy-base but when the temperature is raised to 120-130",it is completely decomposed.C3H4Br.NH.C3H1.NH2,HBr,is formed when bromallylamine is kept for a long time ; the same saltremains when bromallylamine is distilled.Silver nitrate produces awhite amorphous and mercuric chloride a white crystalline precipi-tate in an aqueous solution of free bromallylamine. The hytlroch Zoride,C3H4Bi*-NH2,HCl crystallises in large needles or prisms melts at177-180" and is readily soluble in water or hot alcohol. Theplntinochloride (C,,H,Br.NH,),,H,PtCl crystallises in yellow plates,and is readily soluble in hot water but almost insoluble in absolutealcohol. The awochloride C3H1Br*NHZ,HAuCl4 crystallises in sniall,yellow needles and decomposes when kept for some time in aqueoussolution. The hydrobromide C3H4Br*NH,,HBr crystallises in large,colourless quadratic prisms melts a t 223-224" and is more sparinglysoluble in alcohol and water than the hydrochloride.The oxaZatP:C3H,Br.NH,,C,H,04 crystallises in colourless plates melts a t 136-138",and i s readily soluble in water but insoluble in alcohol and ether.TribrornopropylamirLe hydrochloride C3H4Br3NH,,HC1 prepared byadding bromine (1 mol.) to a well-cooled concentrated aqueous solu-tion of bromallylamine hydrochloride crystallises from absolutealcoliol in colourless needles. The free base is a heavy yellow veryunstable oil with a pungent smell.The aurochloride C3E1Br3*NH2,HAuCl4 crystallises from water inwhich it is moderately soluble in golden-yellow plates melting a t170". The PZatinochZoride ( C,H,Br3*NH,),,H,PtC16 crystallises fromhot water in orange plates and is decomposed when heated at 245".Isob ut y l d i b rornoprop y laniine hydrobromide C4Hg*NH*C3H,Br,HBr,prepared by adding bromine (1 mol.) to a well-cooled glacial aceticacid solution of isobutylallylamine crystallises from hot water inwhich it is readily soluble in slender needles and is sparingly solublein alcohol.The free base is a heavy almost colourless very unstableoil with a feeble basic smell. When auric chloride is added to anaquecus solution of the hydrobromide the aurochZoride separates asa yellow oil and then solidifies.BzLty Zdibronaopro~y Zamine hydrobromide C4H,*NH-C3H5Br2,HBr canbe prepared by treating bntylbromallylamine with excess of dilutehydrobromic acid. It. crystallises in large concentrically groupedneedles and is readily soluble in water and hot alcohol.The m r o -chloride separates from an aqueous solutioii of the hydrobromide inflat needles when auric chloride is added to an aqueous solution of thehydrobromide.Buty ZbromaZZy Zamine C4HgNH*C3H4Br can be prepared by boilingthe isobutyldibromo-derivative with dilute alcohol for a long time,adding alkali and distilling with steam. It can also be obtained bymixing the hydrobromide with excess of alcoholic potash in the cold,keeping the mixture for some time diluting with water and addingpotassium carbonate until the alcoholic solution of the base separatesA crystalline salt probabl118 ABS'I'HAGTS OF CHEMICAL PAPERS.a t the surface of the aqueous solution; the solution of the base isdried over potassium carbonate poured into an alcoholic solution ofoxalic acid and the precipitated salt decomposed with alkali.It is ayellowish oil with a camphor-like odoar ; it cannot be obtained in thepure state as it is partially decomposed when distilled. The oxalnte,C7HI4BrN,CZH2O4 cr,ystallises in colourless needles melts at 230-231',and is moderately soluble in water.Isoam y ldibromopropy 1 am ine hydrobromide C5Rl,*NH.C,H5Br2,HBr,prepared by treating isoamylallylamine with bromine in glacial aceticacid solution and then adding concentrated hydrobromic acid,crystallises in plates melts at 230-231" and is sparingly soluble inalcohol and cold water. The free base resembles the correspondingbutyl base. The platinochloride is a reddish-yellow oil.Amy l d i bromoprop y lamine hydro b romide prepared by treating am pl-allylamine as described above crystallises in needles melts at 150°,and is moderately soluble in cold water and alcohol.Isoamylbronzalll! lamiite C5Hll*NHG3H4Br prepared by treating iso-amyldibromopropylamine hydrobromide w i t h alcoholic potash or hyboiling the free base with dilute alcohol is an oil ; it is insoluble inwater and boils a t about 150" with partial decomposition.F.S. K.Synthesis of Hydroxypropylenediisoamylarnine. By E. LOU~SE( A n n . Ch im. P h ys. 13 433-442 ) .- Hyd~ox!pi*op y 1 e nediisoamy lumine,C,,H,,NO is best prepared by heating propplenechlorhydrin (1 mol.)and diisoamylamine (at least 16 mols.) a t 100" in a closed vessel for30 hours.The product is mixed with concentrated potash to decom-pose the diisoamylamine hydrochloride which is formed in the reaction,the mixture is again heated for 10 hours and the oil which separatesis dried over potassium carbonate and fractionated. The yield is70 per cent. of the theoretical quantity but it is impossible to get ridof the whole of the diisoamylamine by fractional distillation. Thehydroxypropylene-derivative is obtained in the pure state by agitatingthe fractionated liquid with a small quantity of dilute warm hydro-chloric acid and decanting the supernatant oil. It is a colourlessoil with a somewhat disagreeable smell and boils a t 242-2+b0. Itis sparingly soluble in water but readily in alcohol ether and othersolvents of the fatty series.All the simple salts with the exceptionof the picrate which is sparingly soluble are syrupy liquids and veryreadily soluble in water. The platinochloride ( C,,H,,NO)z,H2PtCl,,separates from acidified alcohol in orange crystals but the auro-chloride is a yellow sparingly soluble oil.Propy lenediisoamylamine benzoate CIsH2,N*OBz is prepared bygradually adding a slight excess of benzoic chloride to a well-cooled,dry ethereal solution of the alcohol and after evaporating the ether,heating the mixture a t 100" for six hours in a sealed tube. Theproduct is treated with boiling water the cold mixture shaken withether to remove benzoic acid and the salt separated by addingpotassium cat bonnte. It is a colourless oil readily soluble in alcohol,ether chloroform &c.but insoluble in water. It is hydrolysed whenboiled with potash or when treated with strong acids and is decom-posed when distilled. This salt still has basic properties ; its oxalateORGANIC CHEMISTRY. I1 9C,,H3,NO2,C2H,O4 crystallises from hot water or alcohol in slender,colourless needles and is readily soluble in acetone and chloroform,but insoluble in ether. Most of its other salts do not crystallise andare very readily soluble excepting the platinochloride and the auro-chloride which are only sparingly soluble.Propy lenediiaoamylamine acetate prepared in like manner is acolourless oil readily soluble in alcohol ether &c. b u t only sparinglyin water. Its oxalate crystallises in needles and is very readilysoluble in alcohol and chloroform but only moderately in water andsparingly in ether.Its other salts are very readily soluble in water,and do not crystallise. F. S. K.Glyoxalbutyline and Glyoxalisobutyline. By J. RIXGER(Monatsh. 9 603-612 ; compare Radzissewski Abstr. 1883 308,728 1086 ; 1884 986) .-Glyoxalhufyline prepared according to thedirections given by Radziszewski from glyoxal ammonia and normalbotaldehyde is a viscid hygroscopic oil having a sp. gr. of 1.0125at 20" and boiling under a pressure of 738 mm. a t 266-268". It isfairly soluble in water and when an aqueous solution is treated withoxalic acid the compound (C6HloNz)z,CzH,04 + 2H20 is formed ; thiscrystallises in rhombic plates or long needles and melts at 159-161".The anhydrous oxalate ( C&I,,N2),,C,HzOa is precipitated as an amor-phous white powder on mixing alcoholic solutions of the acid andbase.It partly sublimes a t 170° and melts with decomposition a t290-195". The platinochloride 2C,HloN2,H~PtC16 crystallises inorange-red prisms and on treatment with iodoparaffins gives thefollowing bases :-Omdviethylbutyline C6HgMeN2 is a colourless viscid liquid havinga sp. gr. of 0.9850 at 19.8" and boils at 214-216" under a pressorcof 722 mm. It dissolves readily in cold water alcohol ether andchloroforrn. The platinochloride 2C,H,MeNz,HzPtC;16 crystallises inorange-red rhonibic prisms.Oaalethylbutyline C6H9EtNz has a sp. gr. of 0.9593 a t 16.5" andboils at 218-222" under a pressure of 736 mm.The platinochlorideis a yellow amorphous powder.Oxalpropylbutyline C6HgPrN2 is a liquid of sp. gr. 0.9393 at 18.9".It boils at 226-228" under 8 pressure of 726 mm. and forms aplatinochloride insoluble in alcohol and ether but readily s o h ble inhot water.OxalbzLtylbutyline C4Hg.C6HgN2 has a sp. gr. of 0.9379 at 18.9",and boils a t 242-245" under a pressure of 728 mm. It forms doublesalts with the chlorides of zinc cadmium. and platinum and onoxidation with hydrogen peroxide gives butyloaamide CzH,0LN2*C4H9,crystallising in lustrous needles which sublime at 130" and melt atOxa2i.sobutylbutylie has a sp. gr. of 0.9403 at 13*4" and boils atThe platinochloride formsOxalisoamylbutylilze C5Hll*CBH9N2 has a sp. gr. of 0.9197 a t 18*9",The platino-197-198".231-233" under a pressure of 736 mm.orange-yellow needles soluble in alcohol.and boils at 250-252" under a pressure of 784 mm.chloride crystallises in rhombic needles1-20 ABSTUCTS OF CHEMICAL eAems.GlyoxaZisobuty line prepared from isobutnlde hyde ammonia andglyoxal is a crystalline solid melting at 125-126" and boiling a t256-260'.It readily dissolves in hot water alcohol chloroform,and ether and forms the salts C6HJ!Tq,HCl melting a t 205",C6H,,N,,HBr melting a t 22Z0 and C,H,,N,,C,H,O melting at194-195". By treatment with iodoparaffins it furnishes the follow-ing bases:-Oxalmethyl~sob~tz~lilzP C6H,MeN ; this is a colourless viscid oil ofsp. gr. 0.9576 at 16.6" and boils a t 205-206". The platinochloride crys-tallises from water in orange-red plates the compound CsH,MeN2,MeIin colourless rhombic prisms melting a t 245-246".Oaalpropylisobufyline C6H9PrN2 which has a sp.gr. of 0.9299 andboils at 225-227'. The platinochloride crystallises in orange-redneedles.Oxalisoamylisob~~tyline; this has a sp. gr. of 0.9281 a t 17*3" andboils at 246-248" under a pressure of 738 mm. The platinochlorideis scarcely soluble in alcohol but dissolves readily in water.All the oxalines described above turn yellow on exposure to the air,are miscible with alcohol ether and chloroform and have charac-teristic unpleasant odours. G. T. M.Action of Sulphur on Paraisobutaldehyde. By G. A. BARBAGL14(Gazzettn 18 85-88).-Unlike isobutaldehyde sulphur has no actionon the paraldehyde a t 150" but when heated with it for a long time(100 hours or more) at 180" it becomes reddish-brown and on openingthe tube abundance of gas escapes containing much hydrogen sul-phide.The liquid has an acid reaction and if left for a time sepa-rates into two layers. On submitting it to distillation a liquid i qobtained which by means of fractional distillation c m be separatedinto three portions ; the first distilling between 70" and go" was foundon analysis to be isothiobutaldehyde ; the second distilling between90" and 140" has not yet been examined ; whilst the third 140-160",is isobutyric acid. The reaction is probably in the first place-4CHMe2GOH + S2 = 2CHMe2*CSH + 2CHMe2.COOH,but a t the high temperature necessary for the reaction the excess ofsulphur acts on the isothiobutaldehyde converting i t into polgsulphide,with evolution of hydrogen sulphide-CH3 CH3>HC*CHS + S2 = S<gz>HC*CHS + H,S.In all probability this product exists in the intermediate portion ofthe distillate.C. E. G.Action of Ammonia on Methylethylacraldehyde. By E. HOPPE(Monatsh. 9 634-657 ; compare Waage Abser. 1884 172).-Onpassing ammonia into an ethereal solation of methylethylacraldehyde a tO" a substance separates in white flakes but is of so unstable a naturethat it is impossible to isolate it. When heated in sealed tubes at 100"with excess of alcoholic ammonia methylethylacraldehpde yields ORGANIC CHEMISTRY. 121viscid liquid which has a bitter taste and an odour resembling parroline.No definite compound can be isolated from it but its solution inhydrochloric acid gives white or yellow precipitates with most of thesalts of the heavy metals.When heated in sealed tubes at 200" for12 hours the substoance decomposes and on opening the tube muchammonia is evolved. After several heatings in sealed tubes no moreammonia is produced and the following bases can be isolated fromthe residue :-(1) Picoline ; (2) parvoliiie identical with that G b -tained by Waage and yielding on oxidation a-p-pyridinedicarboxylicacid; ( 3 ) a new base C12H19N which forms a clear mobile liquidhaving a pale blue fluorescence a bitter taste and a smell resembliugparvoline but less intense. It dissolves readily in alcohol and ether,hut is only slightly soluble in water.The platinochloride crystallisesin orange-red monoclinic prisms is very soluble in alcohol but onlyslightly so in water. G. T. M.Action of Sulphurous Acid on Methylethylacraldehyde. ByE. LUDVIG (Monmtsh. 9 658-674).-The author has further investi-gated the compound obtained by Lieben and Zeisel from sodiumhydrogen sulphite and methylethylacraldehyde (Abstr. 1883 570),and finds that it is most conveniently prepared by the direct additionof sulphurous acid to the unsaturated aldehyde. 10 grams of thealdehyde and 30 C.C. of water were introduced into a tube andsaturated with sulphurous acid at 0"; after sealing the tube washeated at 80" for four hours and the contents then neutralised withbarium carbonate. The filtered solution on concentration in a vacuumat 30" gave barium hTdroxyhexanedisulphonate C6H1,0 (SO,) Ha +'LH,O.The salt dissolves readily in water is only slightly soluble inalcohol and is very unstable. On heating with baryta-water methyl-ethylacraldehyde and barium snlphite are formed. If the contents ofthe tube after heating are diluted with an equal volume of water,and three-quarters of the liquid distilled off the residue on neutrali-sation with barium carbonate and concentration in a vacuum oversnlphuric acid gives the barium salt of capraldehydesulphonic acid,( C,Hl1O*SO3),Ra as an amorphous mass. Capraldehydesulphonic acidcan also be prepared by allowing aqueous sulphurous acid to reactwith niethylethylacraldehyde at ordinary temperatures for severalclays when all the oil disappears. From the solution after saturationwith barium carbonate and oxidation with bromine-water bariumsulphocaproate C6HloS05Ba crystalhing in hexagonal plates maybe isolated.Si~Zp7~ocaproic acid may also be prepared from bariumhydroxyhexanedisulphonate. The silver salt C6HloS0,Ag crystal-liees i n small plates the calcium salt C6H,,,So5Ca + l+H,O inscales. On reduction with sodium amalgam in solutions containingfree sulphuric acid both hydroxyhexanedisulphonic acid and cap'.aldehydesulphonic acid yield a siilphonic acid of hexyl alcohol thesodium salt of which C6Hl3So4Na) obtained in a slightly impurecondition forms an amorphous hSgroscopic mass and yields ondistillation with lime a mixture of hexyl and hexenyl alcohols boilingat 149*6-151*6".G. T. &I.VOL. LVI. 122 ABSTRACTS OF CHEBIICAL PAPERS.Action of Potassium Cyanide on Ethyl a-Bromopropionate.Freparation of the Isomeric Symmetrical Dime thylsuccinicAcids. By N. ZELINSKY (Ber. 21 3160-3172).-Ethyl a-cyano-propionate and ethyl dimethylsuccinate are obtained when ethyla-bromopropionate (250 grams) is boiled for about six hours withfinely divided potassium cyanide (96 grams) in alcoholic solution(130 grams) the whole beinq constantly shaken. The yield is greaterwhen the mixture is heated by a stream of hot air. The product iswashed with water dried and fractionated. A small quantity of acrystalline substance is also formed i% this reaction.Efhyl a-cyclnopropionate CN.CHMe*COOEt is a colourless liquid,boils at 197-198' is not miscible with water and yields a veryhygroscopic sodium-derivat ive.E thy1 dimethyls~iccinate (compare Scherks Abstr.1882 38) canbe prepared by gradually adding ethyl a-bromopropionate (56 grams)to a mixture of sodium (0.72 gram) and ethyl a-cyanopropionate(4 grams) in alcoholic solution. It boils at 272-273" (compareScherks Zoc. c i t . ) and yields dimethylsuccinic acid melting at192" and the isomeric acid melting at 123-124" when heated for6-8 hours with hydrochloric acid (compare Otto and Beckurts,Abstr. 1885 753 ; Otto and Rossing Abstr. 1888 45 ; also Bischoffand Hjelt Abstr. 1888 1057). Both acids yield the same anhydridewhen distilled. The anhydride crystallises in small plates melting at87".When the anhydride is boiled for a short time with a smallauantitv of water. it is almost entirelv converted into the acid of 1 d "lower melting point but a small quantity of the isomeric acid isalso formed. F. S. I(.Solubility of the Silver Calcium and Barium Salts ofNormal Caproic and Diethylacetic Acids. By P. KEPPICH(Monatsh. 9 589-602 ; compare ibid. 6 565).-The solubilities ofthe different salts were determined by Raupenstrauch's method. Thoformula? deduced from these determinations are as follows :-Silver normal caproate.. . .Calcium normal capoate..Barium normal caproate . .Silver diethylacetate . . . . .Calcium diethylacetate . . .Barium diethylacetate is so intensely soluble in water that theS = 0.07768 + 0.0008268S +S = 2.727 - 0*01475(t - 0.7) +S = 9.47 - 0 08975 ( t - 0.S) +S = 0.402 + 0.000847 ( t - 0.7) +S = 30.119 - 0.2617 ( t - 0.7) +0 000031213t2.0.0002203 ( t - 0.7)'.0.0014983 ( t - 0.5)'0.000038 ( t - 0.7)20.001498 ( t - C.7)'.author did not succeed in obtaining any analytical results.G.T. M.Chlorine-derivatives of Ethyl Acetoacetate. By P. GENVRESSE(Corryt. rend. 107 687-689).-When chlarine is passed into ethyORGANIC CHEMISTRT. 123acetoacetate the temperature rises to 265" but afterwards falls andthe chief products are the di- and tri-chlorinated derivatives togetherwith small quantities of higher substitution products.When the dichloro-derivative is heated in sealed tubes with dilutehydrochloric acid it yields unsymmetrical dichloracetone water andalcohol and hence it has the constitution CHC1,.CO.CXL.COOEt.When treated with chlorine at l i O " it yields the tri-derivative,together with small quantities of the tetra- and penta-derivatives.The trichloro-derivative when heated with dilute hydrochloric acidin sealed tubes a t 170" yields trichloracetone CCl,*COMe alcohol andcarbonic anhydride so that its constitution is CCI,*CO-CH,.COOEt,and not CHCl,.C(OH):CClGOOEt as supposed by Mew-.Efhy Z tetrachZorcLcetoacetate boils with partial decomposition a t229-231" under ordinary pressure and with less decomposition a t153-157" under a pressure of 40 mm.It is colourless and heavierthan water; when heated with dilute hydrochloric acid underpressure it yields carbonic anhydride alcohol and unsymmetricaltetrachloracetone so that its constitution is CCI,*CO*CHCl-COOEt.Ethyl pentachloi*ncetoac~tate boils a t 240-244" under ordinarypressure or at 164-168" under a pressure of 35 mm.and is acolourless liquid heavier than water. When heated at 160" withdilute hydrochloric acid it yields carbonic anhydride alcohol aiidpentachloracetone so that its constitution is CC13*CO*CC1,.COOEt.If ethyl acetoacetate is subjected to the action of chlorine a t150" to 220" for 10 days derivatives containing 7 and 9 atoms ofchlorine are obtained. The former CC13*CO*CCl,~COOC,H3Clz is aqvupy almost colourless liquid which boils a t 270-272" with muchdecomposition under ordinary pressure or with slight decompositionat 220-225" under a pressure of 110 mm.The derivative with9 atoms of chlorine CC13.C0.CC1,*COOC,HC1 is a syrupy liquidwhich does not solidify a t -23" and boils at 225-230" under a,pressure of 40 inm.Methyl acetoacetate yields similar derivatives. C. EL. B.Dihydroxystearic Acid obtained by the Oxidation of OleicAcid with Potassium Permanganate in Alkaline Solution.By N. SPIRIDONOFF ( J . Russ. Chent. SOC. 1887 19 646-654).-Thedihydroxystearic acid was prepared by Syrneff and Snytzeff's methodfrom ordinary oleic acid and the present paper contains a determitia-tion of its constants. Solubility in ethyl alcohol of 99.5 per cent,. a t19" 100 pts. of solution contain 0.59 pt. of the acid dry ethyl ethera t 18" = 0.19 pt. The ethyl salt (m.p. 9.3 8-100°) was obtained bythe action of hydrogen chloride on an alcoholic solution of the acid.Solubility in alcohol of 91.5 per cent. 100 pts. of the solution at 16"contain &*58 pts. ; a t 18" = 4.72 pts. ; ethyl ether at 18" = 1-75 pts.The methyl salt (m. p. 105-106.5") 1 0 pts. of the alcoholic solu-tion a t 18.5" contain 3.34 pts.; dry ether at 19" = 1.03 pts. Theacetyl-derivative was obtained by the action of acetic anhydride at150" on the acid. It is a colourless viscid liquid and its compositionis Cl8H34Ac204. Oxidation with potassium permanganate in alkaline1; 124 ARSTRACTS OF CHEMICAL PAPERS.soIution yielded as the chief products caprylic suberic and azelai'cacids together with some unchanged dihydroxyst,earic acid. Thiswas proved by t'he analysis of the free acids and their salts.Thesame acids are found among the products of oxidation of oleic acid,and are therefore only products of the oxidation of dihydroxg stenricacid. B. B.Action of Ally1 Iodide and Zinc on Ethyl Malonate. By V.MATV~EFF ( J . Rum. Cl~em. SW. 1887 19 643-646).-Following themethod by which Schukoffsky prepared the ethyl salt of diethyl-malonic acid (Abstr. 1888 1179) the aiithor by the mutual action ofally1 iodide zinc and ethyl malonate has obtained ethyl dially Zmalonate,C(C,H,),(COOEt) together with free propylene. The ethyl salt isan oily liquid boiling a t 239-241" and having the sp. gr. 0.99181at 20" 0.98707 a t 30° and 3.98085 at 35". The free acid obtained byhydrolysis of the ethyl salt is described and also the correspondingsodium calcium and silver salts.B. B.Action of Malei'c Acid on Aniline. By I. OSSIPOFF (J. BUSS.Cltenz. Soc. 1888 20 85-97).-Referring to the work done byPerkin Michael Wing and Palmer and especialIy by Anschutz andWirtz on the constitution of male'ic acid the author tried to solve theproblem in the following manner :-Hydrogen sodium maleate wasdissolved i n water and boiled with aniline in a flask furnished with areflux condenser when crystals were formed which were greenish-yeilow melted a t 141- 143" and left no ash on incineration. They areonly sparingly soluble in ether chloroform benzene and light petro-leum but easily i n alcohol. After purification they become white andthe melting point rises to 144 -145".Elementary analysis however,proved that the substance is not homogeneous; the principal con-stituent is the aniline salt of phenylaspartic acid or its isomeride.The product was treated with baryta-water and the barium lend andsilver salts prepared. With acetic anhydride i t yields acetanilide.With diphenylamine it gives a substance melting a t 207-208" pro-bably phenylaspartanil. The liquid from which the crystals have sepa-rated contains a mixture of sodium salts. The author concludes thatmnle'inanil is the anil of male'ic acid and phenylaspartanil the anil ofa lactone isomeric with phenylaspartic acid. B. B.Isomerism of Fumaric and Malei'c Acids. By I. OSSIPOFF(J. Buss. Chem. Soc. 1888 20 97-lW).-A purely theoreticalp.iper based on the results described above.B. B.Methyl and Ethyl Salts of Ethylenediamidoformic Acidand their Nitro-derivatives. By A. P. N. FRANCHIMONT atldE. A. KLOBBIE (Rec. Trav. Chim. 7 258-262).-The methyl salt,C,K4(N H-COOMe)2 is easily obtained in almost theoretical quantityon mixing methyl carbonate (2 mols.) with ethylenediamine (1 mol.).It is very soluble in boiling water alcohol and chloroform but lesssoluble in ether and benzene and melts a t 138-133". It dissolyes iORGANIC CHEMISTRY. 125concentrated nitric acid with development of heat and on addingwater to this solution a white powder is precipitated having themelting point of the original compound but containing 21-23 peroeiit. N the original compound having only 16.41 per cent.It isnearly insoluble in cold but more soluble in hot water very solublein chloroform and benzene but only slightly in ether and alcohol.From ail solvents it separates in slender needles.The ethyl salt bas already been described by Fischer and Kochunder the name ethylenediurethane. The authors have obtained italong with various bye-products by heating a mixture of ethyl carbo-nate and ethylenediatnine at about 200" for 16 hours as a colourle+~substance soluble in ether. The nitro-derivative is obtained in likemanner to that of the methyl salt. It is a compound of very similarproperties melting at 83-84'. Analysis shows that it is a dinitro-derivative. Distilled with aqueous poIabh i t gives a distillate,which on the addition of potassium carLonate separates into twolayers.The upper contains ethyl alconol and the lower ethjlmedinitratnine. 'This nitro-derivative therefore has the constitnlionCzHk [ N( NO,) *COOE t]z. H. C.Ureides and their Nitro-derivatives. By A. P. N. FRANCHIMONTand E. A. KLOBBIE (Rec. Trav. Cltim. 7 236-257).-The authors diy-tinguish-(1.) Ureides of bibasic acids in which each of the tMoNH-groups is between two CO-groups; these do not yield nitro-deriiatives. (2.) Ureides of monobasic acids i u which one of theNH-groups is betweeu two CO-groups and the other between aCO-group and the hydrocarbon residue these give mononitro-deriva-tives. (3.) Ureides in uhich each NH-group is attached to a hydro-carbon residue and neither lies between two GO-groups.Theselast compounds yield dinitro-dei-ivatives and the name " ureinrs " isproposed for them. A number of the nitro-derivatives of (2) and( 3 ) have been considered i n a former paper (Abstr. 1888 llSO),and the present is a continuation of this work.Nitrohydantoin when boiled with 25 times its weight of waterloses 1 mol. of carbonic anhydride and takes up 1 niol. of water,being converted into nitramidoacetamide which on further evapora-tion of the aqueous solution yields glycolamide. Nitro-lactylcarb-amide treated in the same manner loses carbonic anhydride and nitrousoxide and yields an acid solution which gives with cobalt acetate thereaction for lactic acid.Nit?.oacetonllZcarEar,zide is prepared by evaporating acetonylcarb-amide with five times its weight of nitric acid and recrystallising theresidue from absolute alcohol or benzene.It forms Flender colourlessneedles melting at 140-141". Its probable constitution isWhen boiled with 25 times its weight of water it loses carbonicanhydride and nitrous oxide and appears to yield a-hydroxybutyr-amide and pc- hydroxy butyric acid126 ABSTRACTS OF CHEMICAL PAPERS.Ethylenedinitrureine ~etkyEenedinitrocarbalnide),N(N02)-CHzco<N(NOz)-CH2>9gives a compound with 4 mols. NaOH soluhle in water and insolublein alcohol and with 4 mols. AgNO a white compound which detonatesviolently on heating. On boiling with water it yields ethylenedi-nitramine; this compound forms salts containing 2 mols. of themetal. Heated with dilate sulphuric acid it loses nitrous oxide andgives aldehyde and glycol.Reduction experiments have up to thepresent led to no definite results.A cety ZerLetetramet liy2diureine (t et rame th ylgl ycolnril e),co/NMe*CH*NMe \co,\NMe*AH*NMe/is prepared by evaporating on a water-bath aqueous solutions ofglyoxal and dimethylcarbamide to which a few drops of hydrochloricacid have been added. It crystallises in long colourleas brittleneedles of bitter taste melting a t 217” very soluble in water,alcohol and chloroform and slightly soluble in ether and benzene.On treatment with strong nitric acid it is converted into acetylene-trimethylmononifvodiureine by the displacement of one of the methyl-groups by the nitro-group. The nitro-derivative crystallises in fine,colourless needles melting at 225-226” not very soluble in water oralcohol and still less so in ether and benzene.Dinietliy ZocztyZePcediurein~ (tlimethylglycoluiile),NH-CMe-NH‘NH-CMe-NH’separatcs as a white powder when a mixture of 20 parts of diacetyl,50 parts of water and 35 parts of carbamide is left for 24 hours.It isslightly soluble in water from which it crystallises i n slender needlesor small prisms ; it is very slightly soluble in alcohol and not a t all inether chloroform or benzene. With nihic acid it yields a dinitro-derirative which on boiling with water loses carbonic anhydride andnitrous oxide and gives diacetyl and carbamide. This nitro-deriva-co’ I b o ,NH - Chile-N (NO,)‘XH*CMe*N( NOz)tive probably has the constitution GO’ ] )CO.From the above and the authors’ former experiments it appearsthat the action of nitric acid on the ureides (2) and (3) results inthe displacement of one or more of the hydrogen-atoms of theNH-groups by NOz and the formation of nitramides.H. c.Identity of Methronic Acid and Sylvanecarboxyacetic Acid.By R. FITTIG and A. HANTZSCH (Ber. 21. 3189-3190; compareFittig and Schloesser Ahstr. 1888 1089 Polonowsky ibid. 1175).-The acid obtained from glyoxal and ethyl acetoacetate (comparORGANIC CHEMISTRY. 127Polonowsky Abstr. 1888 1067) is identical with methronic acid pre-pared from ethyl acetoacetate and sodium succinate. The Rame mono-basic acid is obtained by the distillation of carbopyrotritaric acid,methronic acid and sylvanecarboxyacetic acid.Isomeric Changes on Synthesising Aromatic Compoundsby means of Aluminium Chloride.By J. SCHRAMM (Monatsh. 9,613-625).-When isobutyl bromide (300 grams) is allowed todrop very slowly into a mixture of benzene (900 grams) and alumi-nium chloride (300 grams) kept cool with ice a butylbenzene (yield60 per cent.) having a sp. gr. of 0.8718 at 15" and boiling at167-167-5" under a pressure of 736 mm. is formed. It does notagree in its properties with the isobutylbenzene boiling at 170-170*5",sp. gr. 0.8578 at 15" formed by Fittig's method (Gossin Abstr.,1884 MU) for the product on treatment with 1 mol. of bromine inpresence of iodine gives a monobromobutylbenzene boiling a t230-231*5" under a pressure of 736 mm.readily solidifying on cool-ing and melting at 13-14" whilst the monobromobutylbenxene frointhe butylbenzene prepared by Fittig's method boils at 232-233*5",and does not solidify a t -20". The product of the synthesis is there-fore trimethylphenylmethane (tertiary butylbenzerze) CMejPh. Gossin'sbutylbenzene boiling a t 152-155" was not formed.Tertiary butyl chloride (50 grams) benzene (150 grams) andaluminium chloride (50 grams) under similar conditions givetertiary butylbenzene (yield 60 per cent.). In t h i s case no isomericchange takes place but normal butyl chloride (75 grams) benzene(300 grams) and aluminium chloride (80 prams) give secondarybutylbenzene CHMeEtPh boiling at 173-5-1 74*5" under a pressureof 735 mm.) and having a sp.gr. of 0,8669 at 13" ; it is identical withthe butylbenzene which Radziszewski prepared from a-p henylethylbromide and zinc ethyl. Isoamyl chloride (170 grams) benzene (360grams) and aluminium chloride (170 grams) give an amylbenzene(20 per cent. yield) which boils a t 187.5-188.5 under a pressure of757 mm. aiid has a sp. gr. of 0.8683 at 15'. It therefore does notcorrespond with the isoamylbenzene which Essner (Abstr. 1862 46)prepared from isoamyl bromide and bromobenzene and must cuiise-qnently be represented by one of the formula CHMePh-CEIMe orCMe2EtPh isomeric change having taken place.It follows from the above that when the primary monochloro-derivatives of the fatty series act on benzene in presence of aluminiumchloride the phenyl-group does not take up the position of thehalogen but links itscblf to another carbon-atom thereby forming asecondary or tertiary hydrocarbon.The isomeric change is notwalogous to t h a t of normal- into iso-propyl bromide in presence ofaliiminium chloride as observed by Kekule' and Schrotter (Bw. 12,2280) moreover Essner has shown that isoamyl chloride does notbehave similarly. On the contrarF the author finds that ihobutylehloride in presence of aluminium chloride splits up into hydrogenchloride and butylcne and holds the opinion that the isomeric changesdepend on a reaction similar to that observed by Bahlsohn (AbBtr.,1879 78S) who found that ethylbenzene could Le prepared fromF. S . I(188 ABSTRACTS OF CHEMICAL PAPERS.benzene and ethylene in presence of aluminium chloride.He there-fore concludes that the chloroparaffin splits up into hydrogen chlorideand the corresponding olefine which reacts with the benzene in thefollowing way :-PhH + Me,C:CH2 = CPhRle3 the phenyl-groupattaching itself to the carbon-atom which is directly united to thesmallest number of hydrogen-atoms. G. T. &l.Orthocresol. By A. CLAIJS and U. A. JACKSON (J. pr. Chem. [Z] 38,321-336).-Wroblewsky is mistaken in regarding the golden-yellowneedles obtained by the action of nitrous acid on bromorthotoluidineas bromocresol for they are really nitrobromorthocresol. Duringthe action parabromorthocresol is formed as well as the nitro-compound; to separate them the acid liquid is distilled withsteam and the yellow oil thus obtained which partially solidifieson cooling treated with weak sodium carbonate solution; thered solution thus formed is shaken with ether which dissolvesthe bromocresol ; the alkaline solution is then precipitated with weakhydrochloric acid and the precipitate sublimed when nitrobrontortho-cresol [OH Me Br NO = 1 2 4 61 is obtained forming beautifulgolden-yellow needles melting at 88" (uncorr.) and having all theproperties of Wroblemsky's bromorthocresol.The sodiunh salt crystal-Iises in red prisms having a green lustre.Amidobromorthocresol [OH Me Br NH = 1 2 4 61 is formedwhen the nitro-compound is reduced with stannous chloride andstrong hydrochloric acid in alcoholic solution ; it crystallises fromether as a white mass which rapidly becomes brown and sublimesin colourless needles melting at 110" (nncorr.) ; its hydrochloride isdescribed.ParabromorthocresoE [OH Me Br = 1 2 41 may be prepared frombromorthotoluidine as above or by dropping a chloroform solutionof bromine into a similar solution of orthocresol containing one-tenthof its weight of iron wire.It crystallises from hot water and fromalcohol in colourless needles which sublime unchanged ; it melts at64" (uncorr.) and boils at 235" (uncorr.). When oi-thoparadibrorno-cresol (Werner Abstr. 1886 1015) is oxidised by chromic acid in anacetic acid solution,rnetabromofoluquiwne [Me Br 0 0 = 1 3 2 53,is precipitated in yellow flocks which crystallises from ether in yellowprisms subliming as needles which melt at 93" (uncorr.) and aresparingly soluble in water freely so in other solvents; when anethereal solution of it is shaken with it hydrochloric acid solution ofstannous chloride until it is decolorised the corresponding quinoEis obtained; this forms white laminae which melt at 112" (uncorr.)and dissolve easily in the usual solrents ; the acetyl-derivative meltsat 57" (uncorr.).By chlorinating a glacial acetic acid solutionof parabromorthocresol chZorobromorthocresoZ [OH Me Br CI =1 2 4 67 is obtained ; it crystallises i n colourless needles melt-ing a t 48" (uncorr.) and yields chlorotoluquinone on oxidation(comp. Abstr. 1886 614). PLcrachZmorthocresoZ [OH Me CI =1 2 41 is obhined by chlorinating a glacial acetic acid solutionof orthocresol coiitaining some iron ; the oil crystallises with difficultyORQANIO CHEMISTRY.129and by sublimation yields crystals melting a t 33" (uncorr.) and boilingat 220" (uiicorr.).The authors describe orthocresolparasulphonic acid and its potas-sium (2 mols. H,O) and barium salts ; orthocresolorthosu1phon;c acidand its putassium salt ( 1 mol. H,O) ; orthocresolorthoparadisul-phonic acid and its potassium (2 mols. H20) barium copper and leadsalts ; but these acids have been described before. Bromocresolpura-sulphoizic acid [OH Me Br S03H = 1 2 4 61 is obtained as itspotassium salt (1 mol. H20) by brominating potassium orthocresol-parasulphonate and as its barium salt by treating t h i s with bariumchloride; the free acid melts in its water of crystallisation at '3.5"(uncorr.).; the caEcium (3 mols. H20) copper lead (3 mols. H,O) andsilver salts are described. The parabromorthocresolorthosulphonicacid is obtained from orthocrcsolorthosulphonic acid in a similarway. A. G. B.Dinitrortho-xylenols. By E. NOLTING and B. PICK (Rw. 21,3158-3160).-Dinitrortho-~yleno1 [OH Me (NO,) = 1 3 4 2 61 isobtained when the yellow ammonium salt formed in the prepara-tion of nitro-xylene (compare Jacobsen Abstr. 1884 737) is de-composed with acids; it can also be prepared by nitrating 1 . 2 . 4 -ortbo-xylidine and diazotising the product. It crystallises in yellowneedles melts a t 127" and is readily soluble in boiling alcohol hutonly sparingly in water and cold alcohol.The ammonium salt issparingly soluble in cold but more readily in hot water. The iso-meric compound [OH Me (NO,) = 1 2 3 4 61 is obtained inlike manner from 1 .2.3-ortho-xylidine. It crystallises from alcohol insmall yellow needles melts at 82" and forms an ammonium salt whichcrystallises in needles and is moderately soluble in water. Con-centrated aqueous s o h tions of the ammonium saits described abovegive orange or yellow cr~stallirie precipitates with barium or calciumchloride and other inorganic salts.Benzene-derivatives of High Molecular Weight. By I?.KRAFFT and J. GOTTIG (Ber. 21 3180-3188 ; compare Krafft Abstr.,1887 252 ; 1888 1087).-~exadecyZlplrenetoZl C&.3,*C,H4*OEt is pre-pared by heating hexadecplphenol with ethyl iodide and alcoholicpotash.It crystallises from alcohol in plates and melts a t 43-44",It yields parethoxybenzoic acid melting at 195" when heated a tabout 120" with nitric acid of sp. gr. 1.12.Acethexudecylaniiide C16H33*C6H4mRHAc prepared by treating ami-dohexadecylbenzene wikh acetic chloride melts a t 104-104*5" andboils a t about 295" ( 2 5 mm.).Orthomethy Zhexadecylbensene C16H33*C6H4n/Ie is obtained by heatinga mixture of sodium (10 grams) orthobromotoluene (34 grams) andcetyl iodide (48 grams) at about 140". It crystallises from a well-cooled mixture of ether and alcohol melts at 8-Y0 and boils a t238.5-235" (15 mm.). It resembles hexadecylbenxene in its be-haviour towards solvents and the melted substance is fluorescent.The corresponding meta-derivative prepared in like manner meltsat 11-12" boils a t 236.5-237" (15 mm.) and resembles hexadecyl-F.S . I(130 ABSTRACTS OF (3HEMICAL PAPERS.benzene in its behsvioui* towards solvents. The para-derivative meltsat 27.5" and boils a t 239-5-240" (15 mm.). The melted substancesolidifies to a mass of crystals but doe8 not melt again a t 27.5" untili t has been either well cooled or brought into contact with a crystalof the original substance. It yields toluylic acid when heated a t120-130" with nitric acid of sp. gr. 1.12.Sodium para met hy 1 hexndPcyl b enzenesulp hoii d e C 16H3'J*C6H3Me*S 03Na,is obtained in nacreous plates when the preceding compound is dis-solved in fuming sulphuric acid the product poured into ice-coldwHter the acid extracted with ether and treated with sodiumchloride.Yaramefhy Zh exadecylpheitol C c6H3Me*OH prepared by melt-i n g the preceding compound with potash and a little water a t 150",crystallises from alcohol melts a t 6 2 O and boils a t 267-268"(15 mm.).Yaratnethylhexndecylphenetozl obtained by healing the phenol withethyl iodide and alcoholic potash melts a t 26.5."Amidoparanj eth!/lheradecylbenzene C ,H,,* C6EIIMe*NH2 is obtainedwhen paramethyltiexadecylbenzene is dropped into cool.fumingnitric acid and the resulting nitro-compound melting at about 40",reduced with stannous chloride. It melts at about 54" and boils at264-265" (15 mm.).Dirnetlylhexadecylbenzene [Me c,,H = 1 3 41 prepared by heat-ing bromometaxylene and cetyl iodide with sodium crystallises fromz i well-cooled mixture of ether and alcohol melts at 33.5" and boils atZ'rimet~~yZhexu~ecyZbenzene [Me3 C1,H = 1 3 5 61 prepared inlike manner from bromomesitylene seems to melt a t about 40" andboils a t 258-258.5" (15 mm.).249 5-250".F.S. I(.Constitution of Styphnic Acid. By S. KOSTANECKI and B.F E i s s r E r N (Ber. 21 3119-3123).- Consecutive dinitroresorcinol isbest prepared by the method Stenhouse and Groves employed in thecase of dinitroorcinol.S typhnic acid is obtained by boiling consecutive dinitroresorcinolwith dilute nitric acid and by the action of very strong nitric andsulphuric acids on the symmetrical dinitro-derivative in the cold. Theacid has therefore the constitution [(OH) (NO,) = 1 3 2 4 61,ascribed to it by Nolting and Collin (Abstr.1883 1004).(This Journal 1877 i 545.)N. H. M.Action of Carbon Bisulphide on Dimethylaniline in Pre-sence of Nascent Hydrogen-By J. WIERNIK (Ber. 21 3206-3207).-When dimethylmiline and carbon bisulphide are treatedwith zinc-dus t and hydrochloric acid tetrame thyldiamidophen-yl-methane melting at YO" and thioformaldehyde are formed. Theformer compound is identical with that obtained by Troger (Abstr.,1888 287) who took it for the ethane-derivative. This however,crzstalliseJ in slender needles and melts a t 50" (Schoop Abstr. 1881,169). N. H. 31ORQANIC CHEMISTRY. 1311 . 2 . 3-Metaxylidine and its Identity with Wroblewsky'sOrthoxylidine.By E. NOLTING and B. PICK (Ber. 21 3150-3154 ;compare Grevingk Abstr. 1885 144 and Nolting and Forel,Abstr. 1 886 58).-Metaxylidine can be obtained from commercialxylidine as follows :-The bases are converted into the sulphates thesolution is allowed to crystallise and the mixture of bases obtainedfrom the mother-liquor from the last crop of crystals is fractionated.The portion distilling at 212-216" is treated with acetic anhydride,and the mixture of acetyl-derivatives boiled for a few hours withfour times its weight of 25 per cent. sulphuric acid. On cooling thegreater part of the metaceto-xylide separates unchanged and theremainder can be obtained by extracting the dilated mother-liquorwith ether. The acetyl-derivative is then decomposed by heating at150" with concentrated hydrochloric acid or at 200" with three timesits weight of 70-75 per cent.sulphuric acid. Metaxylidene canalso be prepared from commercial xylidine by heating the mixture ofbases obtained from the mother-liquor from the sulphates (see above)for 24 hours with an equal weight of glacial acetic acid and distillingthe product. The portion passing below 300" is then treated withacetic anhydride and the acetyl-derivative boiled with 25 per cent.sulphuric acid and isolated as described above. The fraction passingabove 300" contains a small quantity of metaceto-xylide which can beseparated by heating with 25 per cent. sulphuric acid as alreadydescribed. The sulphate ( C8HgNH2),,H2SO4 crystallises in needles,and is decomposed into hydrogen xylidiue s u b h a t e C8H9NH2,H2S04 +2&H20 when the aqueous solution is evaporated.1 .Z.%Metaxylidine is only with difficulty converted into theacetyl-derivative ; the latter melts at a comparatively high tempera-ture and is hydrolysed only with difficulty. The sulphate is veryreadily soluble.In these respects this base differs from all theisomeric compounds.'l'he compounds described by Wroblen sky (Bey. 18 2304 3106 ;19 235) as srtho-xylidine is idenhical with 1 . 2 .3-metaxylidine.F. S. I(.Metaxylylamidornethane. By W. HIKXICHSEN (Rer. 21 3082-3086) .-&letaxylonitrile prepared from metaxylidine by Sandmeyer'sreaction melts at 23- 25". Met m y l y lainidomethane ( m e t azy lobenzy 1-anvine) C6H,Me2*CH2.NH2 prepared by treating a hot alcoholicsolution of metaxylonitrile (10 grams) with sodium (16 grams),boils at 218-219" is readily soluble in alcohol and ether sparinglyin water and absorbs carbonic anhydride and water on exposure tothe air.The hydrochJoride CgHI3N,HC1 crystallises in needles or platesand melts at 210". The hydriodide is crystalline. The plutinochloride,( GH,,N)2,H2PtC16 crystallises in small yellow needles melting at226-228" with decomposition. The mercuroclrloride CgH,,N,HHgC1,,crystallises in large plate6 or needles melts at 205" and is very sparinglysoluhle i n water. The sulphate crystallises from water in needles,melting at 254". The picrate C9Hl?N,C6H3N30 crystallises in yellowplates and melts at 22.3" with decomposition.The nitrate crystallise132 ABSTRACTS OF CHEMICAL PAPERS.in slender needles melting at 157-158'. The salt C9H,,N,CdI? pre-pared by adding a solation of potassium cadmium iodide to a solutwnof the bfise is crystalliw and moderately soluble in water. Thecndmioiodide (C9H13N)2,2HI,Ccl12 prepared by adding a solution ofpotassium cadmium iodide to an aqueous solution of the hydro-chloride is only moderately soluble in alcohol and very sparingly soin water.Metaxylyl carbinol (mefaxylobenzyl alcohol) C6H3Mea*CH2*OH isprepared by treating. the preceding compound with nitrous acid anddistillirig the product with steam. I t is a colourless aromatic-smellingliquid boils a t about 232" solidifies when cooled in a freezing mixtureand melts a t 22".Dimethylbewzaldehyde (metcrx~ilobenzaldehyde) C6H3Me2.CH0 isformed when the alcohol is oxidised with sulphuric acid and potas-sium dichromate.The product is distilled with steam and purifiedby means of the crystalline sodium hydrogen sulphite compound.It is a colourless oil boils a t 223-225' smells like benzaldehyde andturns yellowish on exposure to the air. F. S . K.Action of Amines on Nitrogenous Organic Compounds.By B. LACHUWICZ (MovLatsh. 9 695-70O).-When hydrobenzamide isgently warmed with the amines decompositions occur which may berepresented by the general equation N,(CHPh) + 3RNH =2NH3 + 3CHPh:NR. By means of this reaction the author hasformed the following derivatives of benzylidene :-C7H6:NPh prepared from aniline agrees with the description givenof it by Cedi (Abstr.1878 408) except that its melting point is 49",whereas Cech gives it as 42'.C7H6:N*C6H1Cl prepared from metachloraniline is a viscid liquidwhich boils at 338".C7K6:NC6H3Cl2 prepared from paradichloraniline (m. p. 63"),crystallises from alcohol in thin plates melting a t 84".C7H6:N.C6H4*N02,. prepared from paranitraniline crystallises inyellow needles melting a t 115" ; the compound prepared from meta-nitraniline crystallises in yellow needles melting at 73".C7H6:N.C7H7 prepared from orthotoluidine forms an oil boiling a t309-310" (745 mm.).C7H6:N*CloH7 prepared from a-naphthylamine crystallises fromalcohol in yellow needles melting a t 7:+". The compound from/3-naphthylamine forms yellow needles melting at 101".CHPh(C,NHE,,)2 prepared from piperidine melts at 81".The amides of the acids react with hydrobenxamide with erolutionof ammonia strong bases such as piperidine and formamide beingsimilarly decomposed.G. T. M.Condensation Products from Bases of the Para-series withPara- and Meta-nitrobenzaldehyde. By A. BISCELER (Rer. 21,3207-3219 ; compare Abstr. 1888 287).- Diacefyl-/3-parar~itropherLyl-diparmnidotolylmef hane NO2*C,H,*CH( C,H,*NHAc) prepared bgboiling the base with a slight excess of acetic anhydride for one or twORGANIC CHEWSTRT. 133hours crystallises from dilute alcohol in light yellow grains meltinga t 136". It is readily soluble in cold alcohol and ether. Thehenzoyl-deriz~ative C,H,NO,( C,H,-NHBz) is obtained by heating thebase with benzoic anhydride a t 120-1 30" ; i t forms yellow needles,melts a t 152" and is readily soluble in warm alcohol and ether.p-Metanitrophenyldiparamidotolylmethane,is prepared by adding strong sulphuric acid to an intimate mixtureof metanitrobenzaldehyde and paratoluidine sulphate ; after three tofour days it is treated with much water and heated ; i t is then filtered,made alkaline and steam distilled.The oily residue which solidifieswhen cold is crystallised from hot alcohol. It crystallises in yellowishneedles melts a t 85-86' dissolves very readily in chloroform readilyirl hot alcohol rather 1.eadi1-y in etber and benzene. The hydrochlorideforms voluminous yellowish needles readily soluble in hot alcoho! ;hot water decomposes it.The pZatirmchZoride CI~Hz,N,02,HzPtCl,,crystallises in yellow voluminous needles sparingly soluble ina1 co hol. The acet y I - conip ouizd N 0 z*C6H** C H ( C,H,*NH Ac) % separatesfroin the aqueous alcoholic solutim in pale yellow needles melts at103-104" and dissolves readily in warm alcohol and benzene. Thebenzoyl-compound C35H?9N304 forms groups of yellowish needles,melts at 1$6" and is readily soluble in alcohol less 80 in ether.Mef~xmid~lienyldipai-amidoto7ylnzet~~ane C2,RL,N obtained byreducing the nitro-compound with tin and hydrochloric acid cr) stnl-lises in white plates readily soluble in alcohol and ether. The hydro-c,hloride forms white plates the p1at;nocliloride crjstallises in small,yellow plates sparingly soluble in hot water.a-1Metanitrophenilldiparamidotolylmetha e Ca,H2,N ?02 is prepared bythe action of hydrochloric acid on metani trobenzaldehydr and para-toluidine.It melts at 125-128". The salts are decomposed bywater.Pnranitrop heny Zdiparanaidophenylisobutyln Lethane,NO,.C,H,*CH( C,H,Bu*NH,),,prepared from paranitrobenzald ehy d e parami doi sobn t y I ben zenesulpl~ate and strong sulphuric acid crystallises in Iustroi~s yellowneedles melts a t 125-126" and is readily soluble in chloroform,benzene and hot alcohol. The h y d r o c h b i d e forms light yellowplates readily soluble in hot alcohol ; the platinochloride crypt al~i'esin yellow plates. The acetyl-compound crystallises in yellow grains,melts at 114' and dissolves readily in benzene and in warm alcoholand ether. The benznyl-derivative forms long yellowish needles meltsat 185-126" and is readily soluble in ether benzene chloroform andboiling alcohol.Meta?iitr~henyldz.yfrram idop herby lisobu fy Zmethaw e CnHJ3N302 formslight yellow plates melts a t 64-65' and resembles the para-compound in solubility.The benzoyl-derivative cr-y stalliseq from hot,aqueous alcohol in yellowish plates melts a t 113-114" and is readilysoluble in hot alcohol134 ABSTRACTS OF CHEMICAL PAPERS.Paranitropheny Wianiidoni etaxyly hethane,NOz'C,H,.C H (CsH8.N Hz),,prepared from paranitrobenzaldehyde (10 grams) unsymmetricalmetaxylidine (10 grams) and sulphuric acid crystslliseN in lightyellow lustrous hair-like needles melts at 89-90' and dissolveswadily in hot alcohol in ether benzene and chloroform.The hydro-chloride forms pale yellow flat needles dissolves readily in hotalcohol and is decomposed by water. The platinochloride separatesin yellow crusts. The acetyl-derivative forms small light yellowgrains melting a t 88" ; the benzoyl-dwivative cpystallises in voluminous,lustrous pale yellow needles melting at 191-192" ; both compoundsdissolve easily in hot alcohol less readily in ether.Netunitrophenyldiamidomefaxylylwiethane C2,H2,N302 crystallisesfrom alcohol in pale yellow sleuder plates melts at 91-92" andresembles the para-compound in solubility. The hydrochloride crys-tallises from alcoholic hydrochloric acid in pale yellow plates ; theplntinochlorid e forms a greyish- yellow crystalline precipitate.Theacetyl-compound separates from ether in small light grey needles,melting at 131-132" ; the benzoyl-compound forms voluminous,yellowish needles and melts at 185-186". N. H. M.Halogen-substituted Acetamido-derivatives of the AromaticSeries and their derived Piazines. By P. W. ABENIUS and 0.WIDMAN (J. pr. Chem. [2] 38 296-312).-The substance of theformula C9H,Br2N0 formed by digesting alcoholic potash (1 mol.)and bromacetodibromorthotoluidide (1 mol.) (see next Abstract) ; isvery sparingly soluble in hot alcohol but may be recrystallised fromglacial acetic acid in colonrless hexagonal lamina melting at 277'.It is an indifferent Substance soluble in neither alkalis nor strongmineral acids.I t s constitution is most probablyCO-CH C6H2Br2Me*N<CH 6>N*C6H,BrzMe.2 A. G. B.Action of Bromine on Orthacetotoluidide at a High Tem-perature. By P. W. ABENIUS and 0. WIDMAN (J. pr. Chew. [2] 38,285-295) .-Brow acetodibromort ho toluid ide C8HzBr2Me.NH*CO*C H,Br,is obtained when orthacetotoluidide (10 grams) is heated a t 160" andbromine (32 grams) added drop by drop; the product solidifies oncooling to a hard brittle black resin which when treated with chloro-form yields besides an oil the bromo-compound as white prismaticneedles ; the needles recrystallised from glacial acetic acid melt a t807" ; they are sparingly soluble in hot alcohol more so in benzene.As this compound can be synthesised from bromacetic chloride anddibroinorthotoluidine its constitution is as expressed by the aboveformula.If it is digested for an hour with alcoholic potash (in mol.proportion) it loses a molecule of hydrogen bromide and a sparinglysoluble substance of the formula C,H,13r2N0 separates ; but whenheated with a considerable excess of alcoholic potash in a refluxapparatus i t is decomposed with formation of dibromorthotoluidinORGANIC CH E MISTR P. 135and potassium bromacetate. DibronaorthotoEuidi1le platinochloridecryvstallises in sparingly soluble yellow needles.Diacetyldibrornort hotoluid ide C6Hi,BrzMe.NAc2 prepared by heatingdibromorthotoluidine for several hours with an excess of aceticanhgdride forms white needles very soluble in alcohol and meltingat 88". When only gently warmed wihh acetic anhydride a substancemelting at 200" is obtained and is doubtless acetyldibromortho-toluidide but has not yet been malysed.dcet~~lgl,ycolyldibromorthotoZuidicZe C6H~Br2Meo~H.CO*CH~*OAc.-Perfectly pure bromacetyldibromorthotoluide (2 grams) is heated withacetamide (6 grams) at 150-170" until blackening begins ; the massis washed with water to remove excess of acetamide and hydrobromicacid and the residual acetyl compound recrpstallised from alcohol ;it forms white needles melting at 172".This substance was alsoobtained by heating bromacetodibromo~*thotoluidide with silver acetate.When heated wihh weak aqueous potash i t i s dissolved and con-verted into gZ~col~/ldl:bromorthotoZuidit€e C6H,Br2Me*NH*CO*CH,-OH,which crystallises as the solution cools in colourless laminae havingcurved edges; with a stronger solution of potash the acetyl com-pound is converted into the laminae without being dissolved.Thelaminm crystallise from alcohol in slender colourless needles whichmelt at 182" and are more easily soluble in weak alkali than inwater ; they are precipitated from the alkaline solution on neutrnlisingit with hydrochloric acid. This compound is also obtained when theacetyl-derivative is heated with aqueous soda or with weak hydro-chloric acid. A. G. B.Phenylenediazosulphide. By P. JACOBSEN (Ber. 21 3104-3107).-Orthophenylenedinzosulphihide C6H4<z>N is formed when thediazo-compound of diamidophenyl disulphide is boiled with water(AEstr. 1887 961) and in much larger amount hy the action ofnitrous acid on amidophenyl mercaptan.It crystallises in plates,melts a t 36-37' has an agreeable aromatic odour and distils readilywith stcam ; it is soluble in strong hydrochloric acid.N. H. M.Azo-xylenes Diamido-dixylyls and Colouring Mattersderived therefrom By E. N~LTING and T. STRICKER (Ber. 21,3138-3149).-Consecz~tive nzortho-zylene C6H,Me2*N:N*C6HI,Me2 [Me2 N= 1 2 31 is obtained when zinc-dust (20 grams) is graduallyadded to a boiling alcoholic solution (100 c.c.) of orthonitro-xylene(20 grams) and 32 per cent. soda (20 grams). After filtering andconcentrating the solution the product is washed with dilute hydro-chloric acid and recrystallised several times from alcohol. It can alsobe obtained by oxidising the hydrazo-compound (see below) withferric chloride or hydrogen peroxide in alcoholic solution.It crys-tallises in orange-yellow needles melts at 110-lll" and is readilysoluble in alcohol ether. and benzene. The hydrazo-componnd can beprepared by treating the azo-derivative with hydrogen sulphide or byreducing orthonitro-xylene as described above employing 25 grams o136 ABSTRACTS OF CHE?vIICAL PAPERS.zinc-dust. It crystallises from alcohol in colourless needles meltsat 139-141" quickly oxidises on exposure to the air aiid is soluble inthe ordinary solvents-although not so readily as the azo-compound.Unsymmetrical azortho-zylene [Me N = 1 2 41 is prepared asdescribed in the case of the isomeric compound except that muchmore alcohol and very little soda must be employed otherwise a redcondensation product is formed (see below). It can also be obtainedby reducing nitrortho-xjlene with the theoretical quantity of sodiumamalgam.It crystallises from alcohol in which it is more sparinglysoluble than the 1 2 3 compound in red needles and melts atThe hydmzo-compound prepared by reducing an alcoholic solutionof nitro-xylene with sodiiim amalgam or by treating the azo-compoundwith zinc-dust and soda ammonium sulphide or sodium amalgam,crystallises from alcoliol in yellowish needles melts a t 106-107° andis tolerably stable in the air.Unsymmetrical azomotaxylene [Me2 N = 1 3 41 melting at129" can be obtained by reducing an alcoholic solution (300 c.c.) ofthe nitro-compound (25 grams) with zinc-dust (25-30 grams) and32 per cent.soda (15 grams). (Compare Schultz Abstr. 1884 902.)The hydrazo-compound is obtained by boiling a mixture of alcohol(250 grams) nitro-xylene (30 grams) 32 per cent. soda (30 grams),and zinc-dust (40 grams) until the solution becomes almost colourless,and treating the crnde product with hydrogen sulphide in alcoholioammonia solution. I t crystallises from alcohol in colourless needles,and melts a t 120-122".X!ynzmetricnl azornrtaxylene [Me N = 1 3 51 prepared by re-ducing an alcoholic solution (GO c.c.) of nitrometaxylene (10 grams)with zinc-dust (10 grams) and 32 per cent. soda (10 grams) crystal-lises in orange needles is readily soluble in the usual solvents andmelts at 136-137".The hydrazo-compound is prepared by treatingnitrometaxylene (10 pams) with soda (3 grams) and zinc-dust (15grams) in alcoholic solution (50 c.c.). It crystallises from alcohol incolourless needles melts a t 124-125" and quickly osidises on expo-sure to the air. It cam also be obtained by reducing the azo-compoundwith ammonium sulphide.Azopnraxylene [Me N = 1 4 21 obtained by treating nitro-paraxylene (20 grams) with zinc-dust (16-20 grams) and 32 percent soda (16 grams) in alcoholic solution (200 c.c.) crystallises inyellow needles and melts at 119". The azo-xyleoe prepared by Werigo(Zeit. f. Chem. [ a ] 1 312) is probably identical with this compound.The hydrazo-compound prepared by reducing nitroparaxylene (30grams) with 32 per cent.soda (25 grams) and zinc-dust (45 grams)i n alcoholic solution (250 c.c.) crystallises from alcohol in colourlessneedles melts a t 14.5" and is moderately stable in the air.The hydrochlorides of the corresponding diamidodixylyls wereprepared by heating the hydi azo-xylencs with moderately dilute hydro-cllloric acid either alone or in alcoholic solution adding excess ofsoda extracting the base with ether and saturating the dried etherealsolution with hydrogen chloride.Hydrazometaxylene [Me2 N = 1 3 41 by this treatment yields140-141"ORGANIC CHEMISTRY. 137chiefly azo-xylene and xylidine ; the last-named compound is separatedfrom the dislmidodixylyl by distilling with steam. Hydrazortho-xylene [Me2 N = 1 2 41 is hardly acted on a t all whenboiled w i t h acids and the hydrochloride of the corresponding di-amidodixylyl was obtained by boiling an alcoholic solution of theazo-compnund with hydrochloric acid and stannous chloride separat-i n g the xylidine by distilling with steam and saturating an etherealsolution of the base with hydrogen chloride.Nitrortho-xylene [Mez NO,= 1 2 41 yields a red and nitrometn-xylene [Me.NO = 1 3 41 a brownish-red condensation productwhen treated with alcoholic soda. The red compound is almost in-soluble in ordinary solvents and when reduced with stannous chlorideand hydrochloric acid is converted into dimethyldiamidostilbene.(Compare Bender and Schultz Absty. 1887 268.)All the bases obtained from the nitro-xylenes after diazotising yieldwith naphthionic acid a-naphthol-a-sulphonic acid and P-naphthol-disulphonic acid R compounds which dye unmordanted vegetablefibres. The diphenyl-derivatives are reddish dyes with a more orless blue or yellowish shade whereas the stilbene-derivative yields a,bluish-violet dye with a-naphthol-a-sulphonic acid.The toluidinesfrom meta- and para-nitrotoluene were also prepared ; these basesyield red dyes with the above-named sulphonic acids. F. S. K.Nitroso-derivatives of Resorcinol Azo-dyes. By S. V. KOSTA-NECKI (Eer. 21 3109-3 114).-NitrosophenyZazoresorcinoZ CI2H9N3OS,is readily obtained by adding a mixture of phenylazoresorcinol(1 mol.) dissolved in dilute alkali and sodium nitrite (1 mol.) tocooled dilute sulphuric acid.The product is filtered washed andcrystallised from alcohol. It separates in lustrous brownish-red plateswhich when heated at 168" detonate ; it dissolves sparingly in hot,water readily in benzene and still more readily in chloroform ; etherdissolves i t sparingly. I t dissolves in alkalis with yellowish-brown,and in strong sulphuric acid with olive-green colour and yields anintense olive-green colour with iron mordants. Similar dyes wereprepared from ortho- and para-toluidine xylidine pseudocumidine,meta- and para-nitraniline amidoazobenzene and nnphthionic acid.Nitrosopseudocum?/Z~xoresorcinoZ Cl5HI5NJO3 crystallises from chloro-form in brown plates decomposes when heated above 190" anddissolves in alkalis and in strong sulphuric acid yielding brownish-yellow and brownish-red soliltions respectively.When nitrosophenylazoresorcinol is reduced with tin and hydro-chloric acid diamidoresorcinol is formed.P h m y lazonitrosoresorcirLoZ C1,H9N303 isomeric with nitrosophenyl-azoresorcinol is obtained by adding nitrosoresorcinol dissolved inaqueous sodium carbonate to a solution of diazobenzene chloridecooled wihh ice.It crystallises from alcohol in golden plates whichdecompose at 225". The solution in dilute soda is reddish-yellow ;the sulphuric acid solution is olive-brown. When reduced it yieldsthe same diamidoresorcinol as that obtained from nitrosophenylazo-resorcinol. N. H. M.VOL. LVI. 138 ABSTRACTS OF CHEMICAL PAPERS.Isomeric Phenyldiazoresorcinols. By S. V.KOSTANFCKI ( Rer.,21 3114-3119).-Syn~metrical diamidoresorcinol C6H2(mH2),( OH),,is isolated in a manner similar to the consecutive derivative (pre-ceding Abstract) ; it is identical with Typke's isodiamidoresorcinol(Abstr. 1883 917). The szdphrtic! (with 2 mols. H,O) crystallisesfrom very dilute alcohol in needles.Symmetrical phenyldiazoresorcinol is formed when resorcinol(1 mol.) is added to a diazotised solution of aniline (2 mols.) andthe whole poured into an excess of dilute alkali. Consecutivephenyldiazoresorcinol is obtained by adding a mixture of diazoben-zene chloride (2 mols.) and resorcinol (1 mol.) to aqueous sodiumacetate or sodium carbonate. Thc consecutive compound is best pre-pared as follows :-Aniline (2 mols.) is dissolved in dilute hydrochloricacid (5 mols.) and diazotised with sodium nitrite.When an excess ofnitrous acid is no longer present resorcinol (1 mol.) is added thewhole added to a dilute solution of sodium acetate or carbonate andafter being kept for some time filtered dried and crystallised from amixture of chloroform and alcohol. The isomerides have the proper-ties already ascribed to them (Liebermann and v. Kostanecki Abstr.,1884 1146).Phenylazoresorcinol is best prepared by adding resorcinol (1 mol.)to the diazotised solution of aniline hydrochloride (1 mol. ) pouringthe mixture in a thin stream into an excess of dilute alkali precipi-t,ating the phenylazoresorcinol with acid and crystallising it fromdilute alcohol.oc-Ethylenephenylhydrazine.By 0. BURCHARD and A. M~CHAELIS(Rer. 21,3202-3204) .-a-~'tlLylenc!phen~jlhydrazine C2H4 NPh-N H,),,is prepared by adding the calculated amount of ethylene bromide tofinely powdered sodium phenylhydrazine covered with benzene. After10 minutes the mixture becomes warm and in a short time thereaction becomes so violent that the flask has to be cooled with icewater. The product is treated with water and the benzene separatedand extracted first with very dilute hydrochloric acid to remove anyphenylhydrazine which is present. and then with strong hydrochlorieacid. The base is precipitated from the aqueous solution with sodaand crystallised twice from alcohol. It forms colourless prisms orplates melts a t go" and is readily soluble in hot alcohol and ether,and in dilute acids.It gradually reduces Fehling's solution whenheated. The hydyoch Zoride ClaH18N6,2HCl crystallises in needles ofa silky lustre When the base is treated with alcohol and thenwith acetaldehyde heat is developed and the condensation product,C,H,(NPh*N:CHMe) separates in long white needles which melt at82". The corresponding benzyzidene-derivative crystallises from hotglacial acet'ic acid in slender needles melts a t 193O and is verysparingly soluble in ether and alcohol.The theoretical yield is readily obtained.N. H. M.N. H. M.Di-phenylmethyltriazole. By J. A. BLADIN (Ber. 21 3063-3065) .-Di-phenylmethyltriazole <cMe.N>CG<N.cMe> is ob- N-NPh NPh-Ntained when cyanophenylhydrazine (Senf Abstr. 1887 929) iORGANIC CHEMISTRY.139heated for a few minutes with excess of acetic anhydride. It crystal-lises from alcohol in colourless prisms melts at 222-223" and isreadily soluble in chloroform moderately so in alcohol but onlysparingly in benzene and ether and insoluble in water. It is verystable and is not decomposed when boiled with alcoholic potash orstrong acids. The hydrochloride CI8Hl6N6,2HC1 separates as a crys-talline powder when concentrated hydrochloric acid is added to aboiling alcoholic solution of the base. It is almost insoluble infuming hydrochloric acid and is decomposed by water. The platino-chloride C,8H,6N6,H2PtC16 + 4H20 crystallises in orange-yellow plates,becomes anhydrous at 125" and is d&omposed by water:F.S. K.Action of Sodium Hypobromite on Nitrogen-derivatives inthe Benzene Series. By G. DEN~GBS (Compt. rend. 107 662).-When an alkaline solution of sodium hypobromite is boiled for a fewminutes with a solution of hippuric acid or R hippurate gas is evolved,and a reddish-yellow precipitate is formed. Benzoic acid gives noreaction and glycocine decolorises the hypobromite with evolution ofnitrogen.With sodium hypobromite benzamide and benzonitrile give noreaction in the cold but a kermes-red precipitate on heating. Anilinegives an orange precipitate and the reaction is almost as delicate asthat with hypochlorites. Methylaniline and dimethylaniline give a,greenish-yellow precipitate in the cold and a red precipitate onheating. Toluidine behaves like aniline but the precipitate is darkerin colour. Anilides give no reaction in the cold but a reddish pre-cipitate is formed on boiling and an odour of methyl cyanide can beperceived.Metaphenylenediamine diamidobenzoic acid and toluylene-diamine yield maroon-red precipitates in both cold and hot solutions.Ferrocyanides ferricyanides and nitroprussides yield a precipitate offerric hydroxide. Pyridine gives no reaction and pure quinolinealso gives no reaction but if as is frequently the case it containsaniline an orange precipitate is formed. C. H. B.Aromatic Derivatives of Oxamide and Oxamic Acid. By J.MAUTHNER 2nd W. SUIDA (Illonatsh. 9 736-750 ; compare Abstr.,1886 886 ; Ber. 3 227)-When ethyl oxalate and orthotoluidine areheated together in molecular proportions ethyl oxalorthotoluidate isformed together with a little oxaltoluidide the latter remainingundissolved on treatment with alcohol.On heating either alone orwith acetic chloride the free acid is converted into oxalorthotoluidide,which can also be obtained by heating together orthotoluidine(1 mol.) and anhydrous oxalic acid (2 mols.) at 220". Oxalortho-toluidide melts at 207-208" and appears to be identical with thepolyformotoluide described by Ladenburg.Oxanilidediorthocarboxy lie acid C2O,(NH*C6H4*COOH) may beobtained by the oxidation of oxalorthotoluidide with permanganateas well as by heating a mixture of anthranilic acid (2 mds.) andethyl oxalate (1 mol.) at 140-150". When sulphuric acid is addedE 140 ABSTK-ACTS OF CEEMICAL PAPERS.to an ammoniacal solution the acid is thrown out in the form of apulverulent precipitate.The copper salt C,6HloN,06Cu + CuO hasa bright green colour ; the silver salt C1,HI,,N2O6Ag forms an in-soluble white precipitate.Oxalxylidic acid C8Hg*NH*CO*COOH is formed by heating a t180-190" a mixture of a-amidometaxylene (1 rriol.) and ethyl potas-sium oxalate (1 mol.). It crystallises in needles containing 1 mol.H,O and melts at 128-129". The silver salt CloHloAgN03 andthe calcium salt are both soluble in water and crystallise in needles.On heating the free acid it is converted into oxdxylidide C,oH20N?02,which crystallises from acetic acid and benzene in flat needles meltingat 210".OxaZ-+-czLmidic acid C9H:Il*NH*CO*COOH is prepared by hefttingat BOO" a mixture of Feumidine melting a t 63" (1 mol.) and ethyloxalnte (1 mol.).It crystallises in needles containing 1 mol. H,Oand melting at 167". The sodium salt CIlH,,N03Na + 3H10 crys-tallises in scales ; the potassium salt CllH12N03K,CllH13N03 inneedles; the calcium salt (C,1H,,N03)2Ca + H,O is a crystallinepowder ; the acid silver salt C11H1~NOSAg,CIlH18N03 forms bundles ofneedles and the normal salt C1,H12N03Ag is a crystalline powder.On heating the free acid it is converted into oxal-y-cumidide whichcan be directly prepared by the action of anhydrous oxalic acid on thebase and crystallises from acetic acid in needles melting a t 230".Phthalimidine. By C. GRAEBE (Awnalert 247 288-301).-Phthalimidine is prepared by the reduction of phthalimide by tin andhydrochloric acid.The tin is precipitated from the crude product bystrips of zinc and the phthalimidine is deposited as the nitroso-compound on the addition of a concentrated solution of sodiumnitrite Nitrosophthdimidine is decomposed by strong hydrochloricacid yielding a mixture of phtlalimidine and its hydrochloride. Theconversion of the nitroso-compound into phthalide and the pro-perties of some of the phthalimidine-derivatives have already beendescribed (Abstr. 1885 167 and 979). Phthalimidine melts a t 150",and boils a t 336-337" under 730 mm. pressure. It is freely solublein alcohol ether and chloroform. On the addition of bromine to thesolution in chloroform the tribromide ( C,H4N0)2Br3 is deposited ;it melts a t 150" with decomposition.The hydrochloride C,H,ON,HC'l,picrate (m. p. 140°) and aurochlorids (C8H,0N)2,HAuC14 are crystnl-line. Phthalimidine silver CsH60NAg is deposited from ammoniacalsolutions in crystals. Acety Zphthalintidine C8H60NAc melts at 151",and does not yield a nitroso-derivative.Nitrosophthdimidine is decomposed by sodium hydrogen sulphide,yielding thiophthazide C8H60S ; this is freely soluble in alcohol andether melts a t 60" and is converted into a thio-derivative of hydr-oxymethylbenzoic acid by solution in alkalis and reprecipitationby acids. Nitrophtha!irnidine melts a t 210" and is deposited fromalcoholic solution in pale yellow scales. It is soluble in alkalis:acids p&cipit;tte from the alkaline solution the compound C,H,O4N ;this is freely soluble in alcuhol ether and in hot water.Dinitrophthal-imidine melts a t 195". w. c. w.G. T. MORGANIC CHEMISTRY. 141Substituted Phthalimidines. By C. GRAEBE and A. P I c T h T(Anr/wZerz 247 302-306) .-Methylphthalimide C8H402NMe andmethylphthaliniidine C8H6O4NMe have been previously described bythe authors (Abstr. 1884 lolH). Methylphthalimide melts at 132"arid boils at 28.5-286". Ethyl phthalimide melts at 79" and boils a t282.5" under 726 mm. pressure. Ethyl phthalimidine melts at 45".The aurochloride ( C,oHloON)2,HAuC14 forms golden prisms meltinga t 145". Phenyl phtha.limidine C,&ONPh prepared by reducing analcoholic solution of phthalanil with tin and hydrochloric acid isidentical with Hessert's phthalidanil obtained by the action ofBy J .VILLE (Compt. rend. 107 659-661) .-Dihydro.cyheiizylene~ho.~hznzcacid PO( CHPh*OH),*OH is obtained by the action of hypophosphorousacid on benzaldehyde and crystallises in white radiating lamellae,which can be purified by solution i n potassium hydroxide and repre-cipitation by hydrochloric acid. It is only slightly soluble in water,chloroform or benzene but dissolves readily in ethyl alcohol or ether,and is still more soluble in methyl alcohol. With acids it formscrystallisable salts and its solution has no reducing action on coppersulphate or amrnoniacal silver solutions. It begins to melt at 165",and forms a yellowish liquid which if more strongly heated gives offhydrogen phosphide and leaves a bulky carbonaceous residue.Whenheated in sealed tubes a t 130" for several hours with dilute sulphuricacid it jields benzaldehyde and phosphoric acid.The silver saltforms a white crystalline precipitate which blackens when exposed tolight and is inscluble in water and nitric acid but dissolves readilyin ammonia. The ethy7 salt is almost insoluble in water and is onlyslightly soluble in ether or chloroform but i t dissolves readily inethyl alcoliol from which it cryhtallises in brilliant prisms. It isslowly saponified by cold solutions of potassium hydroxide and if theliquid is acidified the free acid separates in crystals. With hotpotassium hydroxide the yeaction is more complex and benzaldehydeand phosphoric acid are obtained.When the ethyl salt is treated with acetic chloride it yields thecompound PO( CHPh*OAc),*OEt a viscous transparent substance,soluble in alcohol or ether from which it separates in very whiteci-ystals.The acetyl-derivative is slowly saponified by potash in thecold and if the product is acidified dihydroxybenzylenephosphinicacid separates and the solution contains acetic acid. With hot potash,the products are benzaldehyde phosphates and acetates.aniline on phthalide. w. c. w.Action of Hypophosphorous Acid on Benzaldehyde.Dihydroxybenzylenephosphinic acid is monobasic.C. H. B.On Mono- and Di-nitroparazobenzoic Acids. By Madame A.RODSIANKO (J. Rum. Chem. Soc. 1888 20 18-29).-The action ofnitric acid on parazobenzoic acid was studied and the productcompared with the nitro-compound obtained from azobenzoic acidby Zinin.Solid nitrotoluene is oxidised by chromic mixture toparanitrobenzoic acid and this on treatment with sodium amalga142 ABSTRACTS OF CHEMICAL PAPERS.yields parazobenzoic acid ; the latter after having been dried betweenblotting paper still contains 30-35 per cent. of water. It is treatedwith 16 times its weight of nitric acid of sp. gr. 1.535 graduallywarming the mixture until the temperature reaches 79' and all theacid is dissolved On adding water 90-94 per cent. of a solidproduct is precipitated. This is washed with water and recrystallisedsilccessively from glacial acetic acid and several times from alcohol.The product consists of nitrazobennoic acid ClaHE,(N02) N204 andforms a pale yellow crystalline powder consisting of rhombic scales.It is highly electric.It isinsoluble in water ether and benzene soluble in acetic acid and in26.2 parts of hot and 280.4 parts of cold alcohol. It forms two seriesof salts; the acid salts are stable but the normal salts are decom-posed by water with formation of acid salts. The normal potassiumsalt Ki,C,aH,(N0,)N204 + 3H20 loses its water at U O " and isdecomposed by carbonic acid yielding the acid salt. The calciumsalt CaC14H,(Pu'02)N,04 and the barium and silver salts have ananalogous composition. The ethyl salt obtained from the silver saltand ethyl iodide forms pale yellow rhombic scales melting at 98".Dinitroparazobenzoic acid is obtained when 30 parts of nitric acid.of sp.gr. 1.555 is employed for 1 part of azobenzoic acid and themixture heated nearly to the boiling point. It is purified like themononitro-acid and forms tufts of slender yellow needles. It decom-poses at 257" without melting. Like the mononitro-compound it ISsoluble only in acetic acid and in 16.5 parts of hot and 160.3 parts ofcold alcohol. Its stable normal salts have a composition corre-sponding with that of the potassium salt K2C14H,(N02),N,04 + 4H20.The calcium and barium salts contain 5 mols. H,O ; the silver salt isanhydrous. The ethyl salt) forms slender yellow silky needles meltingat 128". Finally azobenzoic acid obtained by the decomposition ofnitrobenzil (Zinin) was treated with nitric acid and a productobtained which proved to be identical with the mononitroparazo-benzoic acid described above.The two azobenzoic acids are there-fore identical. B. B.It does not melt but decomposes at 270".Reissert's Pyranilpyrok Acid. By R. ANSCH~TZ (Bey. 21,3252-3256) ; A. REISSERT (Bey. 21 3257).-Anschutz's paper is areply to one of Reissert's (Abstr. 1888 954). Reissert mentions thatthe most important evidence in favour of his views depends on theknowledge of the constitution of anilsuccinic and P-milpropionic acids,and that this point is not discussed by Anschutz.Nitro-derivatives of Isophthalic Acid. By A. CLAUS andS. WYNDHAM ( J . pr. Chem. [ 2 1 38 313-320).-Dinitroisophtkalicacid is formed when isophthalic acid (5 parts) is heated with fumingnitric acid (1 part) in a sealed tube for six hours at 150-180". Itis but little soluble in cold water more freely in hot water and inalcohol and ether ; it forms colourless needles or short prisms arrangedin papillary aggregates and containing 5 mols.H20 half of which islost over sulphuric acid ; the anhydrous acid melts at 215" (uncorr.).The sodizcrn and potassium salts (2 mols. H20) the barium saltN. H. MORQANIC CHEMISTRY. 143(7 mols. H,O) the calcium and ?nagnesium salts (4 mols. H,O) andthe lead and silver salts are described. As the same dinitro-compoundcan be obtained by nitrating symmetrical nitroisophthalic acid one ofthe nitro-groups is in the position 5 but the position of the otherremains an open question.Diarnidoisuphthalic acid C6H,(N~,),(COOH) obtained by reduc-ing the above acid crystallises with 1% mol.H,O in shining flatneedles of a very light-brown tint becoming darker on exposure tolight and not melting below 300"; its aqueous solution deposits ablack tarry matter when incautiously evaporated and acquires amusliroom-like odour after a time.Dibromisuphthalic acid obtained when symmetrical nitroisoplithalicacid is heated with bromine €or several hours at 300" in a sealed tube,crystallises in colourless needles melting at 155" (uncorr.) sparinglysoluble in water freely in alcohol and ether and subliming with thesame crystalliue form. The calcium and silver salts form anhydrouscrystals.Nitroisophthalic acid (NO COOH COOH = 4 1 31 may beobtained by oxidising 4-nitrometatoluic acid with potassium per-manganate ; it crystallises with 3 mols.H,O in small white needles,easily soluble in hot water in alcohol and ether. The anhydrous acidmelts at 246" (uncorr.) ; its sodium potassium (1 mol. H20) barium(4 mols. H,O) calcium (i mol. H20) and magnesium (6 mols. H20),lead and silver (7+ mols. H,O) salts are all described. A. G. B.Phenylglycinorthocarboxylic Acid Glycocine-derivatives.By J. MAUTHNER and W-. SUIDA (Monatsh. 9 727-735).-Instead ofemploying 2 mols. of the base to one of chlomcetic acid in the pre-paration of glycocine-derivatives as in the ordinary method theauthors replace the second molecule of the base which is neededto combine with the hydrochloric acid liberated by an equivalentquantity of a metallic carbonate whereby not only is material saved,but the reaction is hastened.Phmy Zg lycinorthocarbox!/lic acid CO OH*C6H4*NH* CH,*C 0 OH isprepared by boiling a mixture of anthranilic acid (25 grams) chlor-acetic acid (20.6 grams) sodium carbonate (32.8 grams) and water(1 litre) for several holm the water as it evaporates being replaced.After cooling the product is supersaturated with hydrogen chlorideacid and allowed to remain for one day when the acid separates as abright-yellow crystalline powder which melts with frothing a t 207".It dissolves readily in alcohol acetic acid and ether but is insolublein benzene and chloroform.The acid potassium salt C9H,N04K,crystallises from dilute alcohol in microscopic scales.The calciumsalt is anhydrous and furnishes aniline on distillation. The bariumsalt CgH,NOaBa 4- 2H20 crystallises in needles ; the silver salt,C9H,N04Ag4 is insoluble in water and the ethyl salt CgH,N04Et,forms an oil which crystallises on standing.If chloracetic acid (50 grams) soda (53 grams) and excess of ammoniaare boiled for 7-8 hours glycocine is formed (16 to 18 per cent. oftheory). If the ammonia be omitted glycollic acid (yield 75 percent. of theory) is the product. G. T. M144 ABSTRAOTS OF CHEMICAL PAPERS.Orthonitranilinesulphonic Acid and some of its Derivatives.By R. KIETZKI and Z. LERCH (Her. 21 3220-Y223).-Orthonitrani-linesulphonic acid (Goslich Abstr. 1876 i 929) is prepared bytreating acetanilidt? (1 part) with fuming sulphuric acid containing18 to 'LO per cent.of anhydride (3 parts) and ordinary sulphuricacid (2 parts). The calculated amount of nitric acid previouslymixed with an equal volume of sulphuric acid is then graduallyadded the whole being kept at 0". The product is poured on to alittle ice when it solidifies to a mass of yellow needles. It is ex-tremely soluble in water less so in alcohol or i n dilute sulphuric orhydrochloric acid. When the potassium salt is boiled with an excessof potash for a long time ammonia is evolved and the potassium salt,OK.C6H3(N02)-S031( (Kolbe and Graebe AnnaZen 147 76) isobtained.Nitrodiazobenzenesu~ponic acid NOz*C6H3<S63 N'N > obtained bytreating the aqueous solution of the amido-acid with hydrochloricacid and potassium nitrite cry stallises in slender light-yellow needles,dissolves sparingly in water and detonates rather violently whenheated.Orthop lzeny lenediam inesulp h onic acid C6H,( NH2),*S 03H is formedwhen the nitranilinesulphonic acid is rediiced with tin and hydro-cliloric acid.When exposed to air it becomes greenish-blue andgives a reddish-brown colour with ferric chloride. The acid is notidentical with Sachsse's acid (this Journal 1877 ii 7511 but possiblyis with the one prepared by Post and Hartung (Abstr. 1880,394).Ortho?iitrophenylh?jdruzineparasulphonic acid,is obtained by adding orthonitrodiaaobenzenesulphonic acid to a well-cooled strongly acid stannous chloride solution. It dissolves in waterand in aqueous alkalis and alkaline carbonates.TVhen reduced withhot acid stannous chloride solution the corresponding urnidoh ydrazine-sulyhonic acid is formed. The hydrochloride crptallises in plates,and dissolves readily in water but only sparingly in strong hydro-chloric acid. N. H. M.The Sulphonic Acid of Methyl Phenylcarbamate. Bg E.NOLTING (Ber. 21 3154-3155).-The compound obtained byHentschel (Abstr. 1885 792) by treating methyl phenylcarbamatewith fuming sulphuric acid is probably the acid,COOMe*NH.C6H4*S 03H.This substance can also be obtained by adding soda (1 mol.) to awarm aqueous solution of sodium sulphanilate (1 mol.) and methylchloroformate (1 mol.). The amidosulphobenzoic acid prepared byHentschel (Abstr. 1884 1016) is probably sulphophenylcarbamicacid SO3H.C6H4*NH*COOH.When methyl phenylcarbamate isheated at about 260" with lime aniline monomethylaniline dimethyl-aniline and carbanilide are formed. F. S. KORGANIC CHEMISTRY. 145Diphenic Anhydride and Orthodiphenyleneketonecarb-oxylic Acid. By C. GRAEBE and C. AUBIN (Aniialen 247 257-%8).-Diphenic acid is convered into diphenic anhydride <c,H:.co>O,by the action of acetic chloride or acetic anhydride (Abstr. 1887,589) also by boiling with stannic chloride or phosphorus trichloride,or by the action of phosphorus pentachloride containing oxychlorjdeat 120". Concentrated sulphuric acid zinc chloride and an excess ofboiling phosphorus oxychloride convert dipheni c acid into ortho-C H C Odiphenyleneketonecarboxylic acid <C6HI>C6H3.COOH.CO-Monomethyl and ethyl diphenates are prepared by boiling diphenicanhydride with methyl or ethyl alcohol. They crystallise in colourlessplates dissolve freely in alcohol and distil without decomposition.The ethyl salt melts at 88" and the methyl salt at 110". Dipherziochloride ClrE16C1 prepared by the action of phosphorus pentachlorideon the anhydride a t 180" is a crystalline substance soluble in benzene,ether and acetic acid. It melts a t 93-94" and distils withoutdecomposition. On reduction dipbenic chloride yields phenanthra-quinol which changes into phenanthraquirione by oxidation.Diphenic anhydride is converted into the anzinic acid,COOH.C6H~.CsH~.CONHz,by boiling it with ammonia. This substance melts at 193" and decom-poses on distillation yielding diphenirnide < c6H4*C0>NH.C6Ha'CO Theimide is deposited from hot alcohol in colourless needles soluble inchloroform. It melts a t 219-220". Warm strong ammonia convertsthe imide into diphenamide NH2.CO*C6H4*C6HI.C0.~H2. The amidenielts at 208-d09" and is insoluble in sodium hydroxide.Phenylhydrazine unites with diphenic anhydride forming ani&do-diphenccmic acid C20H1603N2 molting at 174". ,4t 'LOC)" the acidbegins to lose water and slowly changes into anilidodiphenimide,C6H4'Co>N-NHPh. This substance melts a t 150" and is insolublein alkaline carbonates.The salts of orthodiphenylcarboxylic acid have been previouslydescribed (Abstr. 1887 589). The acid yields a mono- and n tri-chloride on treatment with phosphorus pentachloride.The mono-chloride C1,H,OZC1 melts a t 128O and the trichloride a t 95". Thetrichloride dissolves in alcohol and the solution depo,sit,s crystals of thecomposition <g$>c6Hs*CoOEt. Reduction with zinc and aceticacid converts the trichloride into fluorenecarboxylic acid. Theacetoxime melts at8 263" and decomposes at a high temperature. The<CeH4*COhydrazone <C(N,HPh)>C6H~'COOH C6H4- crystallises in yellow needlesor prisms and is soluble i n alcohol and ether,decomposes at 210".It melts at 205" andr)rtho~zlorenecal.boxylic acid <c6HI>C6H3*COOH CH2 melts a t 175"146 ABSTRACTS OF CHEMICAL PAPERS.and dissolves freely in ether alcohol and acetic acid.salt melts at 64".The methylicHydroxyfluorenecarboxylic acid < zf/oE> C6H3.C0 OH preparedby the action of zinc-dust on an amuonLicaf solution of diphenylene-ketonecarboxylic acid is soluble in alcohol ether benzene chloroform,and in'hot water. The substance which Graebeand Mensching (Abstr.1880 8 1 2 ) described as a phthalejin ofdiphenic acid is a condensation product of phenol and diphenylene-ketonecarboxylic acid and is probably represented by the formulaIt melts at 203".C(CsH4QH),> C,H,.CO OH.On heating a mixture of resorcinol and stannic chloride at 115* ayellowish-brown crystalline powder is produced. The solution inalkali8 has a yellowish-red colour and exhibits an intense greenfluorescence. w. c. w.'C6Hp -Nitro-derivatives of Tetramethyldiamidodiphenylmethane.By P.VAN ROMBURGB (Rec. Trav. Chim. 7 226-235).-TetramethyZ-diamitiodi~henylmsthane was prepared by heatirig methylal anddimethylaniline with zinc chloride. It melt8 a t 9Uo gives a violetcompound with trinitrobenzene melting a t 114" and a dark redcompound with metadinitrobenzene melting a t 74" the first con-taining equal molecular proportions the second 2 mols. of theamine to one of dinitrobenzene. Added in acetic acid solution tonitric acid (sp. gr. 1*48-1-5) it is converted into tetranitrodimethyl-danitrumidodiyheny h e t h a n e OHz[ CGH,(NOz)z.NMe*N0z]2. This nitr-amine is a yellow crystalline substance which darkens in colour at210" and decomposes a t 217-2.?0". I t is nearly insoluble in alcohol,ether petroleum carbon bisulphide and chloroform dissolves readilyin acetic acid and acetone but is best recrystallised from nitric acid.Precipitated as a white powder from the nitric acid solution by theaddition of water and boiled with 12.5 per cent. aqueous potash itgives a brown solution which on evaporation was found to give offmethylamine.When boiled with phenol i t gives tetranitrodiriiethyl-dinmidodiphenylmethane an orange-coloured compound melting withdecomposition a t 250". It is slightly soluble in alcohol petroleum,and benzene but more soluble in acetone acetic acid chloroform andethyl acetate. When treated with nitric acid it is reconverted intoths nitramine.The latter when oxidised with chromic anhydride y.ields a com-pound exactly resembling that obtained by the nitration of tetra-methyldiamidobenzophenone ; on treatment with phenol this gives ateti*anitrodimethyldiamidobenzophenone melting a t 225". Admittingthe formula which the author proposed for the nitramine derivedfrom benzophenone that of the one now in question will be~02.~Me*C6H,(N02),*CHz*C,H2(N02)2~NMe*~o~.The compound obtaiiied from this by boiling with pheaol was alsooxidised in acetic acid solution with chromic anhydride and gave a4 3,5 1 2,6 ORGANIC UHERlTSTRP.147tetranitroaiamidobertznp7renone crystallising in small yellow needlesfrom acetic or phenol and melting with decomposition at 250-260".H. C.Action of Primary Aromatic Amines on Benzil. By F. X.BANDROWSKI (Monatsh. 9 685-694 ; compare Voigt Abstr.1885,1067).-Benzil forms condensation products with the amines whenthey are heated together in open vessels at 100-150". With anilineand orthotoluidine only monosubstituted but with paratoluidine anda-naphthylamine a mixture of both mono- aud di-substituted com-pounds were obtained. All the compounds of benzil described beloware characterised by not forming salts with dilute acids and by theease with which they are reconverted into their generators.Anilbenzil COPh.CPh:NPh melts at 105" and gives characteristiccolours with alcohohic potash (violet) and with cold concentratedsulphuric acid (blood-red turning to green).OrthotoliZbewziZ COPh.CPh:Pu'*C7H crystallises from alcohol inyellow plates which melt at 104" and readily dissolve in ether andbenzerie.Paratolilbenzil crystallises in yellow prisms melting at 116-11 7".ParaditoZiZbenziZ C,H,.N:CPh.CPh:N.C,H is a bright yellow crys-talline powder melting at ltjl" and more soluble in alcohol thanpara tolilbenzil.a-Naphthilbenzil COPh*CPh:N*CloH7 crystallises from alcohol ingolden-yellow needles melting at 1313-139". It dissolves readily inbenzene less readily in ether and with difficulty in light petroleum.Di-oc-naplit~ilbe~~z~l CloH,*N:CPh*CPh:N*CloH is insoluble inalcohol but crystallises from a mixture of benzene and light petroleumin dark yellow needles melting at 218-219".Orthotolilbenzoin OH*CHPh-CPh:N*C,H is obtained by heatingtogether equal quantities of benzo'in and orthotoluidine for three-quarters of an hour at 150".It crystallises from alcohol in lightyellow needles readily soluble in ether and melts at 141".G. T. M.Derivatives of Ethyl Phenacylbenzoylacetate. By S. KAPFand C. PAAL (Ber. 21 3053-3063). The compound melting a t142-145" obtained together with benzoic and benzylpropionic acidby hydrolysing ethyl phenacylbenzoylacetate (compare Abstr. 1888,839) is diphenacyl (diphenyl ethylene diketone) (compare Boltingand Kohn Abstr. 1886 349 ; &,us and Werner Abstr. 1887 827 ;and Hollemann Abstr. 1888 275). It can be obtained by mixingethyl phenacylbenzoylacetate (1 mol.) with a small quantity ofalcohol adding an 8 per cent. aqueous solution of potash (li mol.)and keeping the mixture for 8 to 10 days at the ordinary tempera-ture ; the whole is then filtered the residue extracted with cold ethylacetate to remove the unchanged ethereal salt and recrystallised fromalcohol or from a mixture of benzeue and light petroleum.The yieldis 20-25 per cent. of the ethereal salt employed.Diphenacy Zdihydruzone C2H4( CPh:N,HPh) prepared by boiling thediketone with phenylhydrazine crystallises from alcohol in slender,colourless needles melts at 180" with decomposition and is readilysoluble in ether benzene and hot glacial acetic acid. The impur148 ABSTRACTS OF CHEMICAL PAPERS.compound is unstable especially in the light. The dioxime,C2H4( CPh:N*OH),? prepared by boiling a dilute alcoholic solutionof the diketone with hydroxylamine crystallises from dilute alcoholin colourless needles or plates melts at 203-204" and is readilysoluble in glacial acetic acid alcohol ether alkalis and mineral acids,but sparingly in benzene and light petroleum.aa'-Diphenylfurfuran (Zoc.cit.) is obtained when the diketone isheated a t 130-150" with Concentrated hydrochloric acid. It givesa dark grey coloration with isatin and sulphuric acid and dissolves inconcentrated sulphuric acid forming a green solution which onheating changes to reddish-brown with a bluish-green fluorescence.Diphenacyl gives the same reaction with concentrated sulphuricacid.Dipk enyltetrahydrofurfuran O<CIIPh.CH2> C HP h*CH prepared by treatinga hot alcoholic solution of diphenylfurfuran with sodium is a colour-less viscid oil boiling a t 230-232". It is insoluble in water butmixes with most of the ordinary solvents in all proportions.2 5 Diplzenylthiophen CaSH2Ph2 obtained by heating diphenacyl(1 part) with phosphoric sulphide (14.parts) at 160-186" crystallisesfrom alcohol or acetic acid in yellowish or colourless plates melts a t152-153" is readily soluble in most of the ordinary solvents and distilsunchanged.When ethyl phenacylbenzoylacetate is heated at 150-2W0 withglacial acetic acid and excess of phosphoric sulphide an acid meltingat 216" probably diphenylthiophenuarboxylic acid is obtained.E t h y l aa-di,~henylficrfura.n-/J-carboxylate C1HPh20*COOEt is ob-tained when finely-divided ethyl phenacylbenzoylacetate is boiled withalcohol and excess of moderately concentrated hydrochloric acid.Itseparates from dilute alcohol in large crystals.Phenylacetylenebenzoylacetic acid (Zoc. cit.) yields a monobromo-substitution product which crystallises in colourless needles meltingat 200". When the acid is treated with phosphoric chloride in chloro-form or carbon bisulphide solution and the product poured into well-cooled methyl alcohol it yields a methyl salt which crystallises inorange needles and contains chlorine. A yellow crystalline htydr-azone Cz9H4,N40 is formed when the acid is warmed with phenj-1-hydrazine ; it melts a t about loo" is insoluble in water and resinifieswhen treated with most ordinary solvents. The acid also combineswith hydroxylamine.It shows the indophenin and Laubenheimer's reaction.E t h y l di~henyl~moline-~-carboxylate,C4NH,Ph,*COOEt [= 2 5 31,is obtained when ethyl phenacylbenzoylacetate is heated with ammo-nium acetate and glacial acetic acid. It crystallises from acetic acidin colourless needles melts a t 159" and dist'ils unchanged whenheated in small quantities.It is readily soluble in alcohol ether,benzene and glacial acetic acid sparingly in light petroleum andinsoluble in water. It dissolves in warm concentrated sulphuric acidwith a reddish-brown coloration which changes to reddish-violet witha blue fluorescence when the solution is heated more stronglyORGANIC CHEMISTRY. 1492 5-Diphenylpyrrolinecarboxylic acid (Zoc. cit.) melts at 216".The compound described as ethyl ocz-diphenylpyrroline-b-caaboxylate(Zoc. cit.) is the amide <Cph:CH NH'CPh>C*CONH2.aa-Diphenylpyrrolinecan be obtained by boiling ethyl diphenylpyrrolinecarboxylate withalcoholic potash by boiling diphenacyl with ammonium acetate andglacial acetic acid and by heating the diketone at 150-160" withalcoholic ammonia. It is also obtained by distilling diphenylpyrrole-carboxylic acid over heated lime but considerable decomposition takesplace (compare Baumann Abstr. 1887 735 and Holleman Eoc. cit.).I t gives the same coloration with concentrated sulphuric acid as theethereal salt described above.Et hy 1 trip h my@ yrrolinecarbox y late,C,NHPh,*CO@Et [Ph, COOEt = 1 2 5 31,prepared by boiling ethyl phenacylbenzoylacetnte with aniline andglacial acetic acid crystallises from glacial acetic acid in yellowish,slender needles melts at 169-170"? and is only sparingly soluble inmost ordinary solvents.CJTHPh3*C OOH prepared byboiling the ethereal salt with alcoholic potash crystallises fromglacial acetic acid in needles melts at 273" and is rather sparinglysoluble in most of the ordinary solvents.It sublimes with only slightdecomposition and gives a reddish-brown solution when heated withconcentrated sulphuric acid.2 5-Triphenylpyrroline (compare Baumann Zoc. cit.) and a com-pound melting at 140-142" are obtained when the preceding com-pound is distilled over heated lime. The substaiice melting at140-142" crystallises in colourless needles or plates and has the samecomposition as triphenylpyrroline.Trip heny Zpyr~o Zinecarbox y Zic acid,F. S.K.Derivatives of a-p-Dichloronaphthalene. By P. HELLSTR~M(Ber. 21 3267-3271).-DinitrodichEoronaphthalene C,oH,CI,(NO,)I,is prepared by the action of a mixture of fuming nitric and strongsulphuric acids (equal parts) on dichloronaphthalene. It crystallisevin spherical aggregates of bright yellow slender flat needles meltsat 169*5" and dissolves very sparingly in ether very readily in boilingglacial acetic acid. When distilled with phosphorus pentachloride acompound possibly hexachloronaphthalene is obtained which crystal-lises in long bright yellow needles melting at 135-136".a-P-Dic~~lorona~hthaq~~~none CloH402C12 obtained by adding asolution of a-P-dichloronxphthalene in glacial acetic acid to asolution of chromic acid i n glaciaJ acetic acid (Guareschi Ber.19,1154) melts at Nl" sublimes in long yellow needles and is rathersparingly soluble in alcohol. It yields with hydroxylamine a com-pound which crystallises in reddish-brown needles and carbonises at215". When a solution of the quinone is treatled with aniline dichlor-anilidonaphtliapuinone CloH302Cl,~~ HPh is formed. It is a red,crystalline substauce melts at 254-255" and is very sparinglysoluble i n glacial acetic acid less soluble in alcohol ; it sublimes incarmine-red needles with a greenish- bronze lustre150 ABSTRACTS OF CHEMICAL PAPERS.The above results show that a-/I-dichloronaphthalene is not identicalwith the so-called a-dichloronaphthalene. N. H. M.Disubstituted Naphthalenes from the Isomeric Chloro-phenylparaconic Acids. By H.ERDMANN and R. KIRCHHOFF(Annalm 247 366-3SO).-The isomeric chlorophenylparaconicacids yield chlor-a-naphthols on distillation just as phenylparaconicacid yields a-naphthol (Abstr. 1884 906). The naphthols are con-verted into the corresponding dichloronaphthalenes by the action ofphosphorus pentachloride. Metachlorophenylparaconic acid yieldsthe 1 1'-chloronaphthol.Ortho- and para-chlorobenzaldeb ydes are prepared- by convertingthe chlorotoluenes into chlo~obenzal chlorides and decomposing theproduct by the action of anhydrous oxalic acid at 160". The meta-chlorobenzaldehyde is obtained from metamidobenzaldehyde. Whenthe chlorobenzaldehydes are heated at 120-140" with succinicanhydride and potassium acetate in molecular proportion chloro-phenylparaconic acids are produced.The ortho-acid C,,H&lO + lQHzO crystallises in needles andmelts at 146-147".100 parts of boiling water dissolve 1.4 parts ofthe acid. The para-acid crystallises with Q mol. H,O. 1 part byweight of the acid dissolves in 100 parts of water at loo" and in500 at 16". The acid melts at 119-120". The meta-acid formsprisms and melts at 160-161".Chloronaphthol [Cl OH = 4 1'3 crystallises in plates and meltsat 131.5". Bothsalts are crystalline.The 2 1'-chloronaphthol melts at 123" and the picrate at 139".The acetate is an uncrystallisable oil. R y the action of ammoniumcalcium chloride at '260" the chloronaphthol is converted into chloro-naphthylamine. The hydrochloride melts a t 235-239" and yields acrystalline precipitate with platinum chloride.3 1'-chloronaphtholcrystallises in prisms and melts at 94". The acetate forms rhombicplates and melts at 47". The picrate crystallises in needles andmelts at 165".The three dichloronaph thalenes obtained by the action of phos-phorus pentachloride on the chloronaphthols have the followingmelting points :-C1 C1 = 4 1' melts at 107" and is identical with 1 4' dichloro-naphthalene ; 2 1' dichloronaphthalene melts at 61.5" ; and 3 1' at48". The two last compounds have been previously described byCleve and others. w. c. w.The acetate melts at 53" and the picrate at 160".Dimethylea-Naphthylamine and DiethyL-Naphthylamine.By P. FRIEDLANDER and P. WELMANS (Ber.21 3123-3130).-Di-methyl-a-naphthylamine (Hantzsch Abstr. 1880 813) boils at272-274" (uncorr.) and is very strongly refractive.Amidodimeth y lnaphthylamine NH2*CIoH6*NMez is prepared byreducing the nitroso-compound or from the azo-derivative. It dis-solves readily in the usual solvents and in dilute mineral acids anORGANIC CHEMISTRY. 151separates from the aqueous solution as an oil; it quickly becomesresinous when exposed to air. The acefyl-derivative crystallises inpointed plates melts at 194-195" and dissolves readily in alcoholand glacial acetic acid sparingly in ether.Nitrosodimethyl-a-nuphthylnmine NO*C,,H6.N1\fe2 is obtained byadding a strong solution of sodium nitrite (7 grams) to dimethyl-naphthylamine (17 grams) dissolved in hydrochloric acid (30 c.c.) inpresence of ice.The solid product is freed from adhering liquid bysuction dissolved in cold alcohol and precipitated with ether. Thesubstance which is probably the hydrochloride of the base is readilysoluble in a little water but is decomposed when the solution isdiluted. The free base is precipitated as an oily precipitate whichgradually solidifies when sodium carbonate is added to the solution ofthe hydrochloride. It quickly decomposes into dimethylamine andnitrosonaphthol.Dimeth y lnap ht h!y lam inecarboxyl ic acid COOH-CInH6-NMe2 preparedby heating the base (2 rnols.) with carbonyl chloride (1 mol.) at60-70" for three to four hours crystallises from alcohol in white,pointed needles melting at 163-165".(COOH~CloH,yNMe2),,H,PtC1,,The ylatinochloride,crystallises in yellow needles.The salts of the alkalis are readilysoluble and do not crystallise well.Brornodimet h y lnaphthy larnine h ydrobromid e cryst allises from waterin presence of hydrogen bromide in quadratic plates of a silverylustre. The free base is a strongly refractive oil which boils at 260"with decomposition.Dimethy1naphthylaminesulp;ho.nic acid SO3H-CloH6*NMe2 preparedby heating the base with sulyhuric acid (4 parts) at 150" crystallisesin lustrous plates dissolves sparinqly in water readily in ether andalcohol. The sodium potassium calcium and barium salts form orys-talline precipitates.Diniethylnaphthylamine is readily attacked by nitric acid yieldinqtwo nitro-componnds melting respectively at 87-88" and 126-128".Tetmrnethyldiarnidodinaphthylphenylmethane CHPh(CloH6*NMea)2,is obtained by heating dimethylnnphthylamine (2 rnols.) benzaldehyde(1 mol.) and zinc chloride at 110-120" dissolving the product inthe smallest possible amount of benzene and adding ether. Itseparates in lustrous crystals melts at 188-189" dissolves sparinglyin alcohol and ether readily in glacial acetic acid benzene carbonbisulphide and in dilute mineral acids.The platinochZm*de issparingly soluble.Heaanzethyltriarnidodinaphthylp henylmethane,NMe2*C6H4*CH( C10H6*NMe2)2,prepared by the action of dimethylparamidobenzaldehyde on dimethyl-naphthylamine forms white needles melting at 178-179".Diethyl-a-napht hylamine is readily obtained by heating naphthyl-amine with aqueous soda and ethyl bromide or iodide at 110-120",and is purified in a manner similar to dimethylnaphthylamine. Itforms a clear oil which gradually becomes brown and boils a152 ABSTRACTS OF CHEIlICAL PAPERS.283-28.5" (uncorr.).Sp. gr. = 1.005. The subhate crystallises inthick prisrns readily soluble in water. The carbozylic acid preparedby the action of carbonyl chloride on the base Iorms white platesmelting at 3 66".When naphthylamine is heated with ethyl bromide (1.5 part) andalcohol a t 120" (Smith Trans. 1882 180) a product; consistingessentially of monethylnaphthylamine is formed. N. H. M.a-Naphtholbidiazobenzene and a-Naphthylaminebidiazo-benzene. By C. KROHN (Rer. 21 3240-3242).-a-Naphtholbi-dinsobensene OH*CIoH5(N2*Ph)z [OH N2Ph N2Ph = 1 2 41 isreadily obtained by adding a solution of diazobenzene chloride(2 mols.) to a slightly alkaline solution of a-naphthol (1 mol.).After 12 hours the compound separates as a brown powder andis extracted with boiling dilute alkali.It is purified by crystallisa-tion from aniline and will then crystallise well from any solvent.It melts at 183" and dissolves very readily in chloroform readily inether benzene. and in boiling aniline sparingly in light petroleum,alcohol and glacial acetic acid ; the solution in strong sulphuric nuidis dark-green. When reduced with tin and hydrochloric acid anilineand diamido-2-naphthol are formed.a-Naphthylanzinebidiazobenzene [NH NzPh N2Ph = 1 2 41 isprepared by adding a strong aqueous solution of diazobenzene chloride(1 mol.) to an alcoholic solution of naphthylazobenzene (1 mol.) con-taining sodium acetate; in 12 hours the reaction is finished.Itcrystallises from aniline in red needles melts at 189" and dissolve8readily in chloroform sparingly in most other solvents. The acetyl-derivative is yellow arid melts a t 265" ; the solution in sulphuric acidis brown. When a-naphthylaminebidiazobenzene is reduced with tinand hydrochloric acid aniline and a triamidonaphthalens are formed ;the latter reacts with phenanthraqninone in presence of glacial aceticacid yielding an azine which dissolves in Rtrong sulphuric acid,forming a green solution. The azo-group is therefore in the ortho-position to the amido-group. N.H. M.Naphthoic Acids. By A. G. EKSTRAND ( J . p r . Chem. [2] 38,241-285 ; compare this vol. p. 52).-The acetyl-derivative of amido-a-naphthoic acid (m. p. 2 11') forms microscopic needles meltingabove 280"; the calcium salt crystallises with 3 mols. HzO in verysoluble violet needles ; the hydrochloride forms anhydrous violetneedles soluble in warm water and alcohol melting above 290" ; thesulphate and nitrate are also described. When the acetyl-derivativeis treated with nitric acid (sp. gr. 1-42) nitrncetylamido-a-naphthoic;acid is produced ; it melts a t 259" and is easily soluble i n alcohol.When chlorine is passed through R glacial acetic solution of theSame amido-a-naphthoic acid containing some iodine a mixture ofamm oniurn chloride and dichloroii ap ht haquinonecar box y Zic acid,CloH30aC1,*COOH is obtained. This acid crystallises in violetneedles melting at 255" ; when treated with a,mmonia it is convertedinto red needles of o diammonium salt ONHI.CloH3O2Cl*C0ONH~ORGhSlC CHEMISTRY.153of ch 101.hyaro~yna~hthaquinonRcarboxylic acid. From this the acid isobtained by heating with sodium hydroxide solution until allaniuionia is expelled and then adding hydrochloric acid ; i t crystal-lises in orange-yellow rhombic tables melting a t 246"; the acidt~mmo7~iui1 salt is obtained by the action of mineral acids on thediamni oniu m salt.Ck lo?-rnr tm- a-nap hthoic acid obtained f i-om chlor-a-na pht hoic acid(1 l ' ) crystallises i n broad prisms melting at 227" ; its ethyl saltmelts a t 84".By reduction this acid yields chloramido-z-.ncxphthoicacid which crystallises i n needles beginning to melt at 210" but notfully melted until 285" ; its hydrochloride is described.Dichloronifro-~-na~~~t720iC acid is obtained from dicliloro-a-naphthoicacid (COOH C1 C1 = 1 1' 47 and melts a t 165"; it has a verybitter taste.The sodium salt of dinitro-a-naphthoic acid of melting point 265"(Abstr. 1884 1361) crystallises with 6 mols. H20 arid the bariumsalt with 2$ mols. H20 ; the calcium salt is soluble 111 138 parts ofwater at the ordinal y temperature. The compound formed whenthis acid is reduced with hydrogen sulphide in a n ammoniscal solution(Abstr. 1886 949 ; 1887 373) contains sulphur as part of the mole-cule ; i t would thus appear to be a sulphide of dicxzinerqhthoic acid,S[ <$>CI,H,.COOH],. When th6 dinitro-acid is reduced with tinand hydrocl~loric acid dianiidonaphthalene is formed and at the sametime if the acid is first dissolved in glacial acetic acid a black powderwhich appears t o be di-imido-a-naphthoic acid COOH.C,,H,< NHThe ethyl salt of trinitro-a-naphthoic acid (m.p. 283") crystallisesfrom alcohol in small brown prisms which melt at 131"; the calciimsalt crystallises in brown laminzt or needles with 5 mols. H,O.When nitro-a-naphthamide (Abstr. 1886 948) i s reduced with t i nand h j drochloric acid chZoronaphthostyvi1 is produced ; it crystallisesin green or yellowish-green needles which melt a t 265" and sublime.ChZoronaphthoZacfone ClaH,CIOCO (compare Abstr.1886 716) isformed when chloimine is passed through a carbon bisulphide solutionof naphtholactone containing some iodine ; it melts a t 184-185" ;when it is dissolwd in weak soda solution and hydrochloric acidadded slender needles melt'ing a t 190-191" are obtained ; these arcc h l o r h y d r o z y - a - r ~ ~ ~ l ~ t h o i ~ acid. The rulciurn salt is anhydrous. If thenaphtholactone is dissolved in nitric acid (sp. gr. 1.42) and SotUefuming acid added rzitrona~htholacto?re is formed ; i t cryst:illiqes fromglacial acetic acid in slender yellow needles melting at 242" audsparingly soluble in alcohol ; by treating it like t h e chloronaph tho-lactone a nitrohydvoxytIaphthoic acid is obtained in rhombic tables,melting a t 242" ; its calcizcm salt contains 5+ mols.H,O.By m ~ .PALMAER (Ber. 21 3260-3664) .-Nitronaph thalene is heated ou awater-bath n i t h ordinary sulphuric acid (2 parts) and fuming acid(1 p a r t ) ; after 10 hours the pi*oduct is pourvd into water whenthe a-sulphonic acid separates. The filtrate is neutralised with chalk. NH>A. G. B.Action of Sulphuric Acid on a-Nitronaphthalene.FOL. Lvr. 131 ,4BSTRACTS OF CHEJIICAL PAPERS.and evaporated down; on cooling the calcium salts of the a- and&acids separate. The mother-liquor from the calcium salts is treatedwith potassium carbonate and the potassium salts converted intochlorides. On crystallising from various solcen ts two chlorides,N02*CloH6*S02CI melting respectively at 167" and 126" were separated.The chloride of higher me1 ting point forms slender ye1lowic;h needles,sparingly soluble in glacial acetic acid; when heated with water inclosed tubes the acid is obtained in readily soluble needles.Theethyl salt NO,.C1,H,*SO,E t forms thin yellow needles melting at106-107". The amide NOz*CIoH6*S020NH2 crgstallises in small,yellowish-white needles melting at 228". When the chloride is dis-tilled with phosphorus pentachloride dichloronaphthalene meltingat 62' is formed. The chloride is therefore a derivative of the&acid (a-nitro-&sulphonic acid). The potassium salt NO2.C1,,H6*SO3R-t 4H20 fornis very readily soluble yellow needles ; the sodium saltcyystallises in spherical aggregates of needles ; the silver salt crystal-lises in readily soluble well-formed needles ; the barium salt (with31 mols.H,O) forms groups of needles ; the anhydrous barium saltdissolves in 9.1 parts of boiling water and in 377 parts of water at17". The calcium salt forms long soft needles very soluble; thelead (with 3 mols. H20) naagnpsium (with 9 mols. H,O) rrnanga*nese(with 10 mols. H,O) copper (with 8 mols. H,O) and zinc (with10 11101s. H,O) saZts were also prepared.The sulphochloride me1 ting at 126" forms monoclinic crystalsiden tical with the chloride of /3-nitronaphthalenesulphonic acid ;a b c = 0.9956 1 0.8308 ; ,@ = 81" 28'. N. H. M.6,-Amidonaphthalenesulphonic Acid. By P. T. CLEVE (Ber. 21,NH2*CIoH6*8 03K,and the amnioniisn salt are very readily soluble ; the sodium salt formsreadily soluble scales; the silver salt with 1 mol.H,O separates inwhite microscopic needles ; the calcium and barium (with 1 mol. H,O)salts are readily soluble and crystallise respectively in needles andthin plates ; the lead scrlt forms very lustrous prisms.inrather large yellow crystals.SO,.NH + H20 p'e-pared by reducing the nitrosulphonamide with hydriodic acid,crystallises in small groups of lustrous needles melts at 131" anddissolves readilg in dilute hydrochloric acid. The hydrochloride formssparingly soluble yellow prisms.3271-3276). Potassium r-amidoiia~htltalenesulp~~t~ate,7- Uiazonaphthal enesulphonic acid CloH,< N:N > cry stalli sesy- Arnidon aphtli aleuesulp honamide NH2* Cso3The acetyl-derivative,NH2.S 02*CloH,.NHAc,crystallises from boiling water in tufts of needles which melt a t220-221".The c a r b a d d e NH2*CO*NH.Cl,H,.S0,*NH.C0.NH isformed by the action of potassium cyanide on the hydrochloride ofthe ttmide. It is amorphous melts at 273O is readily soluble inaqueous soda almost insoluble in waterORUANIO CHEMISTRY. 155r-Chloronaphthaleiae sulphochloride c ~ c 1 ~ s 0 c ~ is prepared byheating the diazosulphonic acid with hydrochloric acid neutinalisingthe product with potassium caxbonate and treating the potassiumsalt with phosphorus pentachloride. It is crystallised from lightpetroleum. I t melts at 106". Potassium chloronaphthalenesulphonatecrystallises in thin lustrous scales rather soluble in boiling water ;the silver salt forms small stellate gronps of needles ; the barium salt,with 3 mols.HzO forms very sparingly soluble microscopic needles.The ethyl salt crgstallises from alcohol in long needles melting at,76-79". The amide forms small triangular scales melts at 168',and is very sparingly soluble in water. N. H. 1111.6.Amidonaphthalenesulphonic Acid. By P. T. CLEVE (Ber. 21,3264-3267) .-Yotassiuw 6-a~~zidonu~hthnlenesulphonate)NH2.C ,OH,* S O,K,forms very soluble thin scales the sodium salt (with + mol. H,O)forms readily soluble thin needles ; the nmmonizcrn salt crystallises invery soluble thin plates ; the calcium salt (with 2 mols. HzO) is areadily soluble powder and becomes quickly coloured when exposedto air; the barium salt crystallises in rather sparingly soluble flatneedles.The zinc salt (with 4 mols. HzO) forms lustrous yellow,rather sparingly soluble well-formed needles ; the naqnesium lead,and silver salts are also described. The diazo-acid C10H6N2803 prf-pared by the action of nitrogen trioxide on the anhydrous acidsuspended in absolute alcohol is a powder. When aqueous alcohol isused an intensely violet dye of the formula+ 2+Hz0is obtained ; this is soluble in water and becomes brown when treatedwith alkali. The sulphonamide NH,.C,oH,.SOz*NHz is prepared byboiling the nitrosulphonamide dissolved in glacial acetic acid withhFdriodic acid ; i t crystallises in slender yellowish needles andmelts at 181". The hydvochloride NB z*S02*CloH6*NH2,HC1 + H,O,forms slender needles ; the hydriodide forms lustrous yellowishneedles soluble in water and alcohol ; the acetyl-derivative,NHAc*C,oH,j*SO2*NHZ,crystallises from boiling water in slender white needles melting at213".The carbamide NHa*CO-NH*CloH6*SO2*NH*CO*NH2 is pre-pared by the action of potassium cyanate on the sulphate of theamide ; it is an amorphous powder melts at 225" and dissolves verysparingly in water alcohol glacial acetic acid &c. readily inaqueous soda.Amidothionaphthol 2CloH6*NHz*SH + EtOH is obtained by heatingthe amide with hydriodic acid and phosphorus; the thin lustrousplates of amidothionaphthol hydriodide are treated with ammoniaarid the oil dissolved in alcohol. It separates in sparingly solubleneedles melting at 127".N. H. M.m 156 ABSTRACTS OF CHEMICAL PAPERS.Constitution of Isomeric Naphthalene-derivatives. Part 3.ag-Disubstituted Compounds. By H. ERDMANN (Annalen 247,306-3661) .-The naph tliylaminesulphonic acids yield a- or /3-naphthyl-arnine on the elimination of the sulphonic groups and a- or /%naphtha-lenesulphonic acids on the elimination of the aniide-groups. Thedisubstitution products of naphthalene are divided into four classesfor the purpose of clnssifica tion namely 3-o~~-na~hthylaminesulphonicacids ; S-PP- ; 4-a-j!- ; and 4-/3-a-naphthylaminesulphonic acids.I n the preparation of ar-nitronnphthalenesulphonic acid [I 4'1from a-nitronaphthalene by Cleve's process the more soluble isomeride[l 1'1 is obtained as a bye-pi*oduct.The properties of [ 1 41 az-naphthylaminesulphonic acid havebeeh described by Pirin (as naphthiorzic acid) (Annalen 78 31) andby Witt (Abstr.1586 364). The author has previously shown(Abstr. 1888 %90) that the acid which Wit+ (Abstr. 1886 554)obtained by the action of fuming sulphuric acid on a-nnphthylamine-hydrochloride is the [ 1 4'1 nnphthylaminesulphoniu acid. The[l 1'1 acid is obtained from SchBllkopf's patent iiaphthylaminesul-phonic acid S which consists chiefly of the sparingly soluble sodiumsalt of this acid. 238 parts ofboiling water or 4800 parts of water at 21" dissolve 1 part by weightof the acid. The cold aqueous solution produces a violet colorationin solutions of auric or ferric chloride.The sodium salt crystallisesin compact tables or plates and the potassium salt crystnllises inplates. One litre of water dissolves 26.7 grams of the sodium salt a t100" and 11.3 at 24"; also 149 grams of the potassium salt a t 100"and 35.6 at 19". The lead salt chrystallises in plates and the silversalt in feathery crystals. Benzaldehjde unites with the sodium saltsof the aa-naphthylaminesulphoiiic acids forming sodium benzal-naphthylaniinesulphonate. The sodium salt of the [l 41 acid crystal-lises with 1 mol. H20 in golden plates the [l 4'1 salt is whitre,cont'ains 2 mols. H20 and is distinguished from the preceding salt byits ready solubility in water. An analogous [l 1'1 compound is n dformed.Dilute sulphuric acid a t 180" converts each of the three isomericroc-naphthylaminesulphonic acids into a-naphthylamine.I n preparingthe diazo-compounds the sulphonic acids must be in a finely dividedstate the solutions must be cold and strongly acid and during theoperation the nitrous acid must be present in slight excess. The[l 41 diazonaphthalenesulphonic acid is jellow the [I 4'1 is grey,and the [l 1'1 forms greenish-yellow prisms. The latter compoundis distinguished from the others by melting without detonation.Reduction with tin and hydrochloric acid converts the diazo-com-pounds into a%-naphthyl hydrazinesulphonic acids. The [ 1 41 acidforms white needles soluble in hot water but more freely soluble inhot hydrochloric acid. The sodium salt C,,,H6(N2H,)*SO3Na + 4H10,crystallises in plates.The [l 4 ' j acid forms plates or groups ofneedles. Its sodium salt crystallises with 39 mols. H20. The[l 1'1 acid is deposited in slender plates. The potassium aridsodium salts are anhydrous. The latter is chnracterised by itssparing solubility in water. The ammonium salt is freely soluble.The pure acid forms white needlesORQSNIC CHEMISTRY. 157The three isomeric acids yield a-naphthalenesulphonic acid on boilingwith an acid solution of cupric chloride.The 1 4- and 1 4'-nLcphtholszclp7ionic acids are prepared by dis-solviiig the corresponding diazonaphthaleiiesulphonic acids in boilingsulphuric acid diluted with four times its weight of water. Theformer has been described by Neville and W inther (Trans. 1880 632).The latter is a deliquescent crystalline substance and melts between110' and 120".Under similar conditions [l 1'1 diazonaphthalene-sulphonic acid yields an anhydride naphtkosultons C1,H6<-'->. Thesultones bear the same relation to yhydroxysulphonic acids that thelactones do to y-hydroxycarboxylic acids. Naphthosultone crystallisesin prisms melts at 154" and boils above 360" with partial decompo-sition. It is soluble in chloroform and in warm benzene. A t theordinary temperature alkalis do not act on the sultone but at 130"alcoholic ammonia converts it into the ammonium salt of [l 1'3naphtholsulphonic acid OH*C,oH6*SOsNH,. The ammonium salt isfreely soluble in water and the solution gives a precipitate with leadsalts and also on boiling with an excess of scdium hydroxide thebasic sodium salt C,,H,SO,Na + l&H,O.The free acid crystalliseswith 1 mol. HzO and produces with ferric chloride a deep green color-ation changing to red.The conversion of [ 1 41- and [I 4'1-naphthylaminesulphonic acidsinto the corresponditig dichloronaphthalenes has been previouslydescribed by the author (Abstr. 1838 290) but the [l 1'1-diazosul-phonic acid on treatmenl with phosphorns pentachloride yieldschZoroiinphthosuZto~~e Cl0H5C1SOs. This compound forms yellowneedles and melts a t 174-175". It is not attacked by alkalinesolutions a t the ordinai-y temperature.[ 1 41-Dihydroxynaphthalene is identical with a-naphthahydro-quinol ; [ 1 4'1-dihydroxynaphthalene has been described byBernthsen and Semper (hbstr.1887 674). The [l 1'1-dihydr-oxynaplithalene is obtained from nnphthosultone by fusion withpotassium hydroxide. I t crystallises in needles or plates and melts at157-138" and dissolves freely in ether benzene and toluene. Thedincetute C,H,( Ohc) melts a t 147-148".Two au-dinitronaphthalenes are known; [l 4'1 melts at 218" and[I 1'3 a t 170".Aguiar (Ber. 7 309) has described the preparation and propertiesof [l 4'1- and [l 1'1-diamidonaphthalenes from the correspondingS 0 2dinitronaph t halenes. w. c. w.The Dextrorotatory Terebenthene. By L. PESCI (Chem. Centr.,1888 1097-1098 fi-om Ann. Chirn. Fawn. 7 353-358) .-Theterebenthene was obtained from American turpentine by fractionat-ing in a vaciium and was found to be the principal product; sp.gr.= 0.8641 boiling point 156-157'. Specific rotation [a]= =+ 1394.5". The American turpentine contains also 1aevorotatoi.y sub-stances.Nitroterebenthene was prepared by treating the terebenthene wit11potassium nitrite and dilute sulphuric acid the green oily produc158 ABSTRACTS OF CHEMICAL PAPERS.was shaken with ammonia washed with dilute hydrocliloric acid,and distilled twice in a current of steam. I t is a yellow liquid,having the odour of peppermint oil. Sp. gr. 1.0499 ; specific rotation,[z]D = +2*984. By reduction with zinc and acetic acid the sameamidoterebenthene C10H,5NH3 was obtained as the author preparedfrom the I~evorotatory terebenthene. The hydrochlorides of bothshow the same specific rotation [a] = -48.508" and - 48.629".The hydrochloride of lceuoterehenthene possesses the specific rotation[a]D = -30*687" melting point 125".Lcevoterebenthene hydrobroinide :specific rotation [ a ] = -27.802" and melting point 87".Dextroterebenthene hydrochloride and hydrobronaide are optically in-active. Their melting points are 125" and 91" respectively. Thesefacts go to prove the non-identity of the two terebenthenes.Hydroxycamphoronic Acids. By J. KACHLER and F. V. SPITZER(Monatsh . 9 7O8-726) .-The two isomeric hyclroxycamphoronicacids formed by the action of aqua regia on camphoronic acid car-respond in their crystalline form with the two modifications whichKachler obtained by heating camphoronic acid with bromine and sub-sequent treatment with water.Further investigations of the com-pounds obtained by the action of bromine show that they are notchemically identical as previously suggested. I n order to isolate theisomerides the mixture of acids dissolved in a small quantity of warmwater is treated with aqueous baryta until the solution gives only afeebly acid reaction. Ammonia is added until the solution is distinctlyalkaline and the mixture shaken for some time when bibasic bariuma-hydroxycamphoronate separates out the /3-salt remaining in solution.ac-Hydro.cZ/cam~horonic acid C9H1407 crystallises in monoclinicplates or prisms. It is only slightly soluble in ether dissolvesreadilyin cold water a n d alcohol softelis a t loo" and melts a t 216.5" (corr.).On long exposure to air or more quickly over sulphuric acid thecrystals lose water and are converted into the anhydride CgH,,O,,which on heating loses more water forming the anhydride CgHlo05.This is a crystalline powder which dissolves readily in alcohol andwater and melts a t 135-137'.Botjh anhydrides are reconverted intothe acid by boiling with water.. The salts of the a-acid are mostlyeasily soluble in water. The acid potassium salt CgH,,K07 crys-talliscs in stout needles the dipotassium salt C9H1,K3O7 + +H,O,in scales; when heated a t loo" the latter yields the compoundcgH&06. The calcium salt C~RRII",CRO~ + 4&0 crystallises inbundles of needles ; the barium salt CgH1,BaO7 in thin plates only,slightly soluble in water ; the silver salt CgH,,Ag207 + H,O formsminute crystals ; the copper and lead salts are anhydrous.All theabove-mentioned salts in the anhydrous condition lose the elements ofa molecule of water when heated. The ethyl compound CgHllEt06,crystallises in rbombic plates melting a t 158" (corr.). I f heated itgives the anhydride of a-hydroxycamphoronic acid and alcohol and onpassing ammonia through the ethereal solution the salt C6HloEt06.NHI,crystallising in needles melting a i 168-170" is formed./3-Hypoxycamphoronic crcid is not so soluble as its isomeride.When air-dried it has the formula C9H1107 melts a t 250.9" (corr.),J. W. LORGANIC CHEMISTRY. 159but loses water on heating forming an anhydride and furnishes mono-,di- and tri-basic salts of which the tribasic salts of lead and bariumare insoluble. The potassium salt CgH,,K,07 + +H20 is hygroscopic.The barium salt C9H12Ba07 + 4H20 crystallises in needles.Theethyl-derivative C,H,,F to forms needles melting at 158.5-159.5"(cow.) and resembles its isomeride forming with ammonia the com-pound C,H,,EtO,*NH melting a t 165".The authors find that when camyhoronic acid is heated withbromine no bromo-derivative is produced but the above-mentionedanhvclrides which on treatment with water yield a mixture of a-and /3-hydroxycamphoronic acid. G. T. &I.Syringin. By G. KORNER (Chenz. Cenfr. 1888 1098-1099 fromRend. R. Inst. Loinbardo [2] 21 563-572).-The author finds thatsyringin formerly considered as a glucoside is hydroxymethylconi-ferin C17H2107.He prepares it according t o Kromaycr's method( D i e Bztterstofe 1861 56). It crystallises from water in long,slender white needles which are only sparingly soluble in cold water,but readily in hot. It contains water of crystallisation which is given off:rt 100". Melting point 191-192". It does not form insoluble corn-pounds with solutions of metallic salts ; it reacts with mineral acidssimilar17 to coniferin. By the action of emulsin syringin is split upinto dextrose and syringenin OH*C,H,( OMe,)2*C,H4*OH ( h y d r o q -nzethylconiferyt dcohol) ; the latler resembles- coniferyl alcohol.By oxidising syringin with potassium permanganate g Zucosyringicacid C15HL0010 is formed crystallising from water in slender colour-less needles with 2 mols.H,O. It is sparingly soluble in cold water,readily in hot. Melting point about 208". When crystallised fromalcohol it melts a t 214". Thus prepared it contains no combined water.The lead salt is but little soluble ; the salts of potassium and bariumcrystallise in needles. By heating glucosyringic acid with dilutesull'huric acid it splits up into dextrose and s!/ringic acid CgHl,05.This decomposition is also effected by the action of ePrmlsin at SO".By the oxidation of sgringin with cold very dilute chromic acid,~ZucosyringinnIdeh~jcle is formed; it is soluble in water but onlysparingly in alcohol and insoluble in ether. It combines with phenyl-Iiydrazine the compound crystallising in needles and melting a t 156'.The aldoxinie is decomposed by emulsin or dilute sulphuric acidinto glucose and syri7igi.riaL~eJzytde C9H1004 which has the smell ofvanilla.It reacts readily with phenylhydrazine and hydrogensulphites forming soluble compounds. Syringic acid is sparinglysoluble in cold water more readily in hot water soluble in alcohol.I t is monobasic and melts a t 202". The barium salt crystallises with3 mols. B,O. The methy1 salt CgH,05Me + H20 is soluble in hotwater and melts a t 83.5". Syringic acid when heated with hydrogeniodide a little above loo" decomposes with liberation of methyliodide. With sodium methyl oxide and methyl iodide it forms methylnzethzJlsyrin!iate C,,H1,05 melting at 82.5". Methylsyringic acid,CI0Hl9O5 melts a t 168" and is somewhat soluble in hot water. Dis-till ation with calcium hydroxide produces trime thylpyrognllol.Byheating syringic acid above kLo dimethglpyrogallol 0H*C6H,( OMe),160 ABSTRACTS OF CHEMICAL PAPERS.is formed ; with ferric chloride it gives a t first a blood-red coloration,which changes into copper-red needles. Cedriret was observed inthe solution. Methylsyringic acid was identified as trimethylgallicacid. J. W. L.Arganin. By S. COTTON (J. Pharm. [ 5 ] 18 298-302).-Thisbitter principle is extracted from the kernel of the nut borne by theargan tree of the order Sayotacew growing in Morocco and Mada-gascar. Tho almond itself is bitter but contains over. 66 per cent. ofa sweet fixed oil which congeals a t O" and has a density of 0.914.The bitter principle insoluble in oil ether chloroform cai*bon bisul-phide and light petrc)leum is easily soluble in water and 90" alcohol ;and somewhat less soluble in absolute alcohol.It is ext,racted bytreating the crushed kerne!s with ether or some other solvent toremove the oil then extracting with 99" alcohol with the aid ofheat. The alcoholic solution is then treated fractionally with ethera t intervals so as to obtain the arganin in crystals. After some days,the liquid is decanted and the crystals are dissolved in boiling absolutealcohol from which they recrytallise on cooling. Very short bril-liant prisms are thus ohtained which become gummy on the filterfrom exposure to the moisture of the air. J. T.Homopterocarpin and Pterocarpin from Red Sandal Wood.Bv P. CAZENEUVE and L.HUGOUNENQ (Con@. rend. 107 737-740).-When homopterocarpin is heated just to the point a t which dccompo-sition begins i t yields creosote and a small quantity of catechol andwhen distilled with zinc powder it yields a small quantity of a volatileoil with an odour OF cournarin together with benzene toluene,methane ethylene. and carbonic oxide. The principal product of theaction of hydrochloric acid on homopterocarpin (Abstr. 1887 972)is a black uncrj stallisable resin which dissolves in alkalis andforms fluorescent solutions ; the hydrochloric acid retains in solutiona small quantity of an amorphous red colouring matter which dis-solves in alkalis with fluorescence and probably belongs to thefliiorescein-group. Hydrioclic acid produces similar results. Whenheated in sealed tubes with 10 per cent.sulphuric acid Iiomoptero-carpin undergoes an isomeric change and is converted into an opaline,yellowish non-crystallisable resin similar in appearance to amber,whilst the sulphuric acid remains unaltered. Homopterocarpin isnot affected by aqueous potash at 200" hut is attacked hy fused potashat 250-300" and yields a small quantity of a volatile oil with an odourof conmarin and phloroglucinol but no acid. Ordinary nitric acidatt:icks homopterocarpin in the cold with formation of an amorphous,green unstable nitroso-derivative which contains 5.5 per cent,. ofnitrogen. Fuming nitric acid acts with considerable energy and ontlie addition of water an insoluble red resin separates.The nqneoussolution when evaporated yields a crystalline product from whichcold water extracts oxalic acid whilst hot water dissolves a substancewhich crystallises in yellow needles melting at lRcLo and has alltite properties of trinitro-orcinol. It yields a barium saltC',H,( N02)302Ba + 3H20 which cryshllises in yellow needlesORGANIC CHEJIISTRI' a 161and explodes above 150". The product of the action of nitricacid also coil tains a non-crystallisable isomeric trinitro-orcinol. Ifhomopterocarpin is treated with excess of bromine the compoundC2,H,,Br60 is obtained; it dissolves i n benzene and separates incrystalline plates melting a t 270" when the benzene is mixed withan equal volume of ether. The interaction of equal molecular pro-portions of homopterocarpin and bromine in Rollition in chloroformyields a mono-derivative C,,H,,Br06 which separates from boilingalcohol in white crystals.Phenylhydrazine and ace tic anhydridehave no action on homopterocarpin. Prom these results it followsthat the formula originally ascribed to homopterocarpin must bedoubled and it would seem to be a condensed poly-orcinol but its con-stitution is not yet definitely determined.Pterocarpin yields similar results but the action of nitric acidis more energetic. It yields a crystalline monohomo-derivative,CzoH15BrOs and hence its true formula is C,oH:,606. Pterocarpin isin all probability a lower homologue of homopterocarpin.C. H. B.Dipicolylmethane. By A . LADENBURG (Ber. 21 3099-3104) .-DipicolyZmethn~/e CH,(CH*C,NH,) is obtained by heating a mixtureof picoline (from the mercury salt) with methylal in molecular propor-tion in presence of zinc chloride for 10 hours at 280-290'. Theproduct is treated with dilute hydrochloric acid heated on a water-bathfor some time made alkaline and distilled.The residue is extractedrepeatedly with ether and the base extracted from the ethereal solu-tion with dilute hjdrochloric acid. The solution is treated with mer-curic chloride as long as any resin is precipitated filtered freed frommercury by means of hydrogen sulphide made alkaline with soda andextracted with ether. The base is distilled under reduced pressure.It is a light-yellow oil insolnhle in water readily soluble in alcoholand ether and boils at 319-323" under 760 mm.pressure. Sp. gr. =1.0381 at 0". The hydmchloritie forms deliqumcent needles ; theplatinochlnride C13H14N2,H2PtC16 crystdlises from water in sparinglysoluble lustrous plates which melt at 215" with decomposition ; theciurochloride (C,,H I,N,)2,HiA~iC119 + 1+H,O separates as an oilwhich solidifies to small needles ; the mercurochloride,13H14N1 H2HgAC110,crystallises like ammonium chloride or in large plates and melts a t161" ; the picrate cadmioiodide periodide aiid bismuthoiodide wereprepared.Dipipecolinem ethane C17H?BN2 prepared by reducing the above com-pound with sodium and alcohol forms a white crystalline mass meltsat 52-51" and boils a t 195" under 26 mm. pressure. It dissolvesreadily in benzene and ether very readily in alcohol and is rathersparingly soluble in water.It is a strong base bnt yields mostly oilysalts. The hydrochloricle Cl3Hz6N,,2HC1 is crystalline. Tetramethyl-dipipecolyl methiodide C,,H241LIe,N,,2MeI forms white crystals veryreadily soluble in water ; the aurochloride C1 K24Me2N2,H2Au2C Is168 ABSTRACTS OF CHEMICAL PAPERS.crystallises in needles melting at 170-1 71" with decomposition.The constitution of the base is probably CHz(CHz-C5NMeH,)2.N. H. M.The Two Bidesyls. By J. C. GARRET (Ber. 21 3107-3l.08).-Both bidesyls (Knoevenagel Abstr. 1888 706) yield tetrapheny2-pyrroZine C2eH21N when heated with alcoholic ammonia a t 150".'I'his crystallises in large needles melts at 211-212" and is almostinsoluble in alcohol.On one occasion the preparation from iso-bidesyl melted at 234-235" but was otherwise identical with theother preparations. N. H. M.Methylstilbazole and its Reduction-products. By F. BACH~R(Ber. 21 3071-3082) .-~~eth~ilstilbazole C,,H,,N is formed whena-ylutidine is heated a t 215" with benzaldehyde (1 mol.) and anhy-drous zinc chloride. The product is mixed with alcohol acidifiedwith hydrochloric acid distilled with steam to free it from benzalde-hyde and hydrocarbons and the residual oily liquid separated. Afteradding excess of soda the mixture is distilled with superheated steam ;the unchanged lutidine which passes over first is collected separately,and the new base which is very slightly volatile is extracted from thelatter portions of the distillate with ether the soiution dried overpotash evaporated and the base distilled.The yield is about15.4 per cent. of the theoretical quantity. It is a -yellow viscid,strongly refractive oil boils a t 321-326" with slight decomposition,and is readily soluble in alcohol ether chloroform and carbon bisnl-phide but insoluble in water.The hyhochlorids and the hydrobromide cannot be obtained i ncrystals but the hydriodide prepared by dissolving the base in fumingh ydriodic acid crystallises from hot alcohol in microscopic yellowiieedles melting a t 210-211". The periodide is crystalline andreadily Poluble in alcohol b u t insoluble in water. The picrate,Cl4Hl3N,C6H3N3O7 crystallises from hot alcoholic hydrochloric acid inmicroscopic yellow needles melts a t 192-193" with previous soften-ing and is very sparingly soluble in hot dilute hydrochloric acid.The mercurochloride CliH13N,HHgC13 crystallises in needles has nowell-defined melting point and is soluble in dilute hydrochloric acid.The platinochloride C,4H13N,H?PtClGr crystallises in smal? yellowiieedles with 1 inol.H20 melts at 183" decomposes a t 188 and issoluble in hot dilute alcohol but very sparingly soluble in hothydrochloric acid. The nzLI-ochloride C14Hl,N,HAuC14 prepared byprecipitating a boiling solution of the hydrochloride crptallises ingolden needles melts a t 141-142" and is sparingly soluble in boilingwater. Potassium bismuth iodide potassium cadmium iodide andstannous chloride produce precipitates in a hydrochloric acid solutionof the base.The bromide Cl4HI3Br2N prepared by treating thebase with bromine (1 mol.) in carbon bisulphide solution sepa-rates from hot alcohol in small nodular crystals and melts atUih ydromethylstilhazole CIBH15N is prepared by heating methyl-stilbazole (1 part) with fuming hydriodic acid (10 parts) a t lt;O",treating the resulting periodide with sulphurous anhydride decom-139-1 40"0 RO AS I C C k1 EM1 S T RT . 163posing the iodide with Fola and distilling the base with steam. It isa colourleps oil boiling at 290-295". The picrate CIIHl5N,C,H3N3O,,crystallises in small citron-yellow needles melts a t 154-156* and isreadily soluble in hot alcohol but only sparingly in ether. The p7atino-chloride Cl4HI5N,H2PtCl6 is crystalline melts at 168" with decom-position and is very spaxingly soluble in water but more readilyin dilute alcohol.The msrcurochZoride CllHllN H HgC1 + H20,crystallises from hot dilute hydrochloric acid in which i t is readilysoluble in large needles and melts a t 93-95'. The remaining saltscannot be obtained in a crystalline condition.Me!hyZstiZbuzoZir~e C,,H,,N is prepared by reducing a boilingalcoholic solution of methylstilbazole with sodium and distilling theproduct with steam ; it is a colourless oil boils a t 286-291" andbecomes yellow on keeping. It is readily soluble i n alcohol and ether,hut sparingly in water to which it imparts an alkaline reaction. Ityields an oily nitrosamine and all the salts examined were also oilycompounds.Meth7;l~13yri~inecurbo~yZic acid C5NH,Me*COOH is obtained in smallquantity when a-ylutidine is oxidised with the calculated quantityof a 14 per cent.solution of potassium permanganate but tlie principalproduct is lutidinic acid. Met hylpyridinecarboxylic acid crystallisesfrom hot alcohol in which it is only moderately soluble in smallplates decomposes at about 260" and is very readily soluble in watcr.It gives no reaction with ferrous salts and yields picoline when heatedwith lime.When a-y-lutidine is heated at about 225" with benzaldehyde(2 mols.) and anhydrous zinc chloride an oily seemingly neutralcompound is obtained.p-Ethyl-a-stilbazole and its Derivatives. By G. PLATH (Ber.,21 3986-3099).-P-~ElthyI-a-sti2bazoZe C5NH,EtCH:CHPh [ = 3 61,is formed when collidine (10 grams) prepared from paraldehyde andaldehyde-ammoriia (compare Durkopf Abstr.1887 499) is heated at220-222" with benzaldehyde (9 grams) and zinc chloride. The pro-duct is acidified and distilled with superheated steam to free it frombenzaldehyde and hydrocarbons. Excess of alkali is then added theunchanged collidine distilled with steam and as soon as tbe dis-tillate commences to become turbid the stenni is superheated andthe distillate containing the new base which is only very slightlyvolatile is collected separately. The yield is about 37 per cent. of thetheoretical quantity. It crystallises from dilute alcohol in colourlessplates melts a t 58*5O boils a t 344" and is readily soluble in alcohol,ether benzene acetone and chloroform but insoluble in water.ThehydrochZoride C15H,,N,HCI separates from hot benzene in an oilycondition but solidifies on cooling; it crptallises in needles andmelts a t 193". The platinochloride (C15H15N),,H2PtC16 + 2H20,crystallises in needles melts a t 188" with decomposifion and is solublein dilute hydrochloric acid but insoluble i n cold water. The auro-chloride C15H15N,HA~C14 crystallises in long needles melts a t 1 6 8 O ,and is insolnble in water. The stannochloride Cl5Hl5N,HSnCl3 +3H20 crystallises from hot dilute hydrochloric acid in white needles,F. S. I(164 ABST RA CTS OF CHEMICAL PAPERS.melting at 245.5 -246 ". The mecrurochloride CI5Hl5N H AgC I crys-tnllises from hot dilute hgdrochloric acid in long needles melting a t196".The picrate Cl5HI5N,C6H3N3O7 crystalliPes from alcohol or hotwater in long yellow needles melting at 203". An aqueous solutionof the hydrochloride gives precipitates with ammonium molybdate,potassium dichromate and potassium cadmium iodide. The per-iodide is crystalline but unstable. The bromide C,,Hl5Br,N pre-pared by treating the base with bromine (1 mol.) in carbon bisul-phide solution crystallises from alcohol in small needles melts a t127*5-128" and is very readily soluble in chloroform carbon bisul-phide benzene alcohol and ether but insolnble in water.Diht/droethylstilha,ole C,NLT3Et*CH,-CH2P h [ = 3 61 is obtainedwhen ethylstilbazole is heated a t 160-165" with concentrated hydr-iodic acid.The product is treaked with sulphurous anhydride theresulting iodide diwolved in water and the solution shaken withether ; excess of soda is then added the base extracted with ether anddistilled. It is a colourless oil boils a t 316.3S" (cow.) and is readilysoluble in alcohol and ether but insoluble in water. The aurechloride,C,,H,,N.HAuCI + HzO and the hydrochloride are with difficultyobtained in a crystalline state. Tlteplatinochlorids ( C15H,,N),,H,PtCI,,crystallises from dilute hydrochloric acid in long needles melting a t168". The mercurochloride C15H17N,HHgC13 crystallises from verydilute hydrochloric acid in long needles and melts at 136.5". Thepicrate is sparingly soluble in water from which it crystallises inyellow needles.OctohydroethyZstilbazole C,NH,F,t*CH2*CH2Ph prepared by treatinga boiling alcoliolic solution of ethylstilbazole with sodium and purify-ing the product by mean? of the nitroso-derivative is a colourless oilboiling a t 303" (uncorr.).It lias a strong piperidine-like odour analkaline reaction and is volatile with steam. It is soluble in chloro-form benzene ether and alcohol but only sparingly in water. Nocrystalline salts were obtained. I?. s. K.Paraxyloquinolinesulphonic Acids. By E. NOLTING and J.FR~~HLING (Ber. 2 1 :-I1 56-31 58) .-XylopuinolinesuIp hoiLic cicid,[Me2 SO,H = 1 4 21 (compare Nolting and Kohn Abstr. 1886,355) crystallises in prisms and is very readily soluble in hot waterand dilute acetic acid but only spariiigly in cold water.The bnriunhsalt (CI,NHlo.SO,),Ba + H20 crystallibes in needles loses its water a t150" and is readily soluble in hot water. The potassium salt crys-tallises with 1 mol. HzO and is readily soluble.XzJ1oqui)ioliiaesuIphonic acid [Me S0,H = 1 4 31 can be pre-pared from parasylidineparasulphonic acid by S kraup's reaction orby heating paraxyloquinoline with fuming sulphuric acid for 36 hours.It resembles the preceding compound but is more sparingly soluble.The barium salt crystallises in plates with 1 or 2 mols. H20. Thepotasciunz salt cryI;tallises in anhydrous needles or plates.Paraxyloquinoline is obtained when either of the above acids or anyof their salts is distilled with ammonium chloride but it is moreeasily prepared from paraxylidine.F. S. I(ORGANIC CHEMISTRP. 165Isoquinoline. By G. GOLDSCHMIEDT (21Znnatsh . 9 675-684).-The author has previously shown (Abstr. 1888 306) that papaverineand its compounds with methyl iodide and ethyl iodide yield imidesof hemipinic acid when oxidised witjh permanganate. This property offorming imides on oxidation with permanganate appears to becommon to all isoquinoline-derivatives the base itself giving phthal-imide.I s o q i i i n o l i n e ethobromide on oxidation appears to give ethylphthal-imide but the quantity obtained was insufficient for analysis.Isoquinoliize benzyl chkiride is formed on mixing its constituents inmolecular proportion. It crystallises although not easily in prisms,dissolves readily in water and alcohol but is only slightly soluble inether and benzene.When oxidised with permanganate it givesbenzylph t halimide melting a t 11 5-1 16".Isoquinoliwe phenncy 1 brmnide is most conveniently prepared bymixing moleciilar proportions of itq constituents dissolved in benzene.It crjstallises from alcohol in prisms which melt a t 205" to a golden-red liquid and furnishes a nitro-compound which in its toxicologicalaction resembles the corresponding quinoline-derivative. On oxidationwith permanganate a nearly pure phenacylphthalimide me1 ting a t156-155" was formed. G. '1'. M.Creatinines. By G. S. JOHNSON (Proc. Roy. Xoc. 43 493-534).-Normal urine when boiled with picric acid in alkaline solutioncauses a reduction to picramate. About one-fourth of the cupricoxide reducing power of normal urine is due to uric acid whilst theremaining three-fourths has been variously accounted for.Theauthor finds that it is due t o a creatiiiine which can be bestprecipitated by adding sodium Rcetate and mercuric chloride tonormal urine. A flocculent precipitate is first produced which issucceeded by one which is apparenhly crystalline but which under themicroscope is found to consist of globules. It has a constitution4(C1H,HgN,0,HC1),3HgCl + 2H20. The hydrochloride of the base,C4H7N30,H Cl is prepared by decomposing the mercury salt withhydrogen sulphide. It is soluble in water and alcohol. No precipi-tate is produced with mercuric chloride until sodium acetate has beenadded. With platinum chloride in alcoholic solution it gives ananhydrous salt' ( C,H,N,0),,H2PtCI ; in aqueous solution a salt,(C4HiN30),,H2PtCI + 'LH,O is formed.The free base is obtainedby treating the hydrochloride wi-ch lead hydroxide ; i t can be obtainedin three forms according to the temperature at which the solution isevaporated. If the crystals are dissolved in a small quantity of coldwater and evaporated in a vacuiim. efflorescent creatinine is obtained insyuare prisms which acquii-e a porcelain-like appearance as the waterof crystallisation evaporates. Rut if the evaporation is coiiducted a t60° anhydrous crystals of tabular p-creatinine of urine are obtained.which when dissolved and again evaporated in the coid give efflor-escent creatinine. Finally if effloresced creatinine is dissolved at lOO",t,abular a-creatinine of urine is obtained and this M hen dissolved andevapoiaated in the cold recrystalliLes unchanged ; 2 mols of creatinineof urine are equivalent in reducing power to 1 mol.of glucose whilsl6G ABSTRACTS OF CHEMICAL PAPERS.3 mols. of flesh creatinine are required to effect the same amount ofreduction. The efflorescent oreatinine has tbe same solubility in wateras the tabular a-salt. Urine creatinine differs from flesh creatinine inits power of reduction in the composition of its platinochloride andin its solubility in water and alcohol. Boiled with watev the creati-nine is converted into urinary creatine CdH,N,O + H20. It can beconverted by Liebig's process into a creatinine hydrochloride which isidentical with that obtained from flesh creatine by the same proce-s.Prom this hydrochloride four different creatinines are obtained whichare not identical with the above creatinines directly prepared.C i y -tnllographic measurements of the natural creatinines are given. Thecreatinines from urinary creatine have less reducing powers than thenatural creatinines bu't greater than that of creatinine from fleshcrea t ine.Measurements by Hartley of the absorption-spectra of creatininefrom flesh creatine (Liebig's process) and of the new base fromnrine are given. The spectra are similar the bands being causedby condensation of numerous oxygen- and nitrogen-atoms as in uricacid. The actinic absorption is greater for the urine creatinine thanfor creatinine from flesh.H. K. T.Bases formed by the Action of Potash on Additive Pro-ducts of Papaverine. By A. STRANSKY (Monutsh. 9 751-761 ;compare Claus and Ritzfeld Abstr. 1886 996).-On boiling papa-verine ethobromide with aqueous potash for several hours a brown,resinous substance is formed. I t may be crystallised from water andalcohol and forms prismatic plates which have the formulaO(C,H,,NO,Et) and melt at 72". From this oxide the followingcompounds may be obtained :-The chloride C20H21N04EtC1 whichcrystallises from alcohol in rhombic needles melting at 80"; theplatinochloride ( C,H2,N0,EtCl)2,PtC14 ; the picrate crystallising inlight yellow plates ; and the chromate ( CmH21N04Et)2Cr,07 crystal-lising in yellow needles or plates and melting at 78".Papaverine benzyl chloride under the same conditions gives theoxide (C,H2,NOaC7H7)20 which crystallises in needles melting at165".The chromate (C20H21N04C7H7),Cr207 forms yellow plates,which melt with decomposition at 85" and the picrate,(C2JLN04C7H7) CJ%N&&,crystallises in plates melting at 185".Pavaverine methiodide (30 grams) potash (60 grams) and water(300 grams) when boiled together for 20 minutes give a productcrystallising in greenish-yellow needles melting at 215" efflorescing011 exposure to air and giving the hydroxide C20H,,N0,Me.0H whenheated at 100". The corresponding picrate crystallises in platesmelting at 205" and the chromate in small needles melting at 8.5".G. T. M.Papaverine-derivatives.By G. GOLDSCHMIEDT and C. OSTER-SETZER (Monut~h. 9 762-777 ; compare Abstr. 1886 83 478 ; 1887,163 ; 1888 302 1116 lll8).-The authoi-s find that the two acids oORGAXIC CHEMISTRY. 167the formula CloH,oOs obtained by the oxidation of narcotiiio andpapaverine respectively are not identical as was previously suppose(].The acid from narcotine (hemipinic acid) forms crystals belonging tothe inonoclinic system commences to fuse in open tubes at 160-161",in closed tubes a t 156-158" and gives an orange-red precipitatewith ferric chloride but no precipitate with silver nitrate. The cor-responding anhydride melts a t 166-167" the ethylimide at 96". Theacid from papaverine (metahemzpinic acid) crystallises in the rhornbicsystem commences to fuse in open tubes a t 17&175" in closed tubesa t 172-1 73" gives a deep orange-red precipitate with ferric chloride,and a crvstalline precipitate (needles) with silver nitrate.The corre-spondini anhyd&k milts at 175" the ethylimide a t 230".G. T. M.Constitution of Papaverine. By G. GOLDSCHBIIEDT (Monatsh. 9,778-781 ; compare preceding Abstracts).-Metahemipinic acid ob-tained by the oxidation of papaverine is dimethoxy-orthophthalic acid,C,H,(OMe)2(COOHj [(OMe) (COOH) = 1 2 4 51,and differsfrom hemipinic acid by giving protocatechuic acid [COOH (OH) =1 3 41 on fusion with potash. The cunstitution of papaverine musttherefore be represented by the formula-Strychnine. By W. F. LOEBISCH and H. MALFATTI (Monatsh. 9,626-633 ; compare Abstr.1887 282) .-Stoehr on distilling strych-nine with quicklime obtained a mixture of scatole and /%methyl-pyridiue. The authors find that when the alkalo'id is distilled withsoda-lime in addition to the above-mentioned compounds. carbazoleis formed; in quantitr equal to 0.5 per cent. of the shychn&e used.G. T. M.Relations between Atropine and Hyoscyamine. By A.LADENBURG (Bey. 21 3065-3070).-The author is of the opinion thatatropine is an inactive base and that it stands in the same relation tohyoscyamine as racemic acid to lavotartaric acid ; moreover that thesupposed conversion of atropine into hyoscyamine although possible,has not hitherto been accomplished and that all observations to thecontrary result from the employment of impure atropine.(CompareWill and Bredig Abstr. 1888 1316.) This view is supported by thefollowing experiments :-20 grams of atropine aurochloride preparedfrom " pure " atropine was recrydallised 14 times and yielded1 gram of hyoscyamine aurochloride. Another sample of atropineaurochloride prepared from the purest commercial atropine whichhad been further purified by recrystallising many times and thenmelted at 114" was recrystallised 14 times. 1 gram of atropineaurochloride was obtained; it melted a t about 140" and an 18 percent. solution of the free base prepared from this sample of salt wasoptically inactive168 ABSTRACTS OF CHEMICAL PAPERS.Atropine cadniioiodide crystallises from alcohol in needles and isalmost insoluble in water. F.S. K.Constitution of Berberine. By S. HOOGEWERFF and W. A. VANDORP (Rec. I’rav. Chiin. 7 206-209).-The view is expressed hatberberine is a derivative of isoquinoline and the authors are engagedon experiments with the object of proving this.Commercial Preparation and Partial Synthesis of Cocaine.By C. LIKB~~KMAKN and F. GIESEL (BPT. 21 3196-3202).-Most ofthe amorphous alkaloids obtained in the preparation of coca’ine yieldecgonine whcn boiled for about a n hour with hydrochloric acid(compare Liebermann Abstr. 1888 1210). The ecgoiiine can beisolated by evaporating the filtcrrd solution to d r p e s s boiling theresidue with a small quantity of alcoliol to remove impurities decom-posing the salt with sodium carbonate and recrjstallising the basefrom alcohol.Benzojlecgonine can be easily obtained by treating ecgonine wit)hbenzoic chloride or benzoic anhydride but the yield is not good ineither case.The following method however gives rery goodresults :-Benzoic anhydride (a little more than 1 mol.) is graduallyadded to a hot saturated aqueous solution of ecgonine (1 mol.) andthe mixture is heated on the water-bath for about an hour. The coldproduct is shaken with ether t o remove benzoic acid and anhydride aridthe residue is rubbed and washed u ith a small quantity of water on thefilter-pump. The yield is about 80 per cent. of the ecgonine employed.Small quantities of benzoylecgoiiiiie can be obtained by evaporatingthe mother-liquor and if the filtrate is again treated with benzoicanhydride the greater part of the unchanged ecgonine is convertedinto the benzoyl-derivative.The whole of the excess of benzoic acid(anhydride) employed can be obtained from the ethereal extract.Anhydroecgonine melts a t 235” is far less readily soluble in alcoholthan ecgonine and the crystals effloresce when kept in a partial vacuum.The hydrochloride is horn ever far more readily soiuble in alcohol thanecponine hydrochloride.CocaYne was prepared by Einliorn’s method from the benzoyl-ecgoiiine obtained as described above and the preparation was foundt o be identical with the natuml alkaloi’d in every respect.It has been observed by Lossen that when a solution of coca‘inehydrochloride is precipitated with ammonia the precipitate is redis-solved on adding more ammonia.The authors find that this pheno-menon is simply due to the additional quantity of water and not toany solvent action of the alkali. F. S. I(.Cocaine. By A. EIR’HOXN (Eev. 21 3029-3044) .-Cocay?benzoyl-hydyoxyacetic acid C5NHiMe.CBz(OH)-COOH is obtained whena 3 per cent. solution of potassium permangaiiate (230 c.c.) isgradually added with consta1,t stirring to an aqueous (1 litre ofTT ater) solution of benzoylecgonine ( e 5 grams) and sodium carbonate.The excess of potassium permanpinate is reduced with alcohol in thecold the Gltcred solutioii c a ~ e f u l l ~ acidified with h) drochloric aciORGANIC CHEMISTRY. 169and evaporated ; the crystalline residue is extracted with and recrjs-talli~ed from alcohol and the resulting hydrochloride decomposed byboiling with ammonia.The acid which separates from the ammoni-ncal solution crystallisa from alcohol or hot water in large prisms,melts a t 230" with decomposition and yields benzoic acid and cocayl-hydroxyacetic acid (see below) when heated with concentrated hydro-chloric acid. The hydrochloride CI5Hl7N04,HC1 crystallises fromzdcohol in plates with 2 mols. H20 and melts at 217-218". TheI/,umchioride C15H17N04,HAuC14 crystallises from dilute hydrochlorio:icid in yellow needles melting at 228" with decomposition. Theylatilzochloride C,5H17N04,H2PtC16 separates from water in jellowish-red nodular crystals containing water and melting a t 233'. Theinethyl salt prepared by passing hydrogen chloride into a methyl:ilcohol solution of the acid was obtained in an oily condition; it isreadily soluble in water and the solution in hydrochloric acid yieldsan aurochloride CI6Hl9NO4,HAuCI4 which crystallises in long needles,melts a t 181-182" and is sparingly soluble in water.The ethyZ Ealt,prepared in like manner is also an oil ; the aurochloride,separates from acidified alcohol in yellow crystals melts a t 160.5",and is very sparingly soluble in water.Cocay Zhydroxyacetic acid C5NH7Me*CH( OH)*COOH. is formed inthe preparation of the benzoyl-derivative when the oxidation productis evaporated in an acid solution. It can be obtained by graduallyadding a 3 per cent. solution of potassium permanganate (900 c.c.) toan aqueous (If litres of water) solution of ecgonine hydrochloride(6 grams) and sodium carhonate.The h y d r o c l h i d e C8HI3NO3,HCl +H,O is isolated as described above. The free base is obtained in thepure state by decomposing the aurochloride with hydrogen sulphide,evaporating the filtrate recrystallising the residue from a mixture ofmethyl alcohol and ether and decomposing an aqueous solution of theresulting hydrochloride with silver oxide. It separates in longneedles or in thick prisms when ether is added to am aqueous methylor ethyl alcohol solution and melts a t 233". The aurochloride,CeHl,N03,HAuC14 crystallises from dilute hydrochloric acid in yellowneedles containing 2 mols. H,O and melts a t 211". It crystallisesfrom alcohol in short thick well-defined prisms containing alcohol.Anhydroecgonine can be prepared by heating cocai'ne for four hoursa t 140" with glacial acetic acid saturated with hjdrochloric acid.When anhydroecgonine is oxidised with dilute potassium permamga-nate a s described above small quantities of ecgonine or cocayl-hydroxyacetic acid are formed according to the conditions of theexperiment. A hydrocarbon ammoniiim chloride methyl chloride,very small quantities of a secondary base and resinous products areformed when anhydroecgonine hydrochloride is heated at 230" for along time with glacial acetic acid saturated at 0" with hydrogenchloride. When anhydroecgonine is heated with water a t 150° i t ispartially decomposed into an acid and methylamine but all attemptsto prepare a simple pyridine-derivative from the base were uusuc-cessful.VOL. LVI. r170 ABSTRACTS OF CHEMICAL PAPERS.Cocaine methiodide C1,Hz1NO4,Me1 prepared by heating cocaine(1 mol.) with methyl iodide (1 mol.) a t loo" crystallises from absolutealcohol in shining plates melts a t 164" and is sparingly soluble inalcohol .Cocazne rnefhochloride C17H21NOJ,MeCl prepared by treating &hepreceding compound with silver chloride crystallises from a mixtureof alcohol and ether in small needles or plates melts a t 152*5" and isvery readily soluble in water.MethylanhydroPc.go.niiLe methiodide CloH,,NO,,MeI is formed to-gether with benzoic acid when an aqueous solution of cocajinemethiodide is heated a t 100". It crystallises from alcohol in slender,yellowish needles or in well-defiued prisms and melts a t 195-196'.When cocajine methiodide is heated a t 140" with glacial acttic acid,previously saturated with hydrogen chloride benzoic acid and a,compound containing both iodine and chlorine are produced. Whenthe last-named sulmhnce is treated with silver oxide a crjstalline,hygroscopic base is obtained.Anh!ydroecgorzine methiodide ClnHl6NO2I is formed when an aqueoussolution of the base just described is treated with hydriodic acid. Itcrystallises from alcohol or water in long prisms containing 1 mol.H,O and melts a t 207-208'. The constitution of coca'ine is probablyAn Acid from Cod-liver Oil. By A. GAUTIER and L. MOURGUES(Compt. rend. 107 740-743).-Cod-liver oil contains an acid in theform of an unstable compound resembling the lecithins which decom-poses in contact with acids or alkalis and yields glycerol phosphoricacid and the new complex acid. Lecithins themselves are presentin the oil and add to its value by presenting phosphorus in a readilyassimilable form.The oil is systematically extiacted with alcohol of 35 per cent.containing 3 per cent. of hydrochloric acid and the solution is satu-rated with potassium carbonate and distilled in a vacuum at 45".The residue is acidified heated for a moment a t loo" and extractedwith alcohol a t 85". The latter dissolves the acid,' which separates asa viscid colourless substance on cooling o r on adding water. Thecrude product is dissolved in potash neutralised witli nitric acid andlead acetate added so long as the precipitate is not discoloured. Thelead precipiiate is washed with water decomposed by hydrogen sul-phide and the solution filtered whilst hot. The lead sulphide iswashed with hot alcohol and the washings and the original filtrateare evaporated in a vacuum. The new acid m o r r h u i c acid crystal-lised in soft yellowish square plates of the composition C,Hl,N03,which differs from tyrosine by Hz only.Morrhuic acid has a diRagreeable odour recalling that of kelp ; whenfreshly precipitated it is oily and viscid bat i t gradually solidifies.It dissolves in hot water but separates on cooling and IS soluble inalcohol but only slightly soluble in ether. It reddens litmus decom-poses carbonates and forms crystallisable salts with the alkalis ; itORGANIC CHEJIISTRY. lilsolutions give precipitates with lead and silver but not with coppersalts. Morrhuic acid also combines with acids and forms a crystal-line hydrochlorid<i. which is decomposed by water morrhuic acidseparating in the form of an emulsion ; the platinochloride is solubleand crptallises i n very small prisms; the aurochloride forms auamorphous precipitate which readily alters when heated.When distilled with lime morrhuic acid yields a base whichgives with methyl iodide and potash the reaction characteristicof the pyridines. When oxidised with potassium permangnnate ityields a monobasic pyridinecarboxylic acid which crystallises inprisms and rhomboidal lamell= and forms a platinochloride and anaurocbloride.The silver salt of morrhuic acid contains 2 atoms of the metal andhence i t is bibasic. The fact that it gives no precipitate with copperacetate indicates that the carboxyl is not in direct union with thepyridine-ring and it probably has the constitutionThis formula explains the ready reduction of the silver salt even inthe cold.De Jongh’s gaduirbe is probably identical with morrhuic acid.C. H. B.Action of Phosphorus Qxychloride on Cholic Acid. By R.CAMPANI (Onzzettu 18 88-89).-The cholic acid employed wasprepared from ox-bile by boiling it with dilute hydrochloric:acid for 24 hours and then isolating the acid in the usual way.The phosphorus oxychloride (12 grams) is added drop by drop tothe cholic acid (5 grams) in fine powder ; a powerful reaction takesplace and as soon as it has subsided the product is thoroughlywashed with boiling water and allowed to dry a t the ordinary tem-perature. It is a greenish-yellow powder very sparingly soluble inalcohol but easily in ether ; this on evaporation leaves it as a brown,amorphous vitreous residue. On analysis it gave numbers corre-sponding with the formula C24HJ603. It is insoluble in aqueous alka-line solutions but ou long boiling with alcoholic potash it dissolvesand is reconverted into cholic acid which is precipitated from therolution on adding hydrochloric acid. The compound therefore isthe anhydride of cholic acid. C. E. G.Gelatinous State of Albuminoi’d Substances. By V. MICHAI-LOFF ( J . Russ. Chem. Xoo. 1887 19 666-690; 1888 20 35-72,159-179 274-360 380-388) .-After giving the history of thisand similar subjects (collo’idal matters in general) the author showsthe conditions under which white of egg from different sourcesexists in various solutions precipitates and gelatinous coagulates,and in coagulates obtained by heat how these different niodificationsare formed and transformsd and describes a t some length theirproperties (chemical and physical) especially those of Tarchanoff’s*‘ tata-albumin ” and its behaviour towards solutions of different saltsa t different temperatures as well as the results obtained on dialysis12 172 ABSTRACTS OF UHEMICAL PAPERS.(see Abstr. 1887 856). The mutual actions of different kinds ofalbuminold substances are also studied and it is shown that albuminsare acid and globulins basic compounds. Gelatinisation of albuminin the first phase is dne to hydration; in its subsequent phases todehydration which is more or less complete according to the condi-tions. B. B

ISSN:0368-1769    

DOI:10.1039/CA8895600112

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

172 ABSTRACTS OF UHEMICAL PAPERS. P h y s i o l o g i c a l C h e m i s t r y . Primary and Secondary Oxidation. By 0. NASSE (PJliigds Archiv, 41, 378--389).-A distinction is drawn between direct oxida- tion (oxidation occurring a t the body temperature in the blood and fluids of the body by neutral oxygen combining with some readily oxidisable matter), primary Oxidation (such as occurs in the body chiefly; tbe complex molecules are first altered by some ferment action in order to render them readily oxidisable), and secondary oxidation (oxidation of products of metabolism which have been formed by other processes than oxidation). The influence of readily oxidisable substances, such as fat and phenol, given in the food, on secondary oxidation was investigated, the urine being examined for ethereal hydrogen sulphates and glycuronic acid ; it was found that the burning of fat in the organism furthers secondary oxidation processes, as is shown by the rise in the amount of ethereal hydrogen sulphates and fall in the glycuronic acid on the days on which fat was given with the food. By J.LOEB (PJiiger’s Archiv, 42, 393-407) .-The comparison of plants with animals has suggested the question whether light influences the chemical processes in animals as, according to several experimenters, it does in those plants which contain chlorophyll. Moleschott (Wien. med. Wochensch., 1885) found in frogs that more carbonic anhydride was produced in the light than in the dark. But here no observations were made as to whether the animals moved much or little during the experiments.In the light, animals are more stimulated to move- ment, and muscular activity alone might thus explain the increased production of carbonic anhydride. v. Platen (1JLEiiger’s Archiv, 11, 272) observed also an increase in gaseous metabolism, and found, moreover, that the illuminatiou of the retina by light also produced, apparently reflexly through the central nervous system, a similar effect. Speck (Arch. j: e q . Path. u. Pharmnk., 12), however, arrived atj the conclusion that in the human subject, light of itself produces no increase in oxidation processes. On the local action of light on tissues removed from the body, but still retaining some vitality, the experiments recorded by Fabiiii and others are unsatisfactory and inconclusive, very little care having been taken to avoid putrefaction, W.D. 11. The Influence of Light on Oxidation in Animalg.PHYSIOLOGICAL CHEIIISTRY. 173 and even if this had not occurred the tissues were dying, and not living healthily. Moreover, the influence of changing atmospheric temperature seems also to have been neglected. I n the present research, these sources of error were avoided by taking lepidopterous lam% in the chrysalis stage when movements are practically absent. A number of these were weighed and placed i n a closed glass vessel witliin a beaker of water, and exposed to diffused daylight. 0 them were exactly similarly treated, exceps th&t instead of water, a solution of nigrosine of the same temperature was used, so that t'hey were in darkness.At the end of the experiment, they were again weighed; those which had lost most weight would be t'hose which had undergone most active oxidation ; but in case some i ridividual peculiarities of the pupa themselves might have produced these effects, a control experiment was performed by reversing the conditions; those which before were in the light were now put in the dark, and vice uersd. From a number of experiments the conclusion was finally drawn that light produces in these animals no increase of oxidation pro- cesses; that light has in fact no influence at all on these processes. These simple experinients were fully confirmed by more complex ones in which analyses of the oxygen used and carbonic anhydride produced were measured. This negatives the idea that light has any local action on animal tissues, although it does not at all contradict the conclusion that light may have an indirect effect on animals with intact central nervous system and active muscles, probably in this case a reflex effect through the optic nerves or sensory nerves of the cutaneous surface.The Melting Point and Chemical Composition of Butter as Effected by Nutrition. By A. MAYER (Landw. Versuchs-Stat., 1888, 261-282) .-The examination of butter produced by cows under various conditions was undertaken to explain if possible whey Danish butter has a better sale t'han Dutch in the English markets. All that was known on the subject was that the Danish is harder and of a better colour. Jnquiries showed that whereas in Holland the cows were fed on pasture and calved i n spring, in Denmark they, for the most part, drop their calves late on in the year, and are house fed.The cows under examination were fed at rarious periods on roots, hay, grass, clover, and silage, and the analysis of the butter produced showed that the percentage of volatile acids varies as the specific gravitv ; that the melting point does not march parallel with specific gravity, but is dependent on the percentage of the oleins, butyrin, cnpronin, &c., present ; the percentage of volatile acids and the specific gravity of the butter produced by any one cow varies more considerably than is generally supposed when the experimental con- ditions are changed: the percenlxage of volatile fatty acids is de- pendent on the period of lactation, rising as the period progresses, but it is also dependent on the feeding, being highest when roots, meadow-grass, and clover are giren, and lowest with ensilage : on the contrary, ensilage and hay produced a butter of high melting point, whilst grass or clover, whether as pasture or given cut in the housc, W.D. H.17.1 ABSTRACTS OF CHEMICAL PAPERS. lowers the melting point : the solidifying point follows the melting point, rising and falling with it. Protei‘d Metabolism in Man. By P. H~RSCHFELD (l‘jliiger’s Archiv, 41, 533--565).--The following are the final couvlusions drawn by the author from his research. It is possible for a healthx man (in one case for 15 days, in another for 10 days) to maintain a nitrogenous balance and equal body weight on from 5-8 prams of nitrogen daily: this corisesponds to 30-35 grams of proteid ; or if one excepts the days on which very little nitrogen ( 5 grams) w a s taken, the conclusion that 35-40 grams of proteid per diem is suffi- cient can certainly be drawn.Whether this would be possible for periods longer than thohe mentioned cannot be stated. This is contrary to the generally received opinion that an adult man requires 100-120 grams of prote’id daily, and that it is dangerous to ingest less, or else the tissue-proteids will be disintegrated. On the contrary, so much prote‘id as this increases t lie tissue-proteid (unless great activity Compensates for this hypertrophy), and the fat of the organism also increases. By E. NEISSER (Chew. Centr., 1888, 1083, from Centr.Physiol., 1888, 141-142).-The author conducted experiments with mice fed with about 80 different sorts of food in order to determine the extent to which the glycogen of the liver is affected by them. Morphine, amygdah, and mytilotoxin appear to cause an accumula- tion of glycogen. The health of the animals was no doubt of con- siderable influence on the amount of glycogen, although in one case, that of a, mouse fed on mytilotoxin, and seriously ill, the liver con- tained a considerable quantity of glycogen, whilst, on the other hand, with several animals fed on papain, asparagine, coniferin, coumarin, and in perfect health, the liver contained no glycogen. Synthetical Processes in the Animal Organism. By E. PFL~~GER (Pfliiger’s Archiv, 42, 144--154).-A living liver free from glycogen will again form that substance, not only from carbohydrates but from glycerol, gelatin, or proteid.v. Mering fed dogs on phlo- ridzin, whereby they became diabetic, and in a few dajs all carbo- hydrate material in the body had been discharged in the urine as sugar. If now the same drug was given to the same animals after a few days’ interval, during which they had no food, they once more became intensely diabetic, and the quantAy of sugar passed was so enormous that it cannot be supposed to have come from the drug itself ( Verhandl. VI Congresses inneres Med. Wiesbaden, 1887). One explanation of the way in which glycogen is formed after the ad- ministration of glycerol, is the well-known “ economy tlheory,” another is that glycerol and like substances act as stimuli to liver activity.It certainly cannot be supposed that glycogen is directly formed from the substance administered-or a t least not in all cases ; for instance, from ammonium carbonate. The question then arises as to the genetic relationship existing between glycogen and albumin. Experiments on the decomposition products of proteids have in no case yielded a carbohydrate; and not only that,, but proteids never yield any of E. W. P. W. D. H. Glycogen. J. W. L.PhYSIOLOGlCAT~ CHEMISTRY. 175 the decomposition products of carbohydrates (lactic acid, mncic acid, tartaric acid, &c.). Still, we have the formation of glycogen taking place in the liver when no food b u t albuminous food is taken. The following general considerations will, however, lead to a better understanding ot the snbject.The cliernical differences between animal and vegetable cells are not so great as was at one time hup- posed. Their chemical composition, so far as it is known, is the same ; all living cells breathe oxygen, and produce carbonic anhjdride, water, and amitlo-compounds. If the synthetic prucesws are more high17 developed in chlorophyll-holding plants, that does not mean that synthetic processes are absent from animal cells. As instances of syntlietic processes in animal cells, the formation of hippuric acid frorn glj cocine and benzoic acid, or of ethereal hydrogen sulphates from phenol and sulphuric acid, may be laken. A special kind of synthesis must, moreorer, occur in the retrogressive metamorphoses of proteids which lead to the formation of uric acid and members of the same group.In albumin itself, and in the products of albumin obtained outside the body, the number of carbon-atoms is much greater than that, of niti-ogen-atoms (indole, leucine, tyrosine, &c.) ; b u t in these products of metamorphoses in the body, the nitrogen and carbon- atoms are nearly equal in number, or, as in the cases of urea and guanidine, the nitrogen-atoms are the mme numerous. The im- portance of such synthesis occurring in living cells, resulting i n the formation of cyanogen containing molecules, has been before insisted on by the author. Researches on the formation of fat within the body show that here again there are undoubtedly syntheses occurring as the result of the activity of living cells: in fact, reactions occur which cannot be repeated in the laboratory or explained by any known chemical laws : they are probably, therefore. the result of a breaking down of molecules in the first place, and the living cells then building up entirely new materials of a couip!icated nature from the simple carbon compounds so liberated.The carbohydrates, for example, are derivatives of the hesatomic alcohol C,H,(OH),. Biit by feeding an animal on starch, the fat of the body is increased, and substances containing chains of 16 to 18 atoms of carbon linked one to another are formed ; and in the case of stearic acid at least, we have a number (16) which is not a multiple of 6. By this synthesis, too, we have substanceb which possess the property of circiilar polarisation changed into those which are optically inactive.'The firrt change must, however, be a process of reduction ; metabolic changes m u s t occur. and no nutrient material stimulates metabolism like protejid ; this explains why feeding on starch mixed with a small amount of proteid produces fat, and without it will not. The proteid admixture is, however, so small that it alone will not explain the great increase in fat. I n other parts of the animal kingdom, there are similar occurrences ; for instance, the formation of beeswax from honey. Another sample of the same kind is the formation of fat from proteid, although this is not so well proved as the foregoing cases. I n the synthesis of fat from carbohydrate, the group CH*OH must be changed into CH, ; and in the formation of carbohydrate (glycogen)176 ABSTRACTS OF CHEMICAL PAPERS. from prote’id, the group CB, must be changed into CH-OH; in both cases, numbers of these groups become linked together.The close resemblance between animal and vegetable cells is further shown by the fact that many lower plants (bacteria, monlds, &c.) not only flourish in solutions of albumin and sugar, but actually shed out ferments to convert proteid into peptone, and starch into sugar, and thus aid absorption. They breathe oxygen, produce carbonic anhy- dride, amido-derivatives, and, without the aid of sunlight, fat, carbo- hydrate, and proteid. Nageli (Sitzber. Bnir. Aliad. Wissensch., 2879) has, however, shown that these fungi will assimilate carbon from compounds in which it is cotnbined with hydrogen (amines, &c.), but not from those where it is combined with nitrogen (cyanogen).W. D. H. The Sugar-contents of the Horse’s Stomach. By ELLEN- RERGER and HOFMEISTEB (Pjiiiger’s Am7aiv, 41, 484--489).-Seegen (Abstr., 1888,171) has cGmmented on the small quantities of sugar found in the stomach and intestines, and considers that this may be explained by its rapid absorption immediately it is formed. The authors state that although a similar state of things may occur with peptone formed froin albuniinous food, i t is certainly not the case in horses and pigs fed on starchy food. The quantity of sugar in the alimentary tract of these animals varies, but they have found from 1 to 3.5 per cent. of sugar (30-150 grams) in the stomach of the horse, and from 0.6 to 0.8 in the stomach of the pig.The conditions on which the varying amount of sugar depends are :-(1) Length of time after meal : the highest amount is present 1 to I $ hours after a meal ; (2) abundance or otherwise of hydrochloric acid in the gastric juice, which stops the conversion of starch into wgar ; ( 3 ) condition of the starch in the food, whether cooked or uncooked, com or potatoes, &c. ; (4) another condition which must not be over- looked is the difference of secretion in different parts of the stomach, and if the contents are not properly mixed, more sugar will be found in one part than another (Abstr., 1886, 952; 1887, 743, 744). Seegen appears to have killed his animals too late, 34-13 hours after a meal.W. D. H. Post-mortem Formation of Sugar in the Liver. By H. G~RAKD (P’tiger’s Archiv, 41, 294--YO2).-The table (p. 177) gives the results of estimations of the percentage of sugar and glycogen in pieceq of the liver, a t varying period3 after death. These figures show that the increase in sugar corresponds with the decrease in glycogen ; and the conclusion drawn is that the sugar is formed from the glycogen. This conclusion is contrary, however, to the belief of Seegen, who considers that sugar is formed from pcptone. In addition to this, the following facts were also made out :-That tlie power of liver cells to change a solution of glycogen into sugar is not destroyed after death, even though disease may, during life, have dtJprived the liver of all its glycogen.The presence of blood in the L , e r assists in the process. Other tissues, such as muscles whichAnimal. Sugar. Dog, 1 . . ........ , , 2 .......... , , 3 .......... .. 4 . . ....... Cat, 1 .......... , , 2 .......... Rabbit ......... ........... Glycogen. PHYSIOLOGICAL CHEMISTRY. Sugar. 1.80 3-00 3-50 3.35 2-95 3.15 3.58 4.12 177 Glycogen. 0.76 1-50 1-80 0.80 3-20 2.08 6-35 6-24 ---- 10 minutes after death. 1.75 3-12 3-73 3-30 3-06 3-48 3.85 4.20 Sugar. 0 -55 0 3’4 0 -95 0 -86 0.48 0 -62 0 -75 0.65 0’75 1’38 1-45 0’67 2-88 1-87 4.28 5-05 Glycogen. 2 *12 4 -05 4 -73 3 -56 5 -88 4 -96 9 -56 10-25 24 hours after death. 48 hours after death. contain glycogen, have a similar property, namely, their glycogen is transformed after death into sugar ; a solution of glycogen placed in contact with the muscle, especially when blood is present also, is similarly acted on.If the liver is deprived of glycogen by disease, no sugar is formed in it after death. The liver, after death, moreover, does not possess the property of changing peptone into sugar. W. D. H. Aqueous Humour. By RUHN (P’iiger’s Archiv, 41, 200-202). -Contradictory statements have been made as to the presence or absence of grape-sugar in the aqueous humour. I n the present experiments, the aqueous humour of the rabbit and ox was used ; the humour was withdrawn from the anterior chamber of the eye by a Pravaz sjringe, and the amount drawn from a single eye was suffi- cient to show, with Tromnier’s test, that a substance is always present which reduces copper oxide.This cannot be alcaptone (catechol), as it is not precipitated by lend acetate. It also reduces mercury. Two quantitative estimations were made with large quantities of the fluid, by means of the saccharimeter; the result in one case gave a per- centage of 0.04A sugar, in the other 0.033. vlr. D. H. Lactic Acid in Pale and Red Muscles. By W. GLEISS (l’fliiger’s Archiv, 41, 69--75).-Pde muscles from the frog and the red muscles from the tortoise were tetanised to equal extents ; their acidity was then tested with litmus, the intensity of the change in colour being taken a s a measure of the amount of acid present. In some cases the degree of the yellow tint, produced by lactic acid in dilute solutions of ferric chloride, was used as the test. It was found that the quickly coutracting muscles of the frog became acid much sooner, and to a greater extent, than the slowly-contracting muscles of the tortoise.This was found to be a general rule throughout the animal kingdom; if such a muscle as the gustrocnemius (pale) of a rabbit and the soleus (red) of the same animal were compared in the same way again, the more active muscle was the more acid.178 ABSTRACTS OF CHEMICAL PAPERS. With regnrd to the formation of sarcolactic acid during rigor nzortis, no difference between the t w o sets of muscles could be made out. W. D. H. Citric Acid in Cow’s Milk. By SOXHLET (Chem. Centr., 1888, 1067-1068 ; see also Landw. Verszmhs-Stat., 35, 351-436) .-Henkel has estimated the amount of citric acid in cow’s milk in the author’s laboratory, and finds it contains 0.9 to 1.1 gram per litre.This quaiitity is by no means a small one, being equal i n amount per dzy per cow to that contained by 2 to 3 lemons. The author calculates that the cow’s milk of Bavaria annually contains 40,000 centner (= cwt. approx.) of citric acid. Condensed milk frequently contains crystals of calcium citrate. Glycollic Acid and Pyrotartaric Acid from Suint. By A. BUISTNE and F. BUISINE (C‘ompt. r e d , 107, 789--79l).-GlycoIlic and pyrotartaric acids exist in suint in the form of potassium salts, and are separated from that portion of the suint acids which dissolves in water, alcohol, and ether. After separation of barium rualate and the removal of the excess of hariurn, the solution of the free acid is agitated with washed lead hydroxide, which precipitates basic lead glycollate, whilst pyrotartaric and lactic acids remain in solution.Glycollic acid constitutes about 1 per cent. and pyrotartaric acid about 0.2 per cent. of the dry residue from suint. J. W. L. C. H. B. Fate of certain Ferments in the Organism. By H. HOFFMAN (P’iiger’s ilrchiv, 41, 148-176) .--The result of this investigation are as follows:- 1. In normal human urine, there are varying quantities of pepsin and diastntic ferments present. The amount of these ferments in the urine is related to the intake of food. This point is thoroughly worked ont, and tables and curves are given of the relative amount of pepsin in the urine in connection with the time of day and times of meals. 2. Urine has no power, or hardly any, to destroy pepsin o r diastatic ferments.3. Normal human urine contains no trypsin. 4. Normal human urine easily destlroys small quantities of trypsin. 5. Very large quantities of trypsin are not destroyed by urine. 6. If the flow of the pancreatic secretion into the intestine be hindered or prevented, trypsin appears abundantly i n the urine. 7. Trypsin is found in the liver, spleen, and kidneys of various animals. This will perhaps expIain Herzen’s observation, that a mixture of spleen and pancreas undergoes self-digestion more quickly than the pancreas alone ; the action is a, cumulative one. W. D. H. Composition of Pearls. By J. HARLEY and H. S. HARLET (PTOC. Roy. Soc., 43,461-465) .--A quantitative analysis of oyster pearls gave the following results :-Calcium carbonate, 91.72 per cent.; organic matter (animal) 5.94 per cent. ; water 2.23 per cent. The proportions are quite different from those in mother-of-pearl. Pearls are not solilblePHYSIOLOGICAL CHE NISTRP. 179 in rinegar unless pnlverised. A cocoanut pearl gave on analysis the Fame constituents as oyster pearls, but its origin was doubtful. Hiiman pearls gave water 2.05 per cent., solids 97.95 per cent. ; tiit. solids containing cholesterin, 98.63 per cent., animal matter 1-3T per cent. Hence they appear to be pure choles teriti biliary concretions. H. K. T. Myxcedema. (CZiibicaZ SOC. Frans., Supp. to vol. xxi.)-This volume is a report of a Committee appointed to investigate the disease known as myxmdema. The section rclating to the chemical investigation of the tissues and organs from cases of tlie disease ill human beings, as well as that produced artificially in animals by the r e m o d of the thyroid body, contnius analyses by Drs.Stevenson, Bernnys, and Halliburton. The other sections of the report are of' clirrical interest. Charles (Medico- Chirurg. Trans., 61, 62) stated that in the case examined by him, the skin yielded 50 times more mucin than normal skill does ; hence the name myxcedema given to the disease. The method consisted in extracting the tissue with lime-water (or diluted baryta- water). and then precipitating the much dissolved out by this reagent with excess of acetic acid. This precipitate was collected, washed, dried, and weighed. It is not a method which is absolutely accurate, but it gives fairly good comparative results.The followiug were the average percentages obtained with normal tissues :- Subsequent investigations have not contirmed this. Skin (children). ....................... 0.766 Skin (adults).. ....................... 0.385 Connective tissues.. .................... 0.521 Parotid Heart tendons ........................ .............................. traces. I I n cases of human myxmdema, although there were instances of increase in the amount of mucin in the skin, the average of 10 analyses gives a number (0.374 per cent.) which is approximately the same as i n normal adult skin. With regard to other organs, there waq also noted a slight occasional increase ; the most marked, however, was in the case of the tendons, especially the heart tendons, the average of five analyses giving a percentage of 1.5.Mucin is not only, however, a constituent of the ground substance of connective tissue, but i t also results from the degeneration of proto- ~'lasm as in the goblet cells of mucous membranes, and the acini of 1 he mucous glands. In one case, the parot'id gland was found to con- tain a large increase of rriucin; it normally secretes a clear saliva containing no mucin. This is the only case in which the secreting glands were examined, and the result is interesting, as it coincides with what is seen in the disease produced in monkeys artificially. Monkeys show the disease very typically, and the iiicrease of much can also be demonstrated better than in t'he human subject; for in late st'ages of the disease in man when white fibres or fatt cells have permeated the new connective tissue, the increase of mucin is not a t all marked; in early stages, i t appears to exhibit a percentage of180 -4BSTRACTS OF O1IEMICAL PAPERS.Submaxillary. ------ - trace 6.0 - $-3 0 -16 mucin like that found in the not frilly developed tissues of very young children. Certain classes of animals do not show the typical charac- teristics of the disease. The following table illustrates the quantitative results as obtained in monkeys :- Blood. 0 0 0 -35 trace 0 -54 trace Animal. --- No. la. Normal.. .... No. 9. ........ No. 1. 55 days after operation.. .... No. 3. 32 days after operation.. .... No. 5. 49 days after operation.. .... No. 10. 7 days after operation...... Skin. --- 0.89 0 *9 3 -12 -- 2 - 3 0 -45 Mucin in parts per 1000. Tend on. -- 0 -39 0'5 2 -55 2 *4 0.904 Parotid. -- 0 0 0 '72 -- 1 -7 trace W. D. H.172 ABSTRACTS OF UHEMICAL PAPERS.P h y s i o l o g i c a l C h e m i s t r y .Primary and Secondary Oxidation. By 0. NASSE (PJliigdsArchiv, 41, 378--389).-A distinction is drawn between direct oxida-tion (oxidation occurring a t the body temperature in the blood andfluids of the body by neutral oxygen combining with some readilyoxidisable matter), primary Oxidation (such as occurs in the bodychiefly; tbe complex molecules are first altered by some fermentaction in order to render them readily oxidisable), and secondaryoxidation (oxidation of products of metabolism which have beenformed by other processes than oxidation).The influence of readilyoxidisable substances, such as fat and phenol, given in the food, onsecondary oxidation was investigated, the urine being examinedfor ethereal hydrogen sulphates and glycuronic acid ; it was foundthat the burning of fat in the organism furthers secondary oxidationprocesses, as is shown by the rise in the amount of ethereal hydrogensulphates and fall in the glycuronic acid on the days on which fat wasgiven with the food.By J.LOEB (PJiiger’s Archiv, 42, 393-407) .-The comparison of plantswith animals has suggested the question whether light influences thechemical processes in animals as, according to several experimenters,it does in those plants which contain chlorophyll.Moleschott (Wien.med. Wochensch., 1885) found in frogs that more carbonic anhydride wasproduced in the light than in the dark. But here no observationswere made as to whether the animals moved much or little duringthe experiments. In the light, animals are more stimulated to move-ment, and muscular activity alone might thus explain the increasedproduction of carbonic anhydride. v. Platen (1JLEiiger’s Archiv, 11,272) observed also an increase in gaseous metabolism, and found,moreover, that the illuminatiou of the retina by light also produced,apparently reflexly through the central nervous system, a similareffect. Speck (Arch. j: e q . Path. u. Pharmnk., 12), however, arrivedatj the conclusion that in the human subject, light of itself producesno increase in oxidation processes.On the local action of light ontissues removed from the body, but still retaining some vitality, theexperiments recorded by Fabiiii and others are unsatisfactory andinconclusive, very little care having been taken to avoid putrefaction,W. D. 11.The Influence of Light on Oxidation in AnimalgPHYSIOLOGICAL CHEIIISTRY. 173and even if this had not occurred the tissues were dying, and notliving healthily. Moreover, the influence of changing atmospherictemperature seems also to have been neglected.I n the present research, these sources of error were avoided bytaking lepidopterous lam% in the chrysalis stage when movements arepractically absent. A number of these were weighed and placed i na closed glass vessel witliin a beaker of water, and exposed to diffuseddaylight.0 them were exactly similarly treated, exceps th&t insteadof water, a solution of nigrosine of the same temperature was used,so that t'hey were in darkness. At the end of the experiment, theywere again weighed; those which had lost most weight would bet'hose which had undergone most active oxidation ; but in case somei ridividual peculiarities of the pupa themselves might have producedthese effects, a control experiment was performed by reversing theconditions; those which before were in the light were now put in thedark, and vice uersd.From a number of experiments the conclusion was finally drawnthat light produces in these animals no increase of oxidation pro-cesses; that light has in fact no influence at all on these processes.These simple experinients were fully confirmed by more complexones in which analyses of the oxygen used and carbonic anhydrideproduced were measured.This negatives the idea that light has any local action on animaltissues, although it does not at all contradict the conclusion that lightmay have an indirect effect on animals with intact central nervoussystem and active muscles, probably in this case a reflex effectthrough the optic nerves or sensory nerves of the cutaneous surface.The Melting Point and Chemical Composition of Butter asEffected by Nutrition.By A. MAYER (Landw. Versuchs-Stat.,1888, 261-282) .-The examination of butter produced by cowsunder various conditions was undertaken to explain if possible wheyDanish butter has a better sale t'han Dutch in the English markets.All that was known on the subject was that the Danish is harder andof a better colour.Jnquiries showed that whereas in Holland the cowswere fed on pasture and calved i n spring, in Denmark they, for themost part, drop their calves late on in the year, and are house fed.The cows under examination were fed at rarious periods on roots,hay, grass, clover, and silage, and the analysis of the butterproduced showed that the percentage of volatile acids varies as thespecific gravitv ; that the melting point does not march parallel withspecific gravity, but is dependent on the percentage of the oleins,butyrin, cnpronin, &c., present ; the percentage of volatile acids and thespecific gravity of the butter produced by any one cow varies moreconsiderably than is generally supposed when the experimental con-ditions are changed: the percenlxage of volatile fatty acids is de-pendent on the period of lactation, rising as the period progresses,but it is also dependent on the feeding, being highest when roots,meadow-grass, and clover are giren, and lowest with ensilage : on thecontrary, ensilage and hay produced a butter of high melting point,whilst grass or clover, whether as pasture or given cut in the housc,W.D. H17.1 ABSTRACTS OF CHEMICAL PAPERS.lowers the melting point : the solidifying point follows the meltingpoint, rising and falling with it.Protei‘d Metabolism in Man. By P.H~RSCHFELD (l‘jliiger’sArchiv, 41, 533--565).--The following are the final couvlusionsdrawn by the author from his research. It is possible for a healthxman (in one case for 15 days, in another for 10 days) to maintain anitrogenous balance and equal body weight on from 5-8 prams ofnitrogen daily: this corisesponds to 30-35 grams of proteid ; or ifone excepts the days on which very little nitrogen ( 5 grams) w a staken, the conclusion that 35-40 grams of proteid per diem is suffi-cient can certainly be drawn. Whether this would be possible forperiods longer than thohe mentioned cannot be stated.This is contrary to the generally received opinion that an adultman requires 100-120 grams of prote’id daily, and that it is dangerousto ingest less, or else the tissue-proteids will be disintegrated.On thecontrary, so much prote‘id as this increases t lie tissue-proteid (unlessgreat activity Compensates for this hypertrophy), and the fat of theorganism also increases.By E. NEISSER (Chew. Centr., 1888, 1083, from Centr.Physiol., 1888, 141-142).-The author conducted experiments withmice fed with about 80 different sorts of food in order to determinethe extent to which the glycogen of the liver is affected by them.Morphine, amygdah, and mytilotoxin appear to cause an accumula-tion of glycogen. The health of the animals was no doubt of con-siderable influence on the amount of glycogen, although in one case,that of a, mouse fed on mytilotoxin, and seriously ill, the liver con-tained a considerable quantity of glycogen, whilst, on the other hand,with several animals fed on papain, asparagine, coniferin, coumarin,and in perfect health, the liver contained no glycogen.Synthetical Processes in the Animal Organism.By E.PFL~~GER (Pfliiger’s Archiv, 42, 144--154).-A living liver free fromglycogen will again form that substance, not only from carbohydratesbut from glycerol, gelatin, or proteid. v. Mering fed dogs on phlo-ridzin, whereby they became diabetic, and in a few dajs all carbo-hydrate material in the body had been discharged in the urine assugar. If now the same drug was given to the same animals after afew days’ interval, during which they had no food, they once morebecame intensely diabetic, and the quantAy of sugar passed was soenormous that it cannot be supposed to have come from the drugitself ( Verhandl.VI Congresses inneres Med. Wiesbaden, 1887). Oneexplanation of the way in which glycogen is formed after the ad-ministration of glycerol, is the well-known “ economy tlheory,” anotheris that glycerol and like substances act as stimuli to liver activity. Itcertainly cannot be supposed that glycogen is directly formed fromthe substance administered-or a t least not in all cases ; for instance,from ammonium carbonate. The question then arises as to the geneticrelationship existing between glycogen and albumin. Experimentson the decomposition products of proteids have in no case yielded acarbohydrate; and not only that,, but proteids never yield any ofE.W. P.W. D. H.Glycogen.J. W. LPhYSIOLOGlCAT~ CHEMISTRY. 175the decomposition products of carbohydrates (lactic acid, mncic acid,tartaric acid, &c.). Still, we have the formation of glycogen takingplace in the liver when no food b u t albuminous food is taken.The following general considerations will, however, lead to a betterunderstanding ot the snbject. The cliernical differences betweenanimal and vegetable cells are not so great as was at one time hup-posed. Their chemical composition, so far as it is known, is thesame ; all living cells breathe oxygen, and produce carbonic anhjdride,water, and amitlo-compounds. If the synthetic prucesws are morehigh17 developed in chlorophyll-holding plants, that does not meanthat synthetic processes are absent from animal cells.As instancesof syntlietic processes in animal cells, the formation of hippuric acidfrorn glj cocine and benzoic acid, or of ethereal hydrogen sulphatesfrom phenol and sulphuric acid, may be laken. A special kind ofsynthesis must, moreorer, occur in the retrogressive metamorphosesof proteids which lead to the formation of uric acid and members ofthe same group. In albumin itself, and in the products of albuminobtained outside the body, the number of carbon-atoms is much greaterthan that, of niti-ogen-atoms (indole, leucine, tyrosine, &c.) ; b u t inthese products of metamorphoses in the body, the nitrogen and carbon-atoms are nearly equal in number, or, as in the cases of urea andguanidine, the nitrogen-atoms are the mme numerous.The im-portance of such synthesis occurring in living cells, resulting i n theformation of cyanogen containing molecules, has been before insistedon by the author.Researches on the formation of fat within the body show that hereagain there are undoubtedly syntheses occurring as the result of theactivity of living cells: in fact, reactions occur which cannot berepeated in the laboratory or explained by any known chemical laws :they are probably, therefore. the result of a breaking down of moleculesin the first place, and the living cells then building up entirely newmaterials of a couip!icated nature from the simple carbon compoundsso liberated.The carbohydrates, for example, are derivatives of the hesatomicalcohol C,H,(OH),.Biit by feeding an animal on starch, the fat of thebody is increased, and substances containing chains of 16 to 18 atoms ofcarbon linked one to another are formed ; and in the case of stearic acidat least, we have a number (16) which is not a multiple of 6. Bythis synthesis, too, we have substanceb which possess the property ofcirciilar polarisation changed into those which are optically inactive.'The firrt change must, however, be a process of reduction ; metabolicchanges m u s t occur. and no nutrient material stimulates metabolismlike protejid ; this explains why feeding on starch mixed with a smallamount of proteid produces fat, and without it will not. The proteidadmixture is, however, so small that it alone will not explain the greatincrease in fat.I n other parts of the animal kingdom, there aresimilar occurrences ; for instance, the formation of beeswax fromhoney. Another sample of the same kind is the formation of fat fromproteid, although this is not so well proved as the foregoing cases. I nthe synthesis of fat from carbohydrate, the group CH*OH must bechanged into CH, ; and in the formation of carbohydrate (glycogen176 ABSTRACTS OF CHEMICAL PAPERS.from prote’id, the group CB, must be changed into CH-OH; in bothcases, numbers of these groups become linked together.The close resemblance between animal and vegetable cells is furthershown by the fact that many lower plants (bacteria, monlds, &c.) notonly flourish in solutions of albumin and sugar, but actually shed outferments to convert proteid into peptone, and starch into sugar, andthus aid absorption.They breathe oxygen, produce carbonic anhy-dride, amido-derivatives, and, without the aid of sunlight, fat, carbo-hydrate, and proteid. Nageli (Sitzber. Bnir. Aliad. Wissensch., 2879)has, however, shown that these fungi will assimilate carbon fromcompounds in which it is cotnbined with hydrogen (amines, &c.), butnot from those where it is combined with nitrogen (cyanogen).W. D. H.The Sugar-contents of the Horse’s Stomach. By ELLEN-RERGER and HOFMEISTEB (Pjiiiger’s Am7aiv, 41, 484--489).-Seegen(Abstr., 1888,171) has cGmmented on the small quantities of sugarfound in the stomach and intestines, and considers that this may beexplained by its rapid absorption immediately it is formed.The authors state that although a similar state of things may occurwith peptone formed froin albuniinous food, i t is certainly not thecase in horses and pigs fed on starchy food.The quantity of sugarin the alimentary tract of these animals varies, but they have foundfrom 1 to 3.5 per cent. of sugar (30-150 grams) in the stomach ofthe horse, and from 0.6 to 0.8 in the stomach of the pig.The conditions on which the varying amount of sugar dependsare :-(1) Length of time after meal : the highest amount is present1 to I $ hours after a meal ; (2) abundance or otherwise of hydrochloricacid in the gastric juice, which stops the conversion of starch into wgar ;( 3 ) condition of the starch in the food, whether cooked or uncooked,com or potatoes, &c.; (4) another condition which must not be over-looked is the difference of secretion in different parts of the stomach,and if the contents are not properly mixed, more sugar will be foundin one part than another (Abstr., 1886, 952; 1887, 743, 744).Seegen appears to have killed his animals too late, 34-13 hoursafter a meal. W. D. H.Post-mortem Formation of Sugar in the Liver. By H.G~RAKD (P’tiger’s Archiv, 41, 294--YO2).-The table (p. 177) givesthe results of estimations of the percentage of sugar and glycogen inpieceq of the liver, a t varying period3 after death.These figures show that the increase in sugar corresponds with thedecrease in glycogen ; and the conclusion drawn is that the sugar isformed from the glycogen.This conclusion is contrary, however,to the belief of Seegen, who considers that sugar is formed frompcptone.In addition to this, the following facts were also made out :-Thattlie power of liver cells to change a solution of glycogen into sugar isnot destroyed after death, even though disease may, during life, havedtJprived the liver of all its glycogen. The presence of blood in theL , e r assists in the process. Other tissues, such as muscles whicAnimal.Sugar.Dog, 1 . . ........, , 2 .........., , 3 .......... .. 4 . . .......Cat, 1 .........., , 2 ..........Rabbit ......... ...........Glycogen.PHYSIOLOGICAL CHEMISTRY.Sugar.1.803-003-503.352-953.153.584.12177Glycogen.0.761-501-800.803-202.086-356-24----10 minutes afterdeath.1.753-123-733-303-063-483.854.20Sugar.0 -550 3’40 -950 -860.480 -620 -750.650’751’381-450’672-881-874.285-05Glycogen.2 *124 -054 -733 -565 -884 -969 -5610-2524 hours afterdeath.48 hours afterdeath.contain glycogen, have a similar property, namely, their glycogen istransformed after death into sugar ; a solution of glycogen placed incontact with the muscle, especially when blood is present also, issimilarly acted on.If the liver is deprived of glycogen by disease, no sugar is formedin it after death.The liver, after death, moreover, does not possessthe property of changing peptone into sugar.W. D. H.Aqueous Humour. By RUHN (P’iiger’s Archiv, 41, 200-202).-Contradictory statements have been made as to the presence orabsence of grape-sugar in the aqueous humour. I n the presentexperiments, the aqueous humour of the rabbit and ox was used ; thehumour was withdrawn from the anterior chamber of the eye by aPravaz sjringe, and the amount drawn from a single eye was suffi-cient to show, with Tromnier’s test, that a substance is always presentwhich reduces copper oxide. This cannot be alcaptone (catechol), asit is not precipitated by lend acetate. It also reduces mercury. Twoquantitative estimations were made with large quantities of the fluid,by means of the saccharimeter; the result in one case gave a per-centage of 0.04A sugar, in the other 0.033.vlr. D. H.Lactic Acid in Pale and Red Muscles. By W. GLEISS(l’fliiger’s Archiv, 41, 69--75).-Pde muscles from the frog and thered muscles from the tortoise were tetanised to equal extents ; theiracidity was then tested with litmus, the intensity of the change incolour being taken a s a measure of the amount of acid present. Insome cases the degree of the yellow tint, produced by lactic acid indilute solutions of ferric chloride, was used as the test. It was foundthat the quickly coutracting muscles of the frog became acid muchsooner, and to a greater extent, than the slowly-contracting muscles ofthe tortoise. This was found to be a general rule throughout theanimal kingdom; if such a muscle as the gustrocnemius (pale) of arabbit and the soleus (red) of the same animal were compared inthe same way again, the more active muscle was the more acid178 ABSTRACTS OF CHEMICAL PAPERS.With regnrd to the formation of sarcolactic acid during rigor nzortis,no difference between the t w o sets of muscles could be made out.W.D. H.Citric Acid in Cow’s Milk. By SOXHLET (Chem. Centr., 1888,1067-1068 ; see also Landw. Verszmhs-Stat., 35, 351-436) .-Henkelhas estimated the amount of citric acid in cow’s milk in the author’slaboratory, and finds it contains 0.9 to 1.1 gram per litre. Thisquaiitity is by no means a small one, being equal i n amount per dzyper cow to that contained by 2 to 3 lemons. The author calculatesthat the cow’s milk of Bavaria annually contains 40,000 centner(= cwt.approx.) of citric acid. Condensed milk frequently containscrystals of calcium citrate.Glycollic Acid and Pyrotartaric Acid from Suint. By A.BUISTNE and F. BUISINE (C‘ompt. r e d , 107, 789--79l).-GlycoIlicand pyrotartaric acids exist in suint in the form of potassium salts,and are separated from that portion of the suint acids which dissolvesin water, alcohol, and ether. After separation of barium rualate andthe removal of the excess of hariurn, the solution of the free acid isagitated with washed lead hydroxide, which precipitates basic leadglycollate, whilst pyrotartaric and lactic acids remain in solution.Glycollic acid constitutes about 1 per cent. and pyrotartaric acidabout 0.2 per cent. of the dry residue from suint.J. W.L.C. H. B.Fate of certain Ferments in the Organism. By H. HOFFMAN(P’iiger’s ilrchiv, 41, 148-176) .--The result of this investigation areas follows:-1. In normal human urine, there are varying quantities of pepsinand diastntic ferments present. The amount of these ferments in theurine is related to the intake of food. This point is thoroughlyworked ont, and tables and curves are given of the relative amount ofpepsin in the urine in connection with the time of day and times ofmeals.2. Urine has no power, or hardly any, to destroy pepsin o r diastaticferments.3. Normal human urine contains no trypsin.4. Normal human urine easily destlroys small quantities of trypsin.5. Very large quantities of trypsin are not destroyed by urine.6. If the flow of the pancreatic secretion into the intestine behindered or prevented, trypsin appears abundantly i n the urine.7.Trypsin is found in the liver, spleen, and kidneys of variousanimals. This will perhaps expIain Herzen’s observation, that amixture of spleen and pancreas undergoes self-digestion more quicklythan the pancreas alone ; the action is a, cumulative one.W. D. H.Composition of Pearls. By J. HARLEY and H. S. HARLET (PTOC.Roy. Soc., 43,461-465) .--A quantitative analysis of oyster pearls gavethe following results :-Calcium carbonate, 91.72 per cent. ; organicmatter (animal) 5.94 per cent. ; water 2.23 per cent. The proportionsare quite different from those in mother-of-pearl. Pearls are not solilblPHYSIOLOGICAL CHE NISTRP. 179in rinegar unless pnlverised.A cocoanut pearl gave on analysis theFame constituents as oyster pearls, but its origin was doubtful.Hiiman pearls gave water 2.05 per cent., solids 97.95 per cent. ; tiit.solids containing cholesterin, 98.63 per cent., animal matter 1-3T percent. Hence they appear to be pure choles teriti biliary concretions.H. K. T.Myxcedema. (CZiibicaZ SOC. Frans., Supp. to vol. xxi.)-Thisvolume is a report of a Committee appointed to investigate thedisease known as myxmdema. The section rclating to the chemicalinvestigation of the tissues and organs from cases of tlie disease illhuman beings, as well as that produced artificially in animals by ther e m o d of the thyroid body, contnius analyses by Drs. Stevenson,Bernnys, and Halliburton.The other sections of the report are of'clirrical interest.Charles (Medico- Chirurg. Trans., 61, 62) stated that in the caseexamined by him, the skin yielded 50 times more mucin than normalskill does ; hence the name myxcedema given to the disease.The methodconsisted in extracting the tissue with lime-water (or diluted baryta-water). and then precipitating the much dissolved out by thisreagent with excess of acetic acid. This precipitate was collected,washed, dried, and weighed. It is not a method which is absolutelyaccurate, but it gives fairly good comparative results. The followiugwere the average percentages obtained with normal tissues :-Subsequent investigations have not contirmed this.Skin (children). ....................... 0.766Skin (adults).. ....................... 0.385Connective tissues.. .................... 0.521ParotidHeart tendons ...................................................... traces. II n cases of human myxmdema, although there were instances ofincrease in the amount of mucin in the skin, the average of 10 analysesgives a number (0.374 per cent.) which is approximately the same asi n normal adult skin. With regard to other organs, there waq alsonoted a slight occasional increase ; the most marked, however, was inthe case of the tendons, especially the heart tendons, the average offive analyses giving a percentage of 1.5.Mucin is not only, however, a constituent of the ground substance ofconnective tissue, but i t also results from the degeneration of proto-~'lasm as in the goblet cells of mucous membranes, and the acini of1 he mucous glands. In one case, the parot'id gland was found to con-tain a large increase of rriucin; it normally secretes a clear salivacontaining no mucin. This is the only case in which the secretingglands were examined, and the result is interesting, as it coincideswith what is seen in the disease produced in monkeys artificially.Monkeys show the disease very typically, and the iiicrease of muchcan also be demonstrated better than in t'he human subject; for inlate st'ages of the disease in man when white fibres or fatt cells havepermeated the new connective tissue, the increase of mucin is not a tall marked; in early stages, i t appears to exhibit a percentage o180 -4BSTRACTS OF O1IEMICAL PAPERS.Submaxillary.-------trace6.0-$-30 -16mucin like that found in the not frilly developed tissues of very youngchildren. Certain classes of animals do not show the typical charac-teristics of the disease.The following table illustrates the quantitative results as obtainedin monkeys :-Blood.000 -35trace0 -54traceAnimal.---No. la. Normal.. ....No. 9. ........No. 1. 55 days afteroperation.. ....No. 3. 32 days afteroperation.. ....No. 5. 49 days afteroperation.. ....No. 10. 7 days afteroperation.. ....Skin.---0.890 *93 -12--2 - 30 -45Mucin in parts per 1000.Tend on.--0 -390'52 -552 *40.904Parotid.--000 '72--1 -7traceW. D. H

ISSN:0368-1769    

DOI:10.1039/CA8895600172

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

180 -4BSTRACTS OF O1IEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Bacterio-purpurin. By T. W. ENGELMANN (Pfiiiger’s Archiv, 42, 183--186).-1n P$iiger’s Archiv (30, 95) the author has previously described a bacterium producing a red pigment, to which he gave the name B. photometricurn, as light by varying the %mount of red pigment influences its movements. Since then he has made :L number of observations on different varieties of bacteria which pro- duce a red colour. All belong t o the class of sulphur-bacteria (Winogradsky, Botan. Zeit., 1887, No. 31-37) ; that is, bacteria which in the presence of free hydrogen sulphide, oxidise sulphur, forming sulphuric acid ; all these bacteria are moreover coloured by a purplish- red pigment diffused through their protoplasm-bacterio- purpurin (Ray-Lankester) ; they are all also influenced by light like the B.yhotometricum. This last point distinguishes them from certain col ou rless sulphur- bnc t erin. Different coloured lights affect the bacteria differently ; the most, powerful being the ultra-red, tlie yellow, and part of the green. These are tile places i n the absorption-spectrum of bacteria-purpuriu where the greatest absorption of light occurs. A table is given of the amount of absorption of light of bacterio-purpurin measured by the spectroDhotometer for the different part of the spectrum. Absorp- tion and physiological effects are thus closely related to one another.VEGETABLE PHTSIOLOGIF AND AQRICULTURE. 181 This fact suggested a comparison between this pigment and chloro- pllyll; and i t was then found that bacterio-purpurin is a chromo- phylI, absorbing carbonic anhjdride, and giving out oxygen in the light ; sunlight produces this most readily, but the ultra-red works only a little less efficiently than mixed light’.Beer Yeast. By MARTINAND (Coinpt. rend., 107, 745-748) .- Observations of the time required to form acrospores do not yield results sufficiently precise to distinguish between different species of snccharomyces. Experiments in which various species of saccharoinyces were allowed to act on sierilised solutions of maltose for several days, show t h a t X. cerewisioe from beer yeast acts more rapidly and com- pletely than S. ellipsodeus, S. pastorianus, and S. apiculatus. The times required for the formation of acrospores were somewhat variable.With a solution of saccharose inverted by hydrochloric acid, S. cere- risin! and S. pastorianus were found to act less completely than S. ellipsoideus. Further experiments are required before these observations can be utilised for the practical analysis of yeast. Yeast-poisons. By H. SCKULZ (P’iiger’s Archiw, 42, 517-541). -Previous researches by the author (Virchozu’s Arch., 108, 427) have led him to the conclusion that drugs produce their effect by raising or lowering the physiological processes in animal cells ; and that small and large doses of any one drug may produce opposite effects of this kind. The same thing occurs with vegetable cells, the various substances that, in large amount, produce stoppage of fermentations, produce, when excessively dilute, an increase of the activity of the yeast organisms as measured by the amount and pressure of carbonic anhydride produced.The apparatus used for the investigation is fully described, and the results set out in detail, the pressure of carbonic anhydride being represented graphically in the form of curves. The results, however, may be briefly summarised in the following way for each of the various drugs used :- Mercuric Chloride.-The increase of activity of the yeast showed itself most when the amount of dilution was about 1 : 500,000. 5 Iodine.-Here the optimum was reached when the dilution was 1 : 600,000 in one series of experiments ; 1 : 100,000 in another. Bromine.-Here two sets of experiments both yieIded the dilution 1 : 300,000 as the most favourable for ferment, activity.Arsenious Acid.-The relation found here as the best was somewhat less than in the foregoing cases ; the proportion of 1 : 40,000 gave the most vigorous production of carbonic anhydride : a dilution less than this, 1 : 50,000, produced no effect whatever. Chromic Acid.-This had to be used still more concentrated; a dilution 1 : 8000 producing the most marked stimulating effect on the micro-oi-ganisms, Xalicylic Acid.-The optimum of dilution was here 1 : 4000 ; and in the case of formic acid 1 : 10,000. W. D. H. C. H. B. W. D. H.182 ABSTRACTS O F CHEMICAL PAPERS. Blood Pigment as a Gauge of Gaseous Exchanges in Plants. By T. W. ENGELMANN (PJuger’s Archiv, 42. 186--188).-The prin- ciple of this method is not new, as Hoppe-Seyler showed ( Z e i f .phiisid. Chern., 2, 425) that a piece of living Elodea canadensis in diluted decomposing blood will in direct sunlight cause the venous colour to become arterial, while in the dark the venous colour returns. But this same fact may also be used for microscopical investigations of living cells or small particles of living plant tissues, and as a test for chromophylls. A small spray of spiropyra m7as mounted on a drop of diluted defibrinated ox blood, which had been rendered venous by a stream of hydrogen or carbonic anhydride. I n 10-15 minutes in diffuse dayliqht, in one minute in direct sunlight, the blood in the neighbourhood of the green fragment had become arterial, while in the dark it once more returned to its venous tint, The same change may be watched with a spectral ocular, or better a microspectrophotometer ; the one band of hEmoglobin giving place to the two of oxyhEmoglobin, or the reverse.The change occurs a t different rates under the influence of light from different parts of the spectrum :-A spectrum was projected under the preparation; the change t o the arterial tint occurred in that part of the spray of the spirogyra which was lying over the outermost part of the visible rkd, 1-eaching its height, however, about the C line, and then sank until the beginning of the green was reached. Sometimes a secocd effect was seen in the blue-green, and a slighter one in the violet. Other chromophylls (for instance, bacterio-purpurin, see p. 180) act mutatis mutandis similarly to chlorophyll.W. D. H. A Plant which Destroys the Sense of Taste for Sweets and Bitters. By B. BERTHOLD (Chem. Cenlr., 1888, 1071, from Centr. Ned. Wiss., 1888, 460--461).-This drug comes from an Asclepiadea, Gymmema sylvestre, found in Assam, on the Coromsndel coast, and on the African continent, and is a stronp woody shrub with long thin branches. The Hindoos have used the pulverised bark for a long time as an antidote against snake bites. When chewed, the leaves possess a t first a bitter astringent, later a, slightly acid taste. Directly after chewing, one loses the power of taste for sweet and bitter principles, b u t only for these two effects on the sense of taste. Sugar tastes like sand and quinine sulphate like chalk. A t the end of 2-2 hours, the normal sense of taste is recovered.The author has com- menced the chemical investigat,ion, and has succeeded in separating three substances, but these are not yet sufficiently characterised. Occurrence of Aluminium in Vascular Cryptogams. By J. W. L. A. H. CHURCH (Proc. Roy. Soc., 44, 121--129).--n/lore recent analyses generally recognise the presence of alumina in plants as adventitious. The author has, however, found it to be an important constituent of many Lycopodiae, for instance, L. alpinurn, L. clavaturn, L. selap, and L. cernuurn, whilst in Selnginella spinulosa it is absent. The earth is also absent in L. phlegmaria and L. billurdieri, hilt these were afterwards found to be epiphytic. Plants closely related to theVEGETABLE PH YYLOLOQY AND AG KICULT UIt K.183 Jqcopodiq namely, E'quiseturn, Ophioglossum, Salvinia, Marsilea, Psiloturn, and Selaqinella, gave negative results. Of tree feriis, c!yathea seym gave negative results, whilst the ash of an unknown tree fern from New Zealand contained 19.65 per cent., Cyatherc medu1Zari.s from the same source examined qualitatively gave abundance of alumina, as also did AZsophila australis and to a less extent Dicksonicr, squarrosa. Alumina is also an important constituent of the water- moss, Fonfindis nntipyretica. The alumina in the Lycopodi8 occurs in combination with organic acids. It niay serve to neutraliw the acids produced in the plant. It is noticeable that the essential in- organic constituents of plants have low atomic weights, and fall nithin series 1, 2, 3, and 4 of the periodic arrangement.Formation of Nitric and Nitrous Acids by the Evaporation of Water in Presence of Alkalis and Soil. By A. BAUMANN (Lanclw. Versuchs-Stat.. 1888,217-264).-Schonb~in (Annaleii, 124,4) and others have stated that when water is evaporated, ammonium nitrate and nitrite ale produced. They also stated that calcium carbonate as well as hydrated oxides absorb ammonia and con-rert it into nitrates. The author has made numerous experiments, all of which he here details, and brings forward conclusive evidence that all these experi- ments made by Schiinbein are incorrect. He firstly attributes the false results to the absence of the delicate reagents now a t hand, whereby ammonia, nitrates, nitrites, and ozone, and hydrogen peroxide may he detected.Secondly, he shows that the source of nitrates is the gas flames used for evaporation, and for heating water-baths, &c., and that, when evaporation is conducted without the direct aid of gas flames, for instance, by sun heat, or previously heated sand-baths, uo trace of nitrates is found, if the evaporation is conducted in a rocm where no gas flames have been burning. He further shows that most of the chemical preparations which are sold as pure contain nitric acid, and he instances a case in which to prepare pure calcium car- bonate by precipitation, one portion of the product was dried in a water-bath, the other portion by filter-paper, the former product con- tained nitrate, the latter none. This holds good for all reagents similarly prepared. It is also shown that even the very tests employed to detect nitric acid, such as brucine, may and frequently do contain a trace of nitrate.Passing on to Franks' experiments on the disappearance of the ammonia when ammonium chloride is mixed with soil, he points out that Frank seems to have forgotten the action of alkalis on com- pounds of ammonia, and shows that in forest soils nitrates are not found, nor are they produced from added ammonia. Finally, he warns all who are experimenting on nitrification to beware lest they introduce nitric acid by heating their solutions over gas flames, or ignite solids in open crucibles, &c., also that chemicals or samples must not be kept in rooms where gas is burning, or they will be more or less contaminated. E.W. P. H. I(. T. Composition of Spring Wheats grown in 1887. By M. MARCKER (Bied. Centtr., lb88, 708 --715j.-This is a similar paper to184 ABSTRACTS OF OHEMICAL PAPERS. the following, in which the compositions of varieties of foreign wheats are compared. It appears th;t t. gmernlly, the highest percentage of albuminojids and gluten i s to be found in those wheats which come quickest to maturity (under 130 days), when there would be, of albu- mino'ids, 13.17 per cent., and of dry gluten, 18 08, whereas when the period of growth exceeds 130 days, the albuminojids amount to only 12.47, and gluten t o 9.22 per cent. ; the smaller the grain, the higher the percentage of gluten, whilst a large grain is indicative of a high percentage of starch ; the wheats richest in gluten produce a more bulky dough than other kinds, and the early ripened wheat and the largest grains are most suitable for baking purposes.The greater the percentage of gluten, the higher will the dough made from the flour rise in the aleurometer. E. W. P. Composition of East Indian Wheat. By T. DIETRICH (Landw. Versuchs-Stat., 1888, 309--318).-Several varieties of Indian wheat are fully described, both physically and chemically. On com- paring the percentage of albuminojids, it is found that the mean of 937 analyses of English, Russian, &c., wheats gives 13.90 of crude albuminoids in the dry substance, whilst the Indian wheats contain only 12.66 per cent. m a mean. E. W. P. Composition and Nutritive Value of Oats. By M. MARCEER (Bied. Centr., 1888, 697--704).--Prom a number of analyses and experiments on several varieties of oats, the details of which are given, the following conclusions are drawn :-The heavier-yielding sort is poorer in albumino'ids than the lighter-yielding; there is no definite ratio between the percentages of fat and albuminojids ; that sort which comes quickest to maturity is richest in albuminoids ; the grain poorest in albuminoids has the lowest bushel-weight, and the largest iridividual grains are also the poorest in nitrogen ; the coeffi- cient of digestion does not seem to be influenced by the composition.Those grains which are smallest in size and richest in nitrogen have most hull, and generally this hull is poorer in albuminojids than that of other grains. The thickness of the skin surrounding the seed, measured immediately above the embryo, is not invariable-in one year it may be thickest in the large grains, whilst in other years it is thinnest.A table is also given representing the germinative power and total yield of nutrients per acre, but with one 01- two exceptions the oats are of foreign kiuds and not grown in England. E. W. P. Calcium Sulphite as a Preventative of Loss of Nitrogen in Manure Heaps. By E. JENSCH (Clzern. Zeit., 12, 354--355).--The author draws attention to the enormous losses of nitrogen inherent to the present system of storing farmyard manure. These losses can be reduced by spreading gypsum, superphosphate and gypsum, and kairiite on the manure; b u t such additions are superfluous from a. manurial point of view in many districts, therefore those means have not met with extensive application.Calcium sulphite is now recom- Inended for the purpose ; itl is inexpensive, can be applied everywhere, and not only retains ammoiiia, but also acts as a disinfectant. It isANALYTICAL CHEMISTRY. 185 obtained as a bye-product from the gases evolved from the roasting of zinc-blende, and is specially prepared for the present purpose free from lime and calcium carbonate, and with an ammonia-absorbing efficiency of 85 per cent. as compared with 68 per cent. in the best commercial unburnt gypsum. Its action as a manure on vegetation has yet to be tested. D. A. L.180 -4BSTRACTS OF O1IEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Bacterio-purpurin. By T.W. ENGELMANN (Pfiiiger’s Archiv, 42,183--186).-1n P$iiger’s Archiv (30, 95) the author has previouslydescribed a bacterium producing a red pigment, to which he gavethe name B. photometricurn, as light by varying the %mount of redpigment influences its movements. Since then he has made :Lnumber of observations on different varieties of bacteria which pro-duce a red colour. All belong t o the class of sulphur-bacteria(Winogradsky, Botan. Zeit., 1887, No. 31-37) ; that is, bacteria whichin the presence of free hydrogen sulphide, oxidise sulphur, formingsulphuric acid ; all these bacteria are moreover coloured by a purplish-red pigment diffused through their protoplasm-bacterio- purpurin(Ray-Lankester) ; they are all also influenced by light like the B.yhotometricum.This last point distinguishes them from certaincol ou rless sulphur- bnc t erin.Different coloured lights affect the bacteria differently ; the most,powerful being the ultra-red, tlie yellow, and part of the green. Theseare tile places i n the absorption-spectrum of bacteria-purpuriuwhere the greatest absorption of light occurs. A table is given ofthe amount of absorption of light of bacterio-purpurin measured bythe spectroDhotometer for the different part of the spectrum. Absorp-tion and physiological effects are thus closely related to one anotherVEGETABLE PHTSIOLOGIF AND AQRICULTURE. 181This fact suggested a comparison between this pigment and chloro-pllyll; and i t was then found that bacterio-purpurin is a chromo-phylI, absorbing carbonic anhjdride, and giving out oxygen in thelight ; sunlight produces this most readily, but the ultra-red worksonly a little less efficiently than mixed light’.Beer Yeast.By MARTINAND (Coinpt. rend., 107, 745-748) .-Observations of the time required to form acrospores do not yieldresults sufficiently precise to distinguish between different species ofsnccharomyces. Experiments in which various species of saccharoinyceswere allowed to act on sierilised solutions of maltose for several days,show t h a t X. cerewisioe from beer yeast acts more rapidly and com-pletely than S. ellipsodeus, S. pastorianus, and S. apiculatus. The timesrequired for the formation of acrospores were somewhat variable.With a solution of saccharose inverted by hydrochloric acid, S.cere-risin! and S. pastorianus were found to act less completely thanS. ellipsoideus.Further experiments are required before these observations can beutilised for the practical analysis of yeast.Yeast-poisons. By H. SCKULZ (P’iiger’s Archiw, 42, 517-541).-Previous researches by the author (Virchozu’s Arch., 108, 427) haveled him to the conclusion that drugs produce their effect by raisingor lowering the physiological processes in animal cells ; and thatsmall and large doses of any one drug may produce opposite effectsof this kind.The same thing occurs with vegetable cells, the various substancesthat, in large amount, produce stoppage of fermentations, produce,when excessively dilute, an increase of the activity of the yeastorganisms as measured by the amount and pressure of carbonicanhydride produced.The apparatus used for the investigation is fully described, and theresults set out in detail, the pressure of carbonic anhydride beingrepresented graphically in the form of curves.The results, however, may be briefly summarised in the followingway for each of the various drugs used :-Mercuric Chloride.-The increase of activity of the yeast showeditself most when the amount of dilution was about 1 : 500,000.5 Iodine.-Here the optimum was reached when the dilution was1 : 600,000 in one series of experiments ; 1 : 100,000 in another.Bromine.-Here two sets of experiments both yieIded the dilution1 : 300,000 as the most favourable for ferment, activity.Arsenious Acid.-The relation found here as the best was somewhatless than in the foregoing cases ; the proportion of 1 : 40,000 gave themost vigorous production of carbonic anhydride : a dilution less thanthis, 1 : 50,000, produced no effect whatever.Chromic Acid.-This had to be used still more concentrated; adilution 1 : 8000 producing the most marked stimulating effect on themicro-oi-ganisms,Xalicylic Acid.-The optimum of dilution was here 1 : 4000 ; andin the case of formic acid 1 : 10,000.W.D. H.C. H. B.W. D. H182 ABSTRACTS O F CHEMICAL PAPERS.Blood Pigment as a Gauge of Gaseous Exchanges in Plants.By T. W. ENGELMANN (PJuger’s Archiv, 42. 186--188).-The prin-ciple of this method is not new, as Hoppe-Seyler showed ( Z e i f .phiisid.Chern., 2, 425) that a piece of living Elodea canadensis indiluted decomposing blood will in direct sunlight cause the venouscolour to become arterial, while in the dark the venous colour returns.But this same fact may also be used for microscopical investigationsof living cells or small particles of living plant tissues, and as a testfor chromophylls. A small spray of spiropyra m7as mounted on adrop of diluted defibrinated ox blood, which had been renderedvenous by a stream of hydrogen or carbonic anhydride. I n 10-15minutes in diffuse dayliqht, in one minute in direct sunlight, theblood in the neighbourhood of the green fragment had becomearterial, while in the dark it once more returned to its venous tint,The same change may be watched with a spectral ocular, or better amicrospectrophotometer ; the one band of hEmoglobin giving placeto the two of oxyhEmoglobin, or the reverse.The change occurs a t different rates under the influence of lightfrom different parts of the spectrum :-A spectrum was projectedunder the preparation; the change t o the arterial tint occurred inthat part of the spray of the spirogyra which was lying over theoutermost part of the visible rkd, 1-eaching its height, however, aboutthe C line, and then sank until the beginning of the green wasreached.Sometimes a secocd effect was seen in the blue-green, anda slighter one in the violet. Other chromophylls (for instance,bacterio-purpurin, see p. 180) act mutatis mutandis similarly tochlorophyll.W. D. H.A Plant which Destroys the Sense of Taste for Sweets andBitters. By B. BERTHOLD (Chem. Cenlr., 1888, 1071, from Centr.Ned. Wiss., 1888, 460--461).-This drug comes from an Asclepiadea,Gymmema sylvestre, found in Assam, on the Coromsndel coast, and onthe African continent, and is a stronp woody shrub with long thinbranches. The Hindoos have used the pulverised bark for a longtime as an antidote against snake bites. When chewed, the leavespossess a t first a bitter astringent, later a, slightly acid taste. Directlyafter chewing, one loses the power of taste for sweet and bitterprinciples, b u t only for these two effects on the sense of taste. Sugartastes like sand and quinine sulphate like chalk. A t the end of2-2 hours, the normal sense of taste is recovered.The author has com-menced the chemical investigat,ion, and has succeeded in separatingthree substances, but these are not yet sufficiently characterised.Occurrence of Aluminium in Vascular Cryptogams. ByJ. W. L.A. H. CHURCH (Proc. Roy. Soc., 44, 121--129).--n/lore recent analysesgenerally recognise the presence of alumina in plants as adventitious.The author has, however, found it to be an important constituent ofmany Lycopodiae, for instance, L. alpinurn, L. clavaturn, L. selap,and L. cernuurn, whilst in Selnginella spinulosa it is absent. Theearth is also absent in L. phlegmaria and L. billurdieri, hilt thesewere afterwards found to be epiphytic. Plants closely related to thVEGETABLE PH YYLOLOQY AND AG KICULT UIt K.183Jqcopodiq namely, E'quiseturn, Ophioglossum, Salvinia, Marsilea,Psiloturn, and Selaqinella, gave negative results. Of tree feriis,c!yathea seym gave negative results, whilst the ash of an unknown treefern from New Zealand contained 19.65 per cent., Cyatherc medu1Zari.sfrom the same source examined qualitatively gave abundance ofalumina, as also did AZsophila australis and to a less extent Dicksonicr,squarrosa. Alumina is also an important constituent of the water-moss, Fonfindis nntipyretica. The alumina in the Lycopodi8 occursin combination with organic acids. It niay serve to neutraliw theacids produced in the plant. It is noticeable that the essential in-organic constituents of plants have low atomic weights, and fall nithinseries 1, 2, 3, and 4 of the periodic arrangement.Formation of Nitric and Nitrous Acids by the Evaporationof Water in Presence of Alkalis and Soil.By A. BAUMANN(Lanclw. Versuchs-Stat.. 1888,217-264).-Schonb~in (Annaleii, 124,4)and others have stated that when water is evaporated, ammonium nitrateand nitrite ale produced. They also stated that calcium carbonate aswell as hydrated oxides absorb ammonia and con-rert it into nitrates.The author has made numerous experiments, all of which he heredetails, and brings forward conclusive evidence that all these experi-ments made by Schiinbein are incorrect. He firstly attributes the falseresults to the absence of the delicate reagents now a t hand, wherebyammonia, nitrates, nitrites, and ozone, and hydrogen peroxide mayhe detected. Secondly, he shows that the source of nitrates is the gasflames used for evaporation, and for heating water-baths, &c., andthat, when evaporation is conducted without the direct aid of gasflames, for instance, by sun heat, or previously heated sand-baths, uotrace of nitrates is found, if the evaporation is conducted in a rocmwhere no gas flames have been burning.He further shows that mostof the chemical preparations which are sold as pure contain nitricacid, and he instances a case in which to prepare pure calcium car-bonate by precipitation, one portion of the product was dried in awater-bath, the other portion by filter-paper, the former product con-tained nitrate, the latter none. This holds good for all reagentssimilarly prepared.It is also shown that even the very testsemployed to detect nitric acid, such as brucine, may and frequentlydo contain a trace of nitrate.Passing on to Franks' experiments on the disappearance of theammonia when ammonium chloride is mixed with soil, he points outthat Frank seems to have forgotten the action of alkalis on com-pounds of ammonia, and shows that in forest soils nitrates are notfound, nor are they produced from added ammonia. Finally, hewarns all who are experimenting on nitrification to beware lest theyintroduce nitric acid by heating their solutions over gas flames, orignite solids in open crucibles, &c., also that chemicals or samplesmust not be kept in rooms where gas is burning, or they will bemore or less contaminated.E. W. P.H. I(. T.Composition of Spring Wheats grown in 1887. By M.MARCKER (Bied. Centtr., lb88, 708 --715j.-This is a similar paper t184 ABSTRACTS OF OHEMICAL PAPERS.the following, in which the compositions of varieties of foreign wheatsare compared. It appears th;t t. gmernlly, the highest percentageof albuminojids and gluten i s to be found in those wheats which comequickest to maturity (under 130 days), when there would be, of albu-mino'ids, 13.17 per cent., and of dry gluten, 18 08, whereas when theperiod of growth exceeds 130 days, the albuminojids amount toonly 12.47, and gluten t o 9.22 per cent. ; the smaller the grain, thehigher the percentage of gluten, whilst a large grain is indicative ofa high percentage of starch ; the wheats richest in gluten produce amore bulky dough than other kinds, and the early ripened wheat andthe largest grains are most suitable for baking purposes.The greaterthe percentage of gluten, the higher will the dough made from theflour rise in the aleurometer. E. W. P.Composition of East Indian Wheat. By T. DIETRICH(Landw. Versuchs-Stat., 1888, 309--318).-Several varieties of Indianwheat are fully described, both physically and chemically. On com-paring the percentage of albuminojids, it is found that the mean of 937analyses of English, Russian, &c., wheats gives 13.90 of crudealbuminoids in the dry substance, whilst the Indian wheats containonly 12.66 per cent. m a mean. E. W. P.Composition and Nutritive Value of Oats.By M. MARCEER(Bied. Centr., 1888, 697--704).--Prom a number of analyses andexperiments on several varieties of oats, the details of which aregiven, the following conclusions are drawn :-The heavier-yieldingsort is poorer in albumino'ids than the lighter-yielding; there is nodefinite ratio between the percentages of fat and albuminojids ; thatsort which comes quickest to maturity is richest in albuminoids ; thegrain poorest in albuminoids has the lowest bushel-weight, and thelargest iridividual grains are also the poorest in nitrogen ; the coeffi-cient of digestion does not seem to be influenced by the composition.Those grains which are smallest in size and richest in nitrogen havemost hull, and generally this hull is poorer in albuminojids than thatof other grains. The thickness of the skin surrounding the seed,measured immediately above the embryo, is not invariable-in oneyear it may be thickest in the large grains, whilst in other years itis thinnest. A table is also given representing the germinativepower and total yield of nutrients per acre, but with one 01- twoexceptions the oats are of foreign kiuds and not grown in England.E. W. P.Calcium Sulphite as a Preventative of Loss of Nitrogen inManure Heaps. By E. JENSCH (Clzern. Zeit., 12, 354--355).--Theauthor draws attention to the enormous losses of nitrogen inherent tothe present system of storing farmyard manure. These losses can bereduced by spreading gypsum, superphosphate and gypsum, andkairiite on the manure; b u t such additions are superfluous from a.manurial point of view in many districts, therefore those means havenot met with extensive application. Calcium sulphite is now recom-Inended for the purpose ; itl is inexpensive, can be applied everywhere,and not only retains ammoiiia, but also acts as a disinfectant. It iANALYTICAL CHEMISTRY. 185obtained as a bye-product from the gases evolved from the roasting ofzinc-blende, and is specially prepared for the present purpose freefrom lime and calcium carbonate, and with an ammonia-absorbingefficiency of 85 per cent. as compared with 68 per cent. in the bestcommercial unburnt gypsum. Its action as a manure on vegetationhas yet to be tested. D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8895600180

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 185 A n a l y t i c a1 C h e m i s t r y . Gas Analysis. By H. DREHSCHMIDT (Ber., 21, 3242--3251).-The author describes a new apparatus for gas analysis similar to Hempel’s (Abstr., 1887, 1062) but somewhat improved. A sketch of the appa- ratus is given and also examples of the results obtained by it. N. H. M. Estimation of Iodine. By W. STORTENBEKER (Rec. Trav. Chim., 7 , 141--151).-The estimation of iodine in its compounds with chlorine may readily be effected, according to Bornemann, by deconi- posing the solution with potassium iodide and estimating the liberated iodine: IC1, + xK1 = 3KC1 + (1 + %)I. The author does not, however, find this method satisfactory, especially in cases where the value of x is high. This is also the case with the method proposed by Duflos of distilling with an oxidising agent (in this case a ferric salt and potassium iodide), when the whole of the iodine should pass over into the distillate.The author, therefore, proposes the reaction ‘LxPeS04 + xHzS04 + 2IC1, = zFe,(S04)J + I, + 2~3HC1, which is complete as long as excess of the ferrous salt is carefully avoided or i f a mixture of both a ferrous and a ferric salt is used. All that is necessary is distillation and determination of the iodine in the dis- tillate. The same method may also be used in estimating iodic acid, since 2HI03 + 10FeSo4 + 5H2S04 = I, + 6H,O + .5Pe,(S04)3, but in this case also, excess of ferrous salt must be most carefully avoided. H. C. Estimation of Nitrogen in Nitrate-super phosphate and in Chili Saltpetre. By P.ZIPmKhR (Chenz. Zed., 12, 955 and 987--988).-The author confirms what has been advanced by others, namely that carefully prepared nitrate-superphosphate, containing no free sulphuric acid, suffers no loss of nitrogen even a t 100”. But in the manufacture of nitrate-superphosphate, it is found advantageous to use a slight excess of sulphuric acid, and such superphosphates lose nitrogen on heating, in amounts varying with the quantity of free acid, the bulk of solutioii heated, and the duration and degree of heating. Hence Grandeau’s method of evaporating a measured VOL. LVI. 0186 ABSTRACTS OF CHEMICAL PAPERS. quantity of the solution gives low results, and to avoid this source of error the following plan is suggested :-If the substance contains 2 to 4 per cent.of nitrogen, take 20 grams, if G per cent. 14 grams, and i f 8 per cent. 10 grams, treat in the usual way for dissolving i n water, and make up to 1 litre ; nentmlise 500 C.C. with sodium hydroxide (free from nitrate), and make up this solution to 1 litre. 50 c.c., or in case of a superphosphate containing only 2 per cent. of nitrogen, 100 c.c., o f the neutralised solution is evaporated to dryness and then examined by the Schloesing-Grnndenu method or with the nitrometer. The latter plan the author finds as accurate as the former, and describes a slightly modified apparatus and the mode of using it. For the analysis of nitrate, the author takes a measured quantity of a dilute solution, in preference to a weighed quantity of a concentrated solu- tion, and determines in the nitrometer.D. A. L. Estimation of Phosphoric Acid. By A. STUTZER (Chern. Zeit., 12, 492).-The drawbacks to the method of estimatiug phosphoric acid in manures, &c., by direct precipitation with magnesia mixture in presence of ammdnium citrate, are the length of time required for the complete precipitation, the ificonvenience of the prolonged stir- ring, and the danger of scratching the sides of the vessel so that the ammonium magnesium phosphate becomes firmly attached to the glass. To avoid these difficulties the author adds a small quantity of ashless filter-paper, .pulped to a thick magma in ammonia, previous to stirring for five minutes with a mechanical stirrer; the ammonium magnesium phosphate may then be a t once collected.I n addition to the great saving of time, 10 beakers may be stirred a t once. I). A. L. Wiborg’s Gasornetrib Method for estimating Carbon in Iron and Steel. By H. v. JfiPTNER (Chew. Centr., 1241-1242, from fisten-. Zeit. Berg. Huttenwesen, 34, 67-68).-0.2 gram of iron or steel, or 0.1 gram of pig-iron, so finely pulverised that it passes through a 1.5 mm. sieve, is brought into the carefully dried reaction- tube of the apparatus. 4 C.C. of a saturated solution of cupric sulphate is added a n d allowed to react for 16 minutes, or, if a smell of hydro- carbon is detected, only three to four minutes. This reaction-tube is 140 mm. long, and 20 mm. wide, and is closed a t the top by a doubly bored india-rubber stopper. Through one of the holes passes a funnel with stopcock ; the other is connected with a burette.This has an india-rubber stopper a t its upper end, through whiclr passes a funnel with stopcock; the lower end is connected with a water-flask for regulating the pressure. The burette is surrounded by a tube, through which water may he passed for regulating the temperature. After the cupric sulphate has acted on the iron, 1 2 grams of chromic acid is added to the mixture, stirred up well with a glass rod, and allowed to reach for three to 10 minutes. The tube and contents are next cooled, the burette is tilled with water and connected with the reaction-tube, and 8 c c. of pure sulphuric acid passed gradually into the latter by means of the funnel with stopcock.ANALYTICAL CHEMISTRY. 187 The tube is warmed gently u p to the boiling point f o r 10 minutes, then cooled down, and finally all air and carbonic anhydride expelled out of the reaction-tube into the burette by passing in water through the funnel. The volume of gas in the burette having been read off, aqueous potash is passed in through the funnel, the gas shakeii with it, and, after adjusting the level ot the water, the volume again read off, when from the difference between the two readings the percentage of carbon in the iron may be calculated.J. W. L. Absorption of Carbonic Oxide by Cuprous Chlpride Solu- tions. By T. LONATSCHEFFSKY-PETRUNIAKA (J. Russ. Chem. SOC., 1888, 20,108-12;j) .-The author has analysed mixtures of gases (especially wood-petroleum gas) containing carbonic oxide by Bunsell’s method, that is, absorption of that constituent by cuprous chloride.Clay balls were soaked with a solution of cuprous chloride in hydrochloric acid and introduced into the gaseous mixture to be analysed, but constant results could not be obtained. It was shown that such balls, saturated with carbonic oxide, lose some of thiR gag in pure hydrogen, whereas incompletely saturated balls either lose none or absorb more carbonic oxide when introduced into mixtures o€ hydrogen with little or much carbonic oxide. It is shown in a series of tables that tlie phenomena of absorption depend on the partial pressure of carbonic oxide in mixtures with other gqses. The author’s results were ob- tained independently of Drehschmidt’s. B. B. Action of Sulphuric and Hydrochloric Acids on Wood- Petroleum Gas.BJ T. LONAI‘SCHEFFSKY-PETRUNIAKA ( J . &~ss. Chem. Soc., 1888, 20, l23-124).-By passing the gas into a hydrochloric solution of cuproua chloride, a solid substance and a volatile liquid of an aromatic character, and containing chiorine, are formed. Dilute sulphuric acid g*ives nothing but resinous compouqds. These facts are of importance in connection with gas analysis. B. B. Precipitation of Barium Sulphate in the Presence of Bromine. By M. LUCION (Chew. Zeit., 12, 427) and G. TAURER (ibid., 477).- Both authors independently have observed that bromine does not interfere with the accurate precipitation of barium sulphate ; and, therefore, when it has been used for oxidising sulphur compounds, the removal of any excess, as generally recommended, is superfluous.D. A. L. Analysis of Lead Peroxide. By L. OPIFIGTUS (Chem. Zeit., 12, 477).--Por this purpose the peroxide 01’ red lead may be readily dis- solved without the application of heat hy treatment with nitric acid, sp. gr. 1.20, and chemically pure copper. In the case of red lead, espe- cially, this method is very useful in detecting admixtures, as adulterants are left that would be dissolved by treatment with hot solvents ; these can, therefore, be 1-eadily detected and estimated; further, if it is desired to determine copper also, it is only necessary t o use a weighed quantity of that metal in the first instance. D. A. L..188 ABSTRACTS OF CHEMICAL PAPERS. Electrolytic Estimation of Copper. By F. R~DORFF (Bey., 21, 3050--3051).-In estimating copper electrolytically, it is advantageous to mix the solution with 2 t o 3 grams of potassium or ammonium nitrate, and then to add about 10 C.C. of ammonia for every 100 C.C.of the solution containing from 0.1-0.3 gram of copper. The con- dition of the precipitated metal is very satisfactory, and the strength of the current employed may vary within tolerably wide limits. F. S. K. Estimation of Manganese in Foods. By G. STE~N (Chew,. Zeit., 12, 446).-The ash is boiled with nitric and sulphuric acids and lead peroxide, the resulting permanganate being determined by titra- tion. In this way, by using 5 grams of ash, American coffee beans gave 0.0279 per cent. of manganese in the ash. Estimation of Iron and Alumina in the Presence of Calcium and Phosphoric Acid. By G.KENNEPOHL (Chem. Zeit., 12, 923- 924).-The unsatisfactory results obtained in the estimation of iron aud alumina in natural and artificial phosphates led the author to investigate the methods employed. These are numerous, but map be classified under three heads : those depending on (1) the precipita- tion and estimation as double phosphate of iron and aluminium ; (2) precipitation by means of ammonium acetate and estimation of the calcium and phosphoric acids ; and (3) separation of iron and alumi- nium. The latter is much too tedious for geueral application, and numerous quantitative experiments with mixtures of solutions of ferric chloride, aluminium sulphate, and calcium phosphate, dissolved in nitric acid, i n some cases with ammonium phosphate and calcium, in other cases without one or the other, or both, lead the author to conclude that methods 1 and 2 are far too inconvenient when accurate results are required, owing to the difficulty of separating calcium compounds and phosphoric acid.The following method is, therefore, recommended :-The solution is neutralised, or made slightly am- moniacal with ammonia, in a 100 or 200 C.C. flask ; it is then treated with slight excess of oxalic acid, heated a t 80" for some time, filled to the mark, arid filtered. A measured quantity of the clear filtrate is evaporated to dryness, and gently ignited in a platinum dish. The residue is moistened with concentrated ammonia, dried, and dissolved in concentrated hydrochloric acid. The solution is precipitated by means of ammonia and acetic acid, the iron and alumina being weighed as double phosphate, in which the iron may, if desired, be estimated in the usual way.The method also serves for the estima- tion of calcium, and may be made volumetric by employing standard oxalic acid. Another method, in which phosphoric acid was first eliminated by magnesia mixture in the presence of citric acid, did not prove satisfactory. D. A. L. Separation of Nickel and Cobalt in the Form of Nitrites. By BAUBIGNY (Compt. rend., 107, 685-686) .-Lang showed that barium nitrite forms an insoluble triple compound with potassium and nickel nitrites, and thus prevents the accurate separation of D. A. L.ANALYTICAL CHEMISTRY. 189 nickel and cobalt by this method. The author finds that lead nitrite also forms an insoluble triple compound with the nickel and potas- sium, which separates as an orange-yellow precipitate only slightly soluble in acetic acid.The composition of the precipitate varies with the proportions of the three salts in the solution, but it is evident that it interferes with the separation of nickel from cobalt. C. H. B. Volumetric Estimation of Stannous Chloride. By A JOLLES (Clzem. Zeit., 12, 597).-The following method is found satisfactory for the estimation of stannous chloride :-4 or 5 grams of potassium mangaiiate dissolved in 8 or 10 grams of potassium hydroxide. and made up to a litre, is standardised by means of potassium antimony tartrate. 0.2 or 0.4 grain of the stannous chloride, or metallic tin, is dissolved in hydrochloric acid in a current of carbonic anhydride, and made up to 250 C.C.This solution is then run from a burette into 5 or 10 C.C. of the manganate solution, until the green colour is replaced by a yellowish-brown, the volume is read off and calculated as usual ; the reaction is represented by the equation :-SnCI, + 2KOH + KzMiiO1 = 2KC1 + SnO, + ‘LKOH + MnO,. When the stannous chloride is much contaminated, it is advisable to precipitate the tin by means of zinc, and then proceed as above. D. A. L. Estimation of Titanium and Phosphorus in Iron Ores. By JEKN~NGS (Chem. Centr., 1888, 1234, from Berg. Hutf Zeit., 47, 254). -1 to 5 grams of the ore is digested with hydrochloric acid, the solution neutralised with sodium carbonate, reduced with sulphurous acid, 50 C.C. of acetic acid added, and diluted to 500 C.C.By boiling for one hour, tlie titanic acid is precipitated, a part of the phosphoric acid and iron accompanying it. The precipitate, with the insoluble poition of the ore (the latter is purposely allomed t o remain in the solution, as it assists in the filtration of the titanic acid), is brought on to a filter and washed with dilute acetic acid, dried, ignited, fused with 10 times its weight of sodium carbonate, and the silicste and phosphate of soda dissolved out of the flux. The insoluble sodium and iron titanate is dissolved in dilute sulphuric acid, neutrnlised with sodium carbonate, reduced with sulphurous acid, and the titanic acid precipitated pure with 25 C.C. acetic acid. The first two filtrates are mixed together, oxidised with nitric acid, and the phosphoi*ic acid, as well as some silicic acid, precipitated with ammonia ; the precipi- tate is dissolved and evaporated to dryness, in order to render the silicic acid insoluble, and the phosphoric acid determined with mola b- date solution. J.-W. L. Estimation of Noble Metals in Potassium Cyanide Solu- tions containing them. By L. OPIFICIUS (Chenz. Zeit., 12, 525). -The solution is treated with hJdrochloric acid to destroy the cyanides, warmed, sulphuric acid added, and the gold and silver precipitated by means of zinc, their complete precipitation being indcated by t h e appearance of a deposit of metalllc copper, which is 0 2190 ABSTRACTS OF CHEMlCAL PAPERS, generally present in such solutions. The metallic precipitate is washed, mixed with lead, cupelled, parted, &c., in the usual manner.The method is both rapid and accurate. Modifications in the Methods of Organic Analysis. By m. L. DUDLEY (Ber., 21, 3172- 3177).-The author recommends the employment of a platinum combustion-tube and manganese sesqui- oxide, instead of copper oxide, and states that with such an apparatus a combustion can be made every hour with very satisfactory results. I n the analysis of volatile liquids, the substance is weighed in a small bulb-tube, the t w o ends of which are bent upwards. When the corn- buetion-tube is sufficiently hot, the bulb is interposed between the drying apparatus and the tube, and a stream of ni.trogen passed ; as soon as the air in tlhe combustion-tube is expelled, an iron plate placed a few inches underneath the bulb is heated, so that the liquid quickly volatilises into the combustion- tube without condensing in its passage there.When the liquid has all volatilised, air or oxygen is passed, and the process completed as usual. Source of Error in the Estimation of Benzene in Coal-gas. By F. P. TREADWELL and H. N. STOKE8 (Bey., 21, 3131--3133).-1n Berthelot's method for the analysis of coal-gas, fuming nitric acid is used to absorb the benzene, and bromine-water to absorb the hydro- carbons C,Hzn and CflHzn-z. It is shown by the author that fuming nitric acid absorbs carbonic oxide completely (compare Hasenbach, J. pr. Chem. [2], 50, l), aid that bromine-water absorbs benzene, as well as the hydrocarbons mentioned (compare also Drehschmidt, Post's Chem.Techn. Anal., 1888, 108). By F. L. EKNAN (Chem. Zeit., 12, 564-565).-According to the results of the author's investigations, brandies prepared from potatoes or cereals, with the exception of normal propyl and isobutyl alcohols, contain no other alcohols with boiling points between ethyl and anlyl alcohols; this is at variance with the statements of some previous observers. The fuse1 oils from such spirits contain from 3-12 per cefif. by weight of propyl alcohol, 15-47 of but$ alcohol, 44-71 of aniyl alcohol, with 5-7 per cent. of high-boiling residue. The largest proportion of butyl alcohol was found in spirit from cereals. The various constituents were separated by fractionation, using a Le Be1 tube ; the corn spirits required 20-25 fractionations to get the prop91 alcohol sufficiently pure.The sp. grs. at 1.5" were propyl alcohol (3 8085, isobutyl alcohol 0.8064, amyl alcohol 0.8157. The amount of these oils was estimated colorimetrically by means of sulphuric acid. The types were strong solutions con tainiiig hydrochloric acid and known quantities of cobaltous chloride for red, ferric chloride for yellow, and copper chloride for blue. 200 C.C. of spirit and 25 C.C. of water are rapidly distilled from a brass retort uutil 185 C.C. have passed over. The distillate is diluted to 200 c.c., and 25 C.C. is steadily run into 15 C.C. of snlphuric acid, sp. gr. 1.8436, during about five minutes, with brisk stirring ; they are compared with tbe D. A. L. F. S. K. N. H, 31. The Amount and Estimation of Fuse1 Oil in Spirits.ANALYTICAL CHEMISTRY.191 types after a lapse of a t least three hours. Propyl alcohol is not coloured by sulphuric acid. Aldehyde to the extent of 0.02 per cent. in 46 per cent. alcohol gives no noteworthy reaction with sulphuric acid, but, nevertheless, is objectionable, as it has the property of intensifying the colour reaction of amyl alcohol, and may lead to con- siderable error. D. A. L. Estimation of Sugar in Molasses by Clerget's Inversion Method. By I?. HERLES (Chem. Centr., 1888, 1136-1137, from Zeit. Ziirkerind Bijhnzen, 12, 381-387).-0wing to the presence of raffinose in molasses, the determination of the sugar is not made by directly polarisinq, but, according to Clerget's method, after inversion. As the rafinose is fermentable, the author considers that it should not be omitted from the percentage of sugar, and he proposes the following method and formula.The molasses is clarified with plumbic acetate in a 100 C.C. flask, 50 C.C. is inverted with 5 C.C. coil- centrated hydrochloric acid, by heating at 70" for 15 minutes. After cooling, the degree of rotation is noted as well as the temperature. Then the diEerence between the two readings of the polariscope, before and after inversion, is multiplied by 0.42, and added to the determination according to Clerget. For temperatures approaching Z O O , the author recommends the calculation of the sugar contents from the reduction of the rotation (S) on account of inversion :- . . C=- looS where t = "C. 142 - t]2' J. W. L. Estimation of Saccharose as well as Invert-sugar or Raffinose and on the Quantitative Estimation of Glucose with Levulose.By J. DAXM~LLER (Chem. Centr., 1888, 1248, from Zeit. VeT. Bzd. Zuck. I~td., 25, 742--755).-The author prefers weighing half the normal weight of sugar for inversion (namely, 13.024 grams) dissolving in 75 C.C. of water and inverting with 5 C.C. of concentrated hydrochloric acid by heating at 70" for 7; minutes. The resulting solution is then diluted to 100 C.C. and polarised. Then, since 26.045 grams cane- sugar cause a deviation of +loo", and further, the same weight of cane-sugar after inversion causes a deviation of -32*66", then for each + 1" (= 1 per cent.) rotation before inversion, the same amount of cane-sugar causes a rotation of -0.3266" after inversion.Under the same conditions of inversion, 16.576 grams of raffinose (C18H,,0,, + 5H20), causes before inversion a rotation of + loo", after inversion of +51.82" ; before inversion, therefore, it rotdtes the ray 1.852 times more strongly than cane-sugar. 26.048 grams of anhydrous raffinose, after inversion, would rotate the ray +95.98". If now P = the read- ing in degrees of deviation caused by 26.048 grams sugar before inversion ; J = the reading after inversion ; Z = the percentage of cane-sugar ; and R = the percentage of anhydrous raffinose ; then (1) P = Z + 1.85R. from which we obtain- (2) J = -0.3266 Z + 0.9598 R,192 ABSTRACTS OF CHEMICAL PAPERS. Z = 0.5188 P -J/0.8454 = per cent. cane-sugar, R = P - Z/1*85 = per cent. rafinose. The author has experimented with Sieben's method for destroying levulose, but the results obtained were not altogether satisfactorv.Y ' especially when the proportions of levulose and glicose varied. J. W. L. Estimation of Raffinose in Beet-sugar. By G. LOTMAN (Chern. Zeit., 12, 391--392).-Simple examination of the methyl alcohol extract of sugar gives too high a percentage of ra6nose. The follow- ing method gives accurate results with even 0.1 per cent. of raffinose. 50 grams of the sugar is perfectly dried at 60" with the aid of a water- air-pump, allowed to cool in the drying chamber, and treated with 100 C.C. c f methyl alcohol and pola'rised. 50 C.C. of the solution is then mixed witch 2 C.C. of a solution of lead acetate (sp. gr. 1.4, which precipitates all the raffinose), made up to 55 c.c., and again polarised.This reading +10 per cent. gives the rotation due to cane-sugar, arid by deduction from the first reading, the rotation due to rsffinose is found, and the percentage calculated as usual. One part of raffinose prevents the crysta.llisation of a t least five parts of sugar. D. A. L. Detection of Foreign Starches in Chocolate. By C. HARTWICH (Chem. Zeit., 12, 375).-Owing to the variable amount of starch in rocoa- beans, chemical examination of chocolate cannot be taken as decisive, as regards admixture of foreign starches, unless the per- centage is above 10 per cent. Therefore, microscopical examination is resorted to, and for this purpose the chocolate is best deprived of its fat and sugar before being placed under the microscope.The starch granules are counted in different parts of the object, and a mean taken ; a pure chocolate is then mixed with a corresiwnciin: amount of the supposed foreign starch, and examined in the sicrile manner ; in this way, the quantity of starch may be estimated with sufficient accuracy. When small-grained starches me present, it is not advisable to treat with iodine in potassium iodide beforehand. D. A. L. Butter Analysis. By PAGNOUL and GRENET ( J . Pharnz. [ 5 ] , 18, 353--36O).-The present rapid method of analysis is based on a determination of Loth the volatile and fixed acids in the butter. 10 grams of butter is just melted and transferred to a burette graduated to 70 c.c., into which a few drops of warm water and a little light petroleum have been previously placed.The capsule in which the butter has been melted is washed alteriiately with petroleum and a few drops of water, and the burette is filled up with petroleum to a point below the 70 C.C. mark. The burette is closed above with the moistened hand, and strongly shaken, after which it is allowed to remain five or six minutes. Then the water level is brought up to 10 c c., and the petroleum level up to 70 c.c., and afterANALYTICAL CHEMISTRY. 193 shaking again the tube is closed and allowed to remain for 10 minutes. If the temperature is low, it may be necessary to warm the burette a, little. The aqueous portion is carefully drawn off into a tared platinum dish, a little water being added several times, to remove all that is soluble in water.This solution serves to determine the foreign matters-ash and sodium chloride. 10 C.C. is now run out of the burette and thrown away, then 20 C.C. is run into a flask for the estimation of the fatty acids, and 20 C.C. more is run into a tared capsule for estimation of the total fat. The flask just mentioned is heated on the water-bath for 5 to 10 minutes to expel the petroleum ; then for saponification there is added 50 C.C. of a solution prepared as follows :-60 grams of potash-lime is placed in a flask with 800 C.C. of alcohol of 9 5 O , and agitated from time to time during several days ; this is then filtered and made up to a litre. The flask containing the fatty niatter and alkaline solution is heated a t 100" and agitated from time to time, but more actively towards the end of the operation ; in 30 to 40 minutes the saponification is complete.50 C.C. of water is now added, and warmed a little to dissolve the soap, three or four bits of pumice and 12 C.C. of phosphoric acid of 45" are then added. The flask is shaken and closed with a stopper carrying a funnel with atopcock and a tube with two bulbs in the vertical portion and then bent slightly downwards and leading to a vertical worm condenser. When 45 C.C. has been distilled over, 50 C.C. of water is passed into the flask ; when 95 C.C. has passed over, a second 50 C.C. of water is added, and the distillation is continued until 145 C.C. has passed over. Phenol- phthalein is added to the distillate and decinormal soda solution. The volatile fatty acids expressed as butyric acid, per 100 of butter, equals 0.264 time the number of C.C.of soda solution used. With margarin, only 1 or 2 c c. is required, whilst, pure butter requires about 20 C.C. The presence of sodium chloride in the flask would give rise to hydro- chloric acid, which would be estimated as so much fatty acid. If present, the titrated liquid may be acidified with a few drops of nitric acid, and neutralised with crllcium carbonate in excess, then potassium chromate and standard silver nitrate solution will indicate the amount of hydrochloric acid which is to be deducted. 20 to 25 C.C. of light petroleum is added $0 the warm residue in the flask, and the contents are transferred to the burette, the flask is then washed alternately with petroleum and warm water to collect the whole of the residue.On running off the water from the burette, the phos- phoric acid and glycerol are removed ; three or four washings give a, water which is quite neutral. The solution of fatt1 acids thus com- pletely washed is evaporated on the water-bath, the capsule being sunk in the boiling water, so that the outside level is 2 or 3 cm. higher than t h a t of the inside; the residue is dried a t 105" or 110", and weighed. The platilium capsule containing the other 20 C.C. of petrol~um solution is evaporated, dried at 105" to 110", and weighed. From these figures the amount of fixed and volatile fatty acids per cent. of fatty matter are dediiced. The platinum capsule contain- ing the original 10 C.C. of aqueous solution is evaporated, dried, and weighed ; then gently heated to dull redness and weighed again.Thc ash is dissolved in a little water, filtered, and the liquid is made up to194 ABSTRACTS OF CHEMICAL PAPERS. 100 C.C. 'In 20 c.c., the chlorine is titrated wit11 silver nitrate solution and potassium chromate. Finally, the moisture is determined on 5 grams of butter mixed with 8 or 10 little balls of paper, made from one of two dried and balanced filters. By t u r n i n g over the paper balls two or three times, the drying is completed a t 105" to 110" in about three hours. If boric o r salicylic acid is suspected, special methods then become necessary. eJ. T. Detection of Cotton-seed Oil in Lard. By W. BISHOP and JJ. INGI? (J. Pharnz. [ 5 ] , 18, 348--353).-American lard imported into France is frequently adulterated with 50 to 60 per cent.of other fats ; cotton-seed oil is often used, and the desired consistence is given to the mixture by the addition of pressed tallow. Bechi has shown that cotton-seed oil, to the exclusion of other fats, reduces silver nitrate. (Compare, however, Bizio, this vol., p. 86.) Lnbiche has remarked the production of a special coloration when this oil is treated with lead acetate and ammonia. Finally, the rise in temperature produced by mixing this oil with sulphuric acid is relatively considerable. These t,hree characteristics are sufficient to detect the oil, when mixed with lard, as follows:-100 to 150 grgms of the lard is heated a t 80-100" until it becomes perfectly clear. 5 grams of this limpid material is treated with 20 C.C.of absolute alcohol and 3 C.C. of a solution containing 2 grams of silver nitrate to 250 c c. of absolute alcohol. The mixture is heated at lOOe during 10 minutes, and stirred from time to time. I n presence of cotton-seed oil, a more or less accentuated coloration is produced, and a coloured cake is formed on cooling ; on decanting the alcohol and dissolving the cake in ether or light petro- leum, a cold solution is obtained, having the same PcJour. Again, 25 grams of the liqpid fat is treated with 25 C.C. of a solution, cooled to about 35", made up of crystallised lead acetate 500 grams, and water 1000 c.c., 5 C.C. of pure ammonia of 22" B. is then added, and the mixture is vigorously stirred €or some minutes to form a homogepeous emulsion.After 24 hours the colour is observed. Finally, 25 grgms of the melted fat is cooled to about 30", the temperature is taken, and 20 grams of sul- phnric acid, of dp. gr. a t least 1.836, is added. The mass is strongly agitated, and $he point of maxinium temperature observed. By operating always in the same way, duplicate experiments will give readings not differing by more than two degrees. Comparative experiments are made a t the same time with pure materials. The authors have no$ succeeded in devising a quantitative method. J. T. Estimation of Patty Acids in Soap. By SAMELSON (Chent. Zeit., 12, 355).-The fatty acids are precipitated by nieaus of sul- phuric acid, and are collected and washed OR a tared filter. The filter and precipitates are then transferred to a weighed weighing bottle, treated first with absolute alcohol, which is driven off on a water- bath, then with ether in a similar manner.After this treatment, the tube and contents are placed in 8 water-oven, and are dry in an hour. The method is speedy, and avoids both loss and decomposition of the fatty acids. D. A . L.ANALYTICAL CHEMISTRY. 195 Detection and Estimation of Salicylic Acid, chiefly in Beer. By H. ELION (Rec. I'rau. Chim., 7, 'Lll--219).-The acid is extracted from the solution containing it, by shaking it with two or three times its volume of ether ; the ethereal solution, after separation, is then shaken up with a small quantity of a dilute solution of soda or potash, which takes up the whole of the acid. In a very small portion of the solution, after acidification with hydrochloric acid, the salicylic acid can usually be detected by means of the ferric chloride test.If the acid is extracted as above from beer, the impurities which accompany i t prevent its direct estimation by evaporating the ethereal solution and weighing the residue. Direct titration by means of dilate alkali also gives unsatisfactory results. Excess of bromine converts salicylic acid into the compourid C6H2Br3.013r, and this, by the action of potassium iodide, is converted into patassium tribromo- phenoxide, C',H2Br,.0Br + 2 K I = C6H,Br,*OK + I, + KBr. The author attempted, by determining the iodine liberated in the latter reaction, to estimate the salicylic acid bg this means, but found that the action of the potassium iodide was far from complete a t the or- dinary temperature and with moderately dilute solutions.Ebtimation of the hydrobroniic acid formed when salicylic acid is converted into tribroniophenol by excess of bromine, also gave discordant results in the case of beer, owing to the presence of foreign organic matter. It was finally decided to determine the salicylic acid by separating ancl weighing the tribromophenol itself. This can be done by steam dis- tilling the solution, after removing the excess of bromine by means of potassium iodide and sodium thiosulphate, extracting the clistillate with ether, and evaporating the ethereal solution. This lash method was found t o yield satisfactory results. Detection of Salicylic Acid in Beer. By A. J. C. SNYDERS (Chem. Centr., 1888, 1186, from Rev.internat. fabricat. aliment, 1, 166-170).-25 C.C. of beer, with a few drops of sulphuric acid, is shaken u p with 40 C.C. of ether, and the ether extract is tested with very dilute ferric chloride. By this means, 0.004 gram of salicylic acid per litre of beer may be detected. For the quantitative estima- tion, 250 C.C. is distilled and the first 130 C.C. of the distillate is taken. H. C. J. W. L. The Simand-Kohnstein Method of Estimating the Acids in Tanning Liquors. By R. KOCH (Dingl. polyt. J., 269, 168-182). -In a recent communicatiori (Gerber, 923 and 324), Simand, in defending the gravimetric method of estimating the free acid in tannins (Abstr., 1885,935), refers to the author's criticisms, and asserts that Koch wrongly condemns the method owing t o the fact that, through the formation of sparingly soluble magnesium salts, it con- siderable error arises in the estimation of free acids by the Simand- Kohnstein method.The author in reply states, that although, from a scientific point of view, he quite agrees with this contention, having recently carried out a further series of experiments to prove the correctness of the sup- posed formation of sparingly soluble magnesium salts, he condemned196 ABSTRACTS OF CHEMICAL PAPERS, the method as being useless for practical purposes on account of its extreme tediousness and complexity, and, therefore, advocates the estimation of the free acids in tanning liquors by his titration method. (Compare Abstrs., 1887, 871,1144 ; and 1888, 1138.) Testing Peru Balsam.By C. DENNER ( J . Pharm. [ 5 ] , 18, 259- 360, from CelLe’s Hundelsber., 7 888).-To detect gum benzo’in or storax in Peru balsam, 5 grams of the balsam is treated with 5 grams of sodium hydroxide solution (Ph. Germ., 11) and 10 grams of water. The whole is well shaken twice with 13 grams of ether, each time decanting the ether layers as completely as possible. The residue is boiled, and acidified with hydrochloric a d ; on adding cold water, a resin separates which is dissolved in sodium hydroxide solution. The solution thus obtained is diluted with 20 grams of water, boiled, and precipitated with barium chloride ; the precipitate thus formed is collected on a filter, dried on the water-b;tth, and extracted with alcohol. The residue is treated with concentrated sulphuric acid, and the liquid stirred up with chloroform. The chloroform becomes violet or blue if gum benzo’in or storax is present. This method is capable of detecting the presence of minute yuan ti ties.D. B. J. T.ANALYTICAL CHEMISTRY. 185A n a l y t i c a1 C h e m i s t r y .Gas Analysis. By H. DREHSCHMIDT (Ber., 21, 3242--3251).-Theauthor describes a new apparatus for gas analysis similar to Hempel’s(Abstr., 1887, 1062) but somewhat improved. A sketch of the appa-ratus is given and also examples of the results obtained by it.N. H. M.Estimation of Iodine. By W. STORTENBEKER (Rec. Trav. Chim.,7 , 141--151).-The estimation of iodine in its compounds withchlorine may readily be effected, according to Bornemann, by deconi-posing the solution with potassium iodide and estimating the liberatediodine: IC1, + xK1 = 3KC1 + (1 + %)I.The author does not,however, find this method satisfactory, especially in cases where thevalue of x is high. This is also the case with the method proposedby Duflos of distilling with an oxidising agent (in this case a ferricsalt and potassium iodide), when the whole of the iodine should passover into the distillate. The author, therefore, proposes the reaction‘LxPeS04 + xHzS04 + 2IC1, = zFe,(S04)J + I, + 2~3HC1, which iscomplete as long as excess of the ferrous salt is carefully avoided or i fa mixture of both a ferrous and a ferric salt is used. All that isnecessary is distillation and determination of the iodine in the dis-tillate.The same method may also be used in estimating iodic acid, since2HI03 + 10FeSo4 + 5H2S04 = I, + 6H,O + .5Pe,(S04)3, but inthis case also, excess of ferrous salt must be most carefully avoided.H.C.Estimation of Nitrogen in Nitrate-super phosphate and inChili Saltpetre. By P. ZIPmKhR (Chenz. Zed., 12, 955 and987--988).-The author confirms what has been advanced by others,namely that carefully prepared nitrate-superphosphate, containing nofree sulphuric acid, suffers no loss of nitrogen even a t 100”. But in themanufacture of nitrate-superphosphate, it is found advantageous touse a slight excess of sulphuric acid, and such superphosphates losenitrogen on heating, in amounts varying with the quantity of freeacid, the bulk of solutioii heated, and the duration and degree ofheating.Hence Grandeau’s method of evaporating a measuredVOL. LVI. 186 ABSTRACTS OF CHEMICAL PAPERS.quantity of the solution gives low results, and to avoid this source oferror the following plan is suggested :-If the substance contains 2 to4 per cent. of nitrogen, take 20 grams, if G per cent. 14 grams, and i f8 per cent. 10 grams, treat in the usual way for dissolving i n water, andmake up to 1 litre ; nentmlise 500 C.C. with sodium hydroxide (free fromnitrate), and make up this solution to 1 litre. 50 c.c., or in case of asuperphosphate containing only 2 per cent. of nitrogen, 100 c.c., o f theneutralised solution is evaporated to dryness and then examined bythe Schloesing-Grnndenu method or with the nitrometer.The latterplan the author finds as accurate as the former, and describes aslightly modified apparatus and the mode of using it. For theanalysis of nitrate, the author takes a measured quantity of a dilutesolution, in preference to a weighed quantity of a concentrated solu-tion, and determines in the nitrometer. D. A. L.Estimation of Phosphoric Acid. By A. STUTZER (Chern. Zeit.,12, 492).-The drawbacks to the method of estimatiug phosphoricacid in manures, &c., by direct precipitation with magnesia mixturein presence of ammdnium citrate, are the length of time required forthe complete precipitation, the ificonvenience of the prolonged stir-ring, and the danger of scratching the sides of the vessel so that theammonium magnesium phosphate becomes firmly attached to theglass.To avoid these difficulties the author adds a small quantity ofashless filter-paper, .pulped to a thick magma in ammonia, previous tostirring for five minutes with a mechanical stirrer; the ammoniummagnesium phosphate may then be a t once collected. I n addition tothe great saving of time, 10 beakers may be stirred a t once.I). A. L.Wiborg’s Gasornetrib Method for estimating Carbon inIron and Steel. By H. v. JfiPTNER (Chew. Centr., 1241-1242, fromfisten-. Zeit. Berg. Huttenwesen, 34, 67-68).-0.2 gram of iron orsteel, or 0.1 gram of pig-iron, so finely pulverised that it passesthrough a 1.5 mm. sieve, is brought into the carefully dried reaction-tube of the apparatus. 4 C.C. of a saturated solution of cupric sulphateis added a n d allowed to react for 16 minutes, or, if a smell of hydro-carbon is detected, only three to four minutes.This reaction-tubeis 140 mm. long, and 20 mm. wide, and is closed a t the top bya doubly bored india-rubber stopper. Through one of the holespasses a funnel with stopcock ; the other is connected with a burette.This has an india-rubber stopper a t its upper end, through whiclrpasses a funnel with stopcock; the lower end is connected with awater-flask for regulating the pressure. The burette is surroundedby a tube, through which water may he passed for regulating thetemperature. After the cupric sulphate has acted on the iron, 1 2grams of chromic acid is added to the mixture, stirred up well witha glass rod, and allowed to reach for three to 10 minutes.The tubeand contents are next cooled, the burette is tilled with water andconnected with the reaction-tube, and 8 c c. of pure sulphuric acidpassed gradually into the latter by means of the funnel with stopcockANALYTICAL CHEMISTRY. 187The tube is warmed gently u p to the boiling point f o r 10 minutes,then cooled down, and finally all air and carbonic anhydride expelledout of the reaction-tube into the burette by passing in water throughthe funnel. The volume of gas in the burette having been read off,aqueous potash is passed in through the funnel, the gas shakeii withit, and, after adjusting the level ot the water, the volume again readoff, when from the difference between the two readings the percentageof carbon in the iron may be calculated.J. W. L.Absorption of Carbonic Oxide by Cuprous Chlpride Solu-tions. By T. LONATSCHEFFSKY-PETRUNIAKA (J. Russ. Chem. SOC., 1888,20,108-12;j) .-The author has analysed mixtures of gases (especiallywood-petroleum gas) containing carbonic oxide by Bunsell’s method,that is, absorption of that constituent by cuprous chloride. Clayballs were soaked with a solution of cuprous chloride in hydrochloricacid and introduced into the gaseous mixture to be analysed, butconstant results could not be obtained. It was shown that such balls,saturated with carbonic oxide, lose some of thiR gag in pure hydrogen,whereas incompletely saturated balls either lose none or absorb morecarbonic oxide when introduced into mixtures o€ hydrogen with littleor much carbonic oxide.It is shown in a series of tables that tliephenomena of absorption depend on the partial pressure of carbonicoxide in mixtures with other gqses. The author’s results were ob-tained independently of Drehschmidt’s. B. B.Action of Sulphuric and Hydrochloric Acids on Wood-Petroleum Gas. BJ T. LONAI‘SCHEFFSKY-PETRUNIAKA ( J . &~ss. Chem.Soc., 1888, 20, l23-124).-By passing the gas into a hydrochloricsolution of cuproua chloride, a solid substance and a volatile liquid ofan aromatic character, and containing chiorine, are formed. Dilutesulphuric acid g*ives nothing but resinous compouqds. These factsare of importance in connection with gas analysis. B. B.Precipitation of Barium Sulphate in the Presence of Bromine.By M.LUCION (Chew. Zeit., 12, 427) and G. TAURER (ibid., 477).-Both authors independently have observed that bromine does notinterfere with the accurate precipitation of barium sulphate ; and,therefore, when it has been used for oxidising sulphur compounds,the removal of any excess, as generally recommended, is superfluous.D. A. L.Analysis of Lead Peroxide. By L. OPIFIGTUS (Chem. Zeit., 12,477).--Por this purpose the peroxide 01’ red lead may be readily dis-solved without the application of heat hy treatment with nitric acid,sp. gr. 1.20, and chemically pure copper. In the case of red lead, espe-cially, this method is very useful in detecting admixtures, as adulterantsare left that would be dissolved by treatment with hot solvents ; thesecan, therefore, be 1-eadily detected and estimated; further, if it isdesired to determine copper also, it is only necessary t o use a weighedquantity of that metal in the first instance.D. A. L.188 ABSTRACTS OF CHEMICAL PAPERS.Electrolytic Estimation of Copper. By F. R~DORFF (Bey., 21,3050--3051).-In estimating copper electrolytically, it is advantageousto mix the solution with 2 t o 3 grams of potassium or ammoniumnitrate, and then to add about 10 C.C. of ammonia for every 100 C.C.of the solution containing from 0.1-0.3 gram of copper. The con-dition of the precipitated metal is very satisfactory, and the strengthof the current employed may vary within tolerably wide limits.F. S. K.Estimation of Manganese in Foods.By G. STE~N (Chew,.Zeit., 12, 446).-The ash is boiled with nitric and sulphuric acids andlead peroxide, the resulting permanganate being determined by titra-tion. In this way, by using 5 grams of ash, American coffee beansgave 0.0279 per cent. of manganese in the ash.Estimation of Iron and Alumina in the Presence of Calciumand Phosphoric Acid. By G. KENNEPOHL (Chem. Zeit., 12, 923-924).-The unsatisfactory results obtained in the estimation of ironaud alumina in natural and artificial phosphates led the author toinvestigate the methods employed. These are numerous, but map beclassified under three heads : those depending on (1) the precipita-tion and estimation as double phosphate of iron and aluminium ; (2)precipitation by means of ammonium acetate and estimation of thecalcium and phosphoric acids ; and (3) separation of iron and alumi-nium.The latter is much too tedious for geueral application, andnumerous quantitative experiments with mixtures of solutions offerric chloride, aluminium sulphate, and calcium phosphate, dissolvedin nitric acid, i n some cases with ammonium phosphate and calcium,in other cases without one or the other, or both, lead the author toconclude that methods 1 and 2 are far too inconvenient when accurateresults are required, owing to the difficulty of separating calciumcompounds and phosphoric acid. The following method is, therefore,recommended :-The solution is neutralised, or made slightly am-moniacal with ammonia, in a 100 or 200 C.C. flask ; it is then treatedwith slight excess of oxalic acid, heated a t 80" for some time, filled tothe mark, arid filtered.A measured quantity of the clear filtrate isevaporated to dryness, and gently ignited in a platinum dish. Theresidue is moistened with concentrated ammonia, dried, and dissolvedin concentrated hydrochloric acid. The solution is precipitated bymeans of ammonia and acetic acid, the iron and alumina beingweighed as double phosphate, in which the iron may, if desired, beestimated in the usual way. The method also serves for the estima-tion of calcium, and may be made volumetric by employing standardoxalic acid. Another method, in which phosphoric acid was firsteliminated by magnesia mixture in the presence of citric acid, did notprove satisfactory.D. A. L.Separation of Nickel and Cobalt in the Form of Nitrites.By BAUBIGNY (Compt. rend., 107, 685-686) .-Lang showed thatbarium nitrite forms an insoluble triple compound with potassiumand nickel nitrites, and thus prevents the accurate separation ofD. A. LANALYTICAL CHEMISTRY. 189nickel and cobalt by this method. The author finds that lead nitritealso forms an insoluble triple compound with the nickel and potas-sium, which separates as an orange-yellow precipitate only slightlysoluble in acetic acid. The composition of the precipitate varies withthe proportions of the three salts in the solution, but it is evidentthat it interferes with the separation of nickel from cobalt.C. H. B.Volumetric Estimation of Stannous Chloride. By A JOLLES(Clzem.Zeit., 12, 597).-The following method is found satisfactoryfor the estimation of stannous chloride :-4 or 5 grams of potassiummangaiiate dissolved in 8 or 10 grams of potassium hydroxide. andmade up to a litre, is standardised by means of potassium antimonytartrate. 0.2 or 0.4 grain of the stannous chloride, or metallic tin, isdissolved in hydrochloric acid in a current of carbonic anhydride, andmade up to 250 C.C. This solution is then run from a burette into5 or 10 C.C. of the manganate solution, until the green colour isreplaced by a yellowish-brown, the volume is read off and calculatedas usual ; the reaction is represented by the equation :-SnCI, +2KOH + KzMiiO1 = 2KC1 + SnO, + ‘LKOH + MnO,.When thestannous chloride is much contaminated, it is advisable to precipitatethe tin by means of zinc, and then proceed as above. D. A. L.Estimation of Titanium and Phosphorus in Iron Ores. ByJEKN~NGS (Chem. Centr., 1888, 1234, from Berg. Hutf Zeit., 47, 254).-1 to 5 grams of the ore is digested with hydrochloric acid, thesolution neutralised with sodium carbonate, reduced with sulphurousacid, 50 C.C. of acetic acid added, and diluted to 500 C.C. By boilingfor one hour, tlie titanic acid is precipitated, a part of the phosphoricacid and iron accompanying it. The precipitate, with the insolublepoition of the ore (the latter is purposely allomed t o remain in thesolution, as it assists in the filtration of the titanic acid), is broughton to a filter and washed with dilute acetic acid, dried, ignited, fusedwith 10 times its weight of sodium carbonate, and the silicste andphosphate of soda dissolved out of the flux.The insoluble sodiumand iron titanate is dissolved in dilute sulphuric acid, neutrnlisedwith sodium carbonate, reduced with sulphurous acid, and the titanicacid precipitated pure with 25 C.C. acetic acid. The first two filtratesare mixed together, oxidised with nitric acid, and the phosphoi*ic acid,as well as some silicic acid, precipitated with ammonia ; the precipi-tate is dissolved and evaporated to dryness, in order to render thesilicic acid insoluble, and the phosphoric acid determined with mola b-date solution. J. -W. L.Estimation of Noble Metals in Potassium Cyanide Solu-tions containing them.By L. OPIFICIUS (Chenz. Zeit., 12, 525).-The solution is treated with hJdrochloric acid to destroy thecyanides, warmed, sulphuric acid added, and the gold and silverprecipitated by means of zinc, their complete precipitation beingindcated by t h e appearance of a deposit of metalllc copper, which is0 190 ABSTRACTS OF CHEMlCAL PAPERS,generally present in such solutions. The metallic precipitate iswashed, mixed with lead, cupelled, parted, &c., in the usual manner.The method is both rapid and accurate.Modifications in the Methods of Organic Analysis. By m.L. DUDLEY (Ber., 21, 3172- 3177).-The author recommends theemployment of a platinum combustion-tube and manganese sesqui-oxide, instead of copper oxide, and states that with such an apparatusa combustion can be made every hour with very satisfactory results.I n the analysis of volatile liquids, the substance is weighed in a smallbulb-tube, the t w o ends of which are bent upwards.When the corn-buetion-tube is sufficiently hot, the bulb is interposed between thedrying apparatus and the tube, and a stream of ni.trogen passed ; assoon as the air in tlhe combustion-tube is expelled, an iron plate placeda few inches underneath the bulb is heated, so that the liquid quicklyvolatilises into the combustion- tube without condensing in its passagethere. When the liquid has all volatilised, air or oxygen is passed,and the process completed as usual.Source of Error in the Estimation of Benzene in Coal-gas.By F.P. TREADWELL and H. N. STOKE8 (Bey., 21, 3131--3133).-1nBerthelot's method for the analysis of coal-gas, fuming nitric acid isused to absorb the benzene, and bromine-water to absorb the hydro-carbons C,Hzn and CflHzn-z. It is shown by the author that fumingnitric acid absorbs carbonic oxide completely (compare Hasenbach,J. pr. Chem. [2], 50, l), aid that bromine-water absorbs benzene, aswell as the hydrocarbons mentioned (compare also Drehschmidt,Post's Chem. Techn. Anal., 1888, 108).ByF. L. EKNAN (Chem. Zeit., 12, 564-565).-According to the resultsof the author's investigations, brandies prepared from potatoes orcereals, with the exception of normal propyl and isobutyl alcohols,contain no other alcohols with boiling points between ethyl and anlylalcohols; this is at variance with the statements of some previousobservers.The fuse1 oils from such spirits contain from 3-12 percefif. by weight of propyl alcohol, 15-47 of but$ alcohol, 44-71of aniyl alcohol, with 5-7 per cent. of high-boiling residue. Thelargest proportion of butyl alcohol was found in spirit from cereals.The various constituents were separated by fractionation, using a LeBe1 tube ; the corn spirits required 20-25 fractionations to get theprop91 alcohol sufficiently pure. The sp. grs. at 1.5" were propyl alcohol(3 8085, isobutyl alcohol 0.8064, amyl alcohol 0.8157. The amount ofthese oils was estimated colorimetrically by means of sulphuricacid. The types were strong solutions con tainiiig hydrochloric acidand known quantities of cobaltous chloride for red, ferric chloridefor yellow, and copper chloride for blue.200 C.C. of spirit and 25 C.C.of water are rapidly distilled from a brass retort uutil 185 C.C. havepassed over. The distillate is diluted to 200 c.c., and 25 C.C. issteadily run into 15 C.C. of snlphuric acid, sp. gr. 1.8436, duringabout five minutes, with brisk stirring ; they are compared with tbeD. A. L.F. S. K.N. H, 31.The Amount and Estimation of Fuse1 Oil in SpiritsANALYTICAL CHEMISTRY. 191types after a lapse of a t least three hours. Propyl alcohol is notcoloured by sulphuric acid. Aldehyde to the extent of 0.02 per cent.in 46 per cent. alcohol gives no noteworthy reaction with sulphuricacid, but, nevertheless, is objectionable, as it has the property ofintensifying the colour reaction of amyl alcohol, and may lead to con-siderable error.D. A. L.Estimation of Sugar in Molasses by Clerget's InversionMethod. By I?. HERLES (Chem. Centr., 1888, 1136-1137, fromZeit. Ziirkerind Bijhnzen, 12, 381-387).-0wing to the presence ofraffinose in molasses, the determination of the sugar is not madeby directly polarisinq, but, according to Clerget's method, afterinversion. As the rafinose is fermentable, the author considers that itshould not be omitted from the percentage of sugar, and he proposesthe following method and formula. The molasses is clarified withplumbic acetate in a 100 C.C. flask, 50 C.C. is inverted with 5 C.C. coil-centrated hydrochloric acid, by heating at 70" for 15 minutes.Aftercooling, the degree of rotation is noted as well as the temperature.Then the diEerence between the two readings of the polariscope,before and after inversion, is multiplied by 0.42, and added to thedetermination according to Clerget. For temperatures approachingZ O O , the author recommends the calculation of the sugar contentsfrom the reduction of the rotation (S) on account of inversion :- . .C=- looS where t = "C.142 - t]2' J. W. L.Estimation of Saccharose as well as Invert-sugar or Raffinoseand on the Quantitative Estimation of Glucose with Levulose.By J. DAXM~LLER (Chem. Centr., 1888, 1248, from Zeit. VeT. Bzd.Zuck. I~td., 25, 742--755).-The author prefers weighing half thenormal weight of sugar for inversion (namely, 13.024 grams) dissolvingin 75 C.C.of water and inverting with 5 C.C. of concentrated hydrochloricacid by heating at 70" for 7; minutes. The resulting solution is thendiluted to 100 C.C. and polarised. Then, since 26.045 grams cane-sugar cause a deviation of +loo", and further, the same weight ofcane-sugar after inversion causes a deviation of -32*66", then foreach + 1" (= 1 per cent.) rotation before inversion, the same amountof cane-sugar causes a rotation of -0.3266" after inversion. Underthe same conditions of inversion, 16.576 grams of raffinose (C18H,,0,, + 5H20), causes before inversion a rotation of + loo", after inversionof +51.82" ; before inversion, therefore, it rotdtes the ray 1.852 timesmore strongly than cane-sugar. 26.048 grams of anhydrous raffinose,after inversion, would rotate the ray +95.98".If now P = the read-ing in degrees of deviation caused by 26.048 grams sugar beforeinversion ; J = the reading after inversion ; Z = the percentage ofcane-sugar ; and R = the percentage of anhydrous raffinose ;then (1) P = Z + 1.85R.from which we obtain-(2) J = -0.3266 Z + 0.9598 R192 ABSTRACTS OF CHEMICAL PAPERS.Z = 0.5188 P -J/0.8454 = per cent. cane-sugar,R = P - Z/1*85 = per cent. rafinose.The author has experimented with Sieben's method for destroyinglevulose, but the results obtained were not altogether satisfactorv. Y ' especially when the proportions of levulose and glicose varied.J. W. L.Estimation of Raffinose in Beet-sugar.By G. LOTMAN (Chern.Zeit., 12, 391--392).-Simple examination of the methyl alcoholextract of sugar gives too high a percentage of ra6nose. The follow-ing method gives accurate results with even 0.1 per cent. of raffinose.50 grams of the sugar is perfectly dried at 60" with the aid of a water-air-pump, allowed to cool in the drying chamber, and treated with100 C.C. c f methyl alcohol and pola'rised. 50 C.C. of the solution is thenmixed witch 2 C.C. of a solution of lead acetate (sp. gr. 1.4, whichprecipitates all the raffinose), made up to 55 c.c., and again polarised.This reading +10 per cent. gives the rotation due to cane-sugar, aridby deduction from the first reading, the rotation due to rsffinose isfound, and the percentage calculated as usual.One part of raffinoseprevents the crysta.llisation of a t least five parts of sugar.D. A. L.Detection of Foreign Starches in Chocolate. By C. HARTWICH(Chem. Zeit., 12, 375).-Owing to the variable amount of starch inrocoa- beans, chemical examination of chocolate cannot be taken asdecisive, as regards admixture of foreign starches, unless the per-centage is above 10 per cent. Therefore, microscopical examinationis resorted to, and for this purpose the chocolate is best deprived ofits fat and sugar before being placed under the microscope. Thestarch granules are counted in different parts of the object, and amean taken ; a pure chocolate is then mixed with a corresiwnciin:amount of the supposed foreign starch, and examined in the sicrilemanner ; in this way, the quantity of starch may be estimated withsufficient accuracy.When small-grained starches me present, it is not advisable to treatwith iodine in potassium iodide beforehand.D. A. L.Butter Analysis. By PAGNOUL and GRENET ( J . Pharnz. [ 5 ] , 18,353--36O).-The present rapid method of analysis is based on adetermination of Loth the volatile and fixed acids in the butter.10 grams of butter is just melted and transferred to a burettegraduated to 70 c.c., into which a few drops of warm water anda little light petroleum have been previously placed. The capsulein which the butter has been melted is washed alteriiately withpetroleum and a few drops of water, and the burette is filled up withpetroleum to a point below the 70 C.C.mark. The burette is closedabove with the moistened hand, and strongly shaken, after which itis allowed to remain five or six minutes. Then the water level isbrought up to 10 c c., and the petroleum level up to 70 c.c., and afteANALYTICAL CHEMISTRY. 193shaking again the tube is closed and allowed to remain for 10 minutes.If the temperature is low, it may be necessary to warm the burette a,little. The aqueous portion is carefully drawn off into a taredplatinum dish, a little water being added several times, to remove allthat is soluble in water. This solution serves to determine the foreignmatters-ash and sodium chloride. 10 C.C. is now run out of theburette and thrown away, then 20 C.C. is run into a flask for theestimation of the fatty acids, and 20 C.C.more is run into a taredcapsule for estimation of the total fat. The flask just mentioned isheated on the water-bath for 5 to 10 minutes to expel the petroleum ;then for saponification there is added 50 C.C. of a solution prepared asfollows :-60 grams of potash-lime is placed in a flask with 800 C.C.of alcohol of 9 5 O , and agitated from time to time during several days ;this is then filtered and made up to a litre. The flask containing thefatty niatter and alkaline solution is heated a t 100" and agitated fromtime to time, but more actively towards the end of the operation ; in30 to 40 minutes the saponification is complete. 50 C.C. of water isnow added, and warmed a little to dissolve the soap, three or fourbits of pumice and 12 C.C.of phosphoric acid of 45" are then added.The flask is shaken and closed with a stopper carrying a funnel withatopcock and a tube with two bulbs in the vertical portion and then bentslightly downwards and leading to a vertical worm condenser. When45 C.C. has been distilled over, 50 C.C. of water is passed into the flask ;when 95 C.C. has passed over, a second 50 C.C. of water is added, andthe distillation is continued until 145 C.C. has passed over. Phenol-phthalein is added to the distillate and decinormal soda solution. Thevolatile fatty acids expressed as butyric acid, per 100 of butter, equals0.264 time the number of C.C. of soda solution used. With margarin,only 1 or 2 c c. is required, whilst, pure butter requires about 20 C.C.The presence of sodium chloride in the flask would give rise to hydro-chloric acid, which would be estimated as so much fatty acid.Ifpresent, the titrated liquid may be acidified with a few drops ofnitric acid, and neutralised with crllcium carbonate in excess, thenpotassium chromate and standard silver nitrate solution will indicatethe amount of hydrochloric acid which is to be deducted. 20 to25 C.C. of light petroleum is added $0 the warm residue in the flask,and the contents are transferred to the burette, the flask is then washedalternately with petroleum and warm water to collect the whole ofthe residue. On running off the water from the burette, the phos-phoric acid and glycerol are removed ; three or four washings give a,water which is quite neutral.The solution of fatt1 acids thus com-pletely washed is evaporated on the water-bath, the capsule beingsunk in the boiling water, so that the outside level is 2 or 3 cm. higherthan t h a t of the inside; the residue is dried a t 105" or 110", andweighed. The platilium capsule containing the other 20 C.C. ofpetrol~um solution is evaporated, dried at 105" to 110", and weighed.From these figures the amount of fixed and volatile fatty acids percent. of fatty matter are dediiced. The platinum capsule contain-ing the original 10 C.C. of aqueous solution is evaporated, dried, andweighed ; then gently heated to dull redness and weighed again. Thcash is dissolved in a little water, filtered, and the liquid is made up t194 ABSTRACTS OF CHEMICAL PAPERS.100 C.C.'In 20 c.c., the chlorine is titrated wit11 silver nitrate solutionand potassium chromate. Finally, the moisture is determined on5 grams of butter mixed with 8 or 10 little balls of paper, made fromone of two dried and balanced filters. By t u r n i n g over the paperballs two or three times, the drying is completed a t 105" to 110" inabout three hours. If boric o r salicylic acid is suspected, specialmethods then become necessary. eJ. T.Detection of Cotton-seed Oil in Lard. By W. BISHOP andJJ. INGI? (J. Pharnz. [ 5 ] , 18, 348--353).-American lard imported intoFrance is frequently adulterated with 50 to 60 per cent. of other fats ;cotton-seed oil is often used, and the desired consistence is given tothe mixture by the addition of pressed tallow.Bechi has shown thatcotton-seed oil, to the exclusion of other fats, reduces silver nitrate.(Compare, however, Bizio, this vol., p. 86.) Lnbiche has remarkedthe production of a special coloration when this oil is treated withlead acetate and ammonia. Finally, the rise in temperature producedby mixing this oil with sulphuric acid is relatively considerable.These t,hree characteristics are sufficient to detect the oil, when mixedwith lard, as follows:-100 to 150 grgms of the lard is heated a t80-100" until it becomes perfectly clear. 5 grams of this limpidmaterial is treated with 20 C.C. of absolute alcohol and 3 C.C. of a solutioncontaining 2 grams of silver nitrate to 250 c c. of absolute alcohol.Themixture is heated at lOOe during 10 minutes, and stirred from timeto time. I n presence of cotton-seed oil, a more or less accentuatedcoloration is produced, and a coloured cake is formed on cooling ; ondecanting the alcohol and dissolving the cake in ether or light petro-leum, a cold solution is obtained, having the same PcJour. Again,25 grams of the liqpid fat is treated with 25 C.C. of a solution, cooledto about 35", made up of crystallised lead acetate 500 grams, and water1000 c.c., 5 C.C. of pure ammonia of 22" B. is then added, and the mixtureis vigorously stirred €or some minutes to form a homogepeous emulsion.After 24 hours the colour is observed. Finally, 25 grgms of the meltedfat is cooled to about 30", the temperature is taken, and 20 grams of sul-phnric acid, of dp.gr. a t least 1.836, is added. The mass is stronglyagitated, and $he point of maxinium temperature observed. Byoperating always in the same way, duplicate experiments will givereadings not differing by more than two degrees. Comparativeexperiments are made a t the same time with pure materials. Theauthors have no$ succeeded in devising a quantitative method.J. T.Estimation of Patty Acids in Soap. By SAMELSON (Chent.Zeit., 12, 355).-The fatty acids are precipitated by nieaus of sul-phuric acid, and are collected and washed OR a tared filter. The filterand precipitates are then transferred to a weighed weighing bottle,treated first with absolute alcohol, which is driven off on a water-bath, then with ether in a similar manner. After this treatment, thetube and contents are placed in 8 water-oven, and are dry in an hour.The method is speedy, and avoids both loss and decomposition of thefatty acids.D. A . LANALYTICAL CHEMISTRY. 195Detection and Estimation of Salicylic Acid, chiefly in Beer.By H. ELION (Rec. I'rau. Chim., 7, 'Lll--219).-The acid is extractedfrom the solution containing it, by shaking it with two or three timesits volume of ether ; the ethereal solution, after separation, is thenshaken up with a small quantity of a dilute solution of soda or potash,which takes up the whole of the acid. In a very small portion of thesolution, after acidification with hydrochloric acid, the salicylic acidcan usually be detected by means of the ferric chloride test.If the acid is extracted as above from beer, the impurities whichaccompany i t prevent its direct estimation by evaporating the etherealsolution and weighing the residue.Direct titration by means ofdilate alkali also gives unsatisfactory results. Excess of bromineconverts salicylic acid into the compourid C6H2Br3.013r, and this, bythe action of potassium iodide, is converted into patassium tribromo-phenoxide, C',H2Br,.0Br + 2 K I = C6H,Br,*OK + I, + KBr. Theauthor attempted, by determining the iodine liberated in the latterreaction, to estimate the salicylic acid bg this means, but found thatthe action of the potassium iodide was far from complete a t the or-dinary temperature and with moderately dilute solutions.Ebtimationof the hydrobroniic acid formed when salicylic acid is converted intotribroniophenol by excess of bromine, also gave discordant results inthe case of beer, owing to the presence of foreign organic matter. Itwas finally decided to determine the salicylic acid by separating anclweighing the tribromophenol itself. This can be done by steam dis-tilling the solution, after removing the excess of bromine by means ofpotassium iodide and sodium thiosulphate, extracting the clistillatewith ether, and evaporating the ethereal solution. This lash methodwas found t o yield satisfactory results.Detection of Salicylic Acid in Beer. By A. J. C. SNYDERS(Chem. Centr., 1888, 1186, from Rev. internat. fabricat. aliment, 1,166-170).-25 C.C. of beer, with a few drops of sulphuric acid, isshaken u p with 40 C.C. of ether, and the ether extract is tested withvery dilute ferric chloride. By this means, 0.004 gram of salicylicacid per litre of beer may be detected. For the quantitative estima-tion, 250 C.C. is distilled and the first 130 C.C. of the distillate is taken.H. C.J. W. L.The Simand-Kohnstein Method of Estimating the Acids inTanning Liquors. By R. KOCH (Dingl. polyt. J., 269, 168-182).-In a recent communicatiori (Gerber, 923 and 324), Simand, indefending the gravimetric method of estimating the free acid intannins (Abstr., 1885,935), refers to the author's criticisms, and assertsthat Koch wrongly condemns the method owing t o the fact that,through the formation of sparingly soluble magnesium salts, it con-siderable error arises in the estimation of free acids by the Simand-Kohnstein method.The author in reply states, that although, from a scientific point ofview, he quite agrees with this contention, having recently carried outa further series of experiments to prove the correctness of the sup-posed formation of sparingly soluble magnesium salts, he condemne196 ABSTRACTS OF CHEMICAL PAPERS,the method as being useless for practical purposes on account of itsextreme tediousness and complexity, and, therefore, advocates theestimation of the free acids in tanning liquors by his titration method.(Compare Abstrs., 1887, 871,1144 ; and 1888, 1138.)Testing Peru Balsam. By C. DENNER ( J . Pharm. [ 5 ] , 18, 259-360, from CelLe’s Hundelsber., 7 888).-To detect gum benzo’in or storaxin Peru balsam, 5 grams of the balsam is treated with 5 grams ofsodium hydroxide solution (Ph. Germ., 11) and 10 grams of water.The whole is well shaken twice with 13 grams of ether, each timedecanting the ether layers as completely as possible. The residue isboiled, and acidified with hydrochloric a d ; on adding cold water,a resin separates which is dissolved in sodium hydroxide solution.The solution thus obtained is diluted with 20 grams of water, boiled,and precipitated with barium chloride ; the precipitate thus formed iscollected on a filter, dried on the water-b;tth, and extracted with alcohol.The residue is treated with concentrated sulphuric acid, and the liquidstirred up with chloroform. The chloroform becomes violet or blueif gum benzo’in or storax is present. This method is capable ofdetecting the presence of minute yuan ti ties.D. B.J. T

ISSN:0368-1769    

DOI:10.1039/CA8895600185

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

197 General and P h y s i c a l Chemistry. Refractive Indices of Turbid Media. By A. HASCHEK (Afonatsh., 9, 900--902).--Solutions were made in alcohol of shellac, mastic and guaiacum, 8.9, 10.01,and 12.83 grams of each being taken to 100 grams of alcohol. 20 grams of each solution was added to 100 grams of water, and the refractive index then measured. These were for the sodium and lithium lines, mastic 1.3454 and 1.3341, guaiacum 1.3429 and 1.3401, shellac 1.3461 and 1.3410. A solution of water and alcohol alone, in the proportions in which each was pre- sent in the above liquids, gave 1.3365 and 1 3341. Nine square centirnetres of filter-pgper were boiled in 100 C.C. sul- phuric acid for half an bcur, and the refi-active index of the solution found to be 1.4320 and 1.4313, that of the acid alone being 1.4317 and 1.4310.On again boiling for half an hour the solution gave 1.4328 and 1.4320, and the acid 1.4318 and 1.4311. Since in each solution there has been an increase in the refractive index, due to the suspended particles, it must be assumed that these particles cause a retardation in the velocity of light, the more so as thib retardation appears to increase as the size of the particles decreases. H. C. Refraction of Liquids within wide Limits of Temperature. By E. KETTELER (Ann. Phys. Chem. [2], 35, 662-699).-1n former papers (Abstr., 1888,541), the author established, in the case of water and alcohol, the two formulse (n2- l ) ( v -/3) = M, and M = C ( l + Of the four constants, p, C, a, k, occurring in these formulae, p, 0, and k have to be determined by refraction observations, whilst C may be assumed to be known independently.In the present paper, the author describes an elaborate series of experiments on the refraction of carbon bisulphide, from the results of which he deduces the following conclusions :- (1.) The coefficient p can be determined most accurately from the results of Zehnder's and Quincke's pressure researches. (2.) The refraction of carbon bisulphide within the limits of tem- perature of the observations -20" to 160°, is approximately given by the formula (n2 - l ) ( w - 6 ) = constant. ( 3 . ) The dispersion, given by the expression (nf - l ) / ( n ; - 1) - 1 , diminislies with the density, the decrease being such as would be accounted for by a change in the maximum absorption, proportiold to the change of density.(4.) Assuming these relations, the temperature-coefficient can be de terrriined for all temperatures and wave-lengths. Tables are given showing the indices of refraction for wave-lengths corresponding with the iines A, C, D, F, G, and H of the solar spcctrum for different temperatures, with the corresponding values of the tern- perature-coefficient, and the incorrectness of the principql older formulae. G. W. 'l'. P VOL. LTI.19s ABSTRACTS OF CHEMICAL PAPERS. Molecular Refraction of Furnaric, Maleic, Mesaconic, Citraconic, and Itaconic Acids, and of Thiophen. By C. KNOPS (Annulei,, 248, 175-231) .-The author has determined the index of refraction of the methyl, ethyl, and propyl salts of fumaric:, maleic, mesaconic, citraconic, and itaconic acids.A comparison of the molecular refraction of these acids and their ethereal salts, leads the author to the conclusion that fumaric and maleic acids contain only one double-linked carbon-atom, and that fumaric acid stands in the same relation to maleic acid that mesaconic acid does to citraconic acid (Abstr., 1885, 938). Briihl's theory is a t present incapable of indicating in what points the constitution of fumaric and mesaconic acids differ respectively from the isomeric maleic and citraconic acids. According to Anschiitz (Abstr., 1887, 916 ; 1888, 448), ethyl fumarate and mesaconate contain two double-linked oxygen-atoms, but the isomeric maleate and citraconate only contain one clouble- linked oxygen-atom. The molecular refraction of thiopheii indicates that this compound contains only one double-linked carbon-atom. Further investigation is required in order to decide whether the formula (1 1 >S CH-CH CH-CH w.c. vv. correctly represents the constitution of thiophen. Preparation of Phosphorescent Calcium and Strontium Sul- phides. By E. BECQUEREL (Compt. rend., 107, 892--894).-When calcium carbonate, as piire as possible, is calcined with sulphur, i t yields calcium sulphide which is only feebly phosphoresvent. If, however, traces of a sodium compound are added before calcination, the product shows a brilliant and persistent green phosphorescence. Manganese or bismuth alone has very little influence on the result, but, in presence of traces of sodium, the former produces a brilliant yellow and the latter a brilliant blue phosphorescence.Lithium is even more active than sodium, and the phosphorescence is green. Potas- sium, on the contrary, has very little effect. From these results, i t follows that the simultaneous presence of an alkali is essential to the production of any phosphorescence by manganese or bismuth. Oyster shells and other shells, and aragonite and gypsum from somt- localities, contain sodium, and hence the phosphorescent pro- perties of the calcium sulphide prepared from these substances. If 0.1 part of rubidium carbonate is added to calcium carbonate which also contains a small quantity of sodium, and the mixture is heated with sulphur to a moderate temperature, the middle of the mass has a red coJour, whilst t'he outer parts in contact with the crucible show a green phosphorescence.When the product is re- calcined, the red disappears and only the green remains. Strontium sulphide shows similar phenomena, which, however, are less strongly marked ; if free from sodium, it shows a feeble, greenish- blue phosphorescence. I n presence of lithium, the phosphorescence is yellow. TVith rubidium, no red colour is observed. Pure strontium oxide and pure sulphur yield a sulphide with a violet-blue phosplior-GEKERAL AND PHYSICAL CHENISTRT. 199 escence, which, in presence of sodium or lithium, becomes greenish o r yellowish in parts. C. H. B. Decomposition of the Halo'id Salts of Silver by the Action of Light. By F. GRIVEAUX (Con@. rend., 107, 837-839).-Thti author's experiments lead him to the conclusion that the decomposi- tion of the haloid salts of silver by the action of light is a phenomenon of dissociation similar to the decomposition of the same compounds when heated.This view is supported by the following phenomena which are especially well marked in the case of silver iodide. When a heam of light is allowed to fall on one of two silver plates coated with silver iodide and immersed in a cell filled with liquid, an electro- motive force is developed, and attains a maximum after a certain time. Tf iodine solutions of different concentrations are allowed to circulate in the cell, the plates coated with silver iodide remaining the same, the electromotive force diminishes as the concentration of the iodine increases, and at a particular concentration it becomes nil.If the distance between the cell and the source of light is gradually increased, the concentration of the iodine solution required to produce zero E.M.F. gradually diminishes, and vice %,em&. If the cell is gradually moved to or from the light,, and finally placed a t a distance d. the E M.F. developed is the same as if the cell had been placed a t d a t the beginning. When the concentration of the iodine solution in the cell gradually varies, the E.M.F. also varies gradually, but, in the inverse direction. If when the E.M.F. has reached its maximum value the circulation of the iodine solution is stopped, the E.M.F. increases gradually and regularly, but when the circulation is restored the E.M.F. gradually sinks to its norlrial value for the particular degree of concentration. This result ma-j- be ascribed to the decrease in the concentration of the solution, due to the action of the iodine on water under the influence of light, a decomposition which is rendered evident by the decolorisation of the solution. Similar phenomena are observed with silver bromide and silver chloride, but the Concentration of the solution required to produce zero E.M.F.varies with the nature of the halo'id. C. H. B. Decoloration and Recoloration of Litmus Solution by Light. By F. BELLAMP ( J . Plznrrn. [ S ] , 18, 493-43.5).-That litmus solution loses its colonr when kept in a closed vessel, and regains it on ex1 osure to air, is well known. The author boiied 50 grams of litmus three times with three successive litres of water.Four flasks were filled with the last solution and hermetically sealed, so as t o include o d y a small bubble of air. The flasks were placed on a table near to a window where, as a rule, only diffused light fell on them. Between August 24 and October 2 the four liquids became qiiite colourless. On October 15, one of the flasks had become somew.h:~t coloured, a,nd this grew in intensity until November 12, when i t had reached its original intensity ; the other three remained colourless. The coloured flask, placed alternately in darkness and light, became c~~lourless, arid rolonred four and three times respectively, finally the Bask was broken by expansion of the liquid caused by the direct action of sunlight. P 2200 ABSTRACTS OF CHEMICAL PAPERS.The author has only been able to repeat the experiment once, and that less satisfactorily; he has not pet made out the cause of the changes of colour, but is working at the question. Minimum-point of Change of Potential of a Voltaic Couple. By G. GORE (Proc. Ro!y. Soc., 44, 294--296).-The effect of dissolved substances on the electromotive force of a magnesium-platinum couple in distilled water (this lol., p. 90) can be easily shown by balancing one couple against another through a galvanometer, the salts experi- mented with being added to one of the couples. The plates must be cut from the same piece of metal, and immemed at the same time in separate qcantities of the same water. The results are compared with those obtained by means of a thermopile. The minimum-point of change depends on the couple and liquid used, temperature, and particular galvanometer.The latter effect is probably dependent on the inertia of the needle. The minimum-point is dependent on the free chemical energy, and, with certain exceptions, on the chemical heat of the substance dissolved. J. T. H. I(. T. Change of Potential of a Voltaic Couple. By G. GORE (23.0~. Roy. Soc , 44, 296--300).-The effect of potassium chlorate and chloride, hydrochloric acid, and bromine at different temperatures in increasing the voltaic potential of a zinc-platinum couple is examined (see precedinq Abstract). The electromotive force increases more or less regularly with increase of the strength of the solution ; in some cases (potahsium chlorate and chloride) it reaches a maximum before the saturation point is reached; in others (potassium chloride and bromine) a momentary decrease is observed ; in others the electro- motive force becomes constant for a time, and then again increases, The amount of salt required for minimuui change is greatest with potaqsium chlorate, least with bromine.The total increase in elec- tromotive force is given. H. K. T. Influence of the Chemical Energy of Electrolytes on the Minimum-point and Change of Potential of a Voltaic Couple. By G. GORE (Proc. Roy. SOL, 44, 300--308).-A continuation of experiments on the " minimum-point " (see preceding Abstracts). The quantities of dissolved salt required for the minimum-point of change for the oxyhalogen salts of potassium are in the order chlo- rate, bromnte, iodate, beginning with the greatest; hence the more feebly united the negative constituent, the smaller the proportion of salt required to disturb the voltaic balance.With the haloid salts, the minimum quantity was much smaller and in the order iodide, bromide, chloride ; hence the action is more powerful, and the order of activity reversed. With the halogens themselve4, the quantity required is still less, the order remaining the same; hence the effect is greater the greater the chemical energy of the substance and the greater the freedom of that energy. At low potentials the rate of incwase of the electromotive force per unit weight of substance is larger the greater the effect of the substance. The curve of variation of potential is characteristic for each substance.H. I(. T.GEXU’EHXL -4XD PHYSICAL UHE3IISlKY. 201 Effects of different Positive Metals on the Change of Poten- tial of a Voltaic Couple. By G. GORE (PYOC. Boy. SUC., 44, 368- 377) .-A continuation of the above experiments, in which the metals and form of galvanometer are varied. The more easily the positive plate, or the less easily tlie negative plate is corroded, the smaller the quantity of dissolved substance required to disturb the balance. With chlorine and bromine, the quantities vary directly as the atomic weights of the positive metals in the couples magnesium-platinum, zinc-platinum, cadmium -platinum. Aq the smallness of the quantity of substance required to disturb the balance depends both on the sensitiveness of the galvanometer and on the chemical energy of the substance, it is probable that the effect really begins with the first addition of substance, but is too small to detect.H. K, T. Certain Generic Electrical Relations of the Alloys of Platinum. By C. BARUS (Amer. ,T Sci., 36, 427--44d).-Measure- i~ients of the conductivity of a large number of alloys of platinum uith other metals are given, and also the observed temperature- coefficient for ett ch alloy. P 1 o t t iri g the temperature- coefficien ts against the specific resistance, it appeam that the effect of alloying platinum with less than 10 per cent. of any other met,al is to produce a variation in the temperature-coefficient which is quite independent G f the special ingredients, and depends only on the resistance of the alloy.Also, although the resistance of the alloys examined varied from 10 t o 65 microhms. per c.c., throughout the whole of this enor- mous variation the temperature-coefficient was found to vary as a linear function of the conductivity. The author shows that a similar relation holds good in the case of alloys of other metals. H. C. Electrical Resistance of Mercury. By F. KOHLRAUSCH (Ann. Phys. Chew. [2], 35, 700--764).-This paper contains a very full account of a determination of the absolute resistance of mercury carried out by Weber’s method of damping with some modifications of Darn’s. The result of the determination gives 94060 centimetre- seconds as the resistance of ft cubic centimctre of mercury a t 0”. Glazebrook has compared one of the author’s mercury standards with the B.A. unit in the Cavendish Laboratory, and the result of the com- parison gives one B.A.unit = 0 9866 ohm. It will be remembered that at tke Paris Conference it was deter- mined t h a t the legal ohm should be the resistance of a column of mercury 1 square centimetre in sectional area, and 106 centimetres in length a t 0”. It was considered practically certain a t the time that this length was a, little too short, but as the amount of the excess was doubtful it was considered advisabl3 to adopt the whole number. According to the author the true value lies between 106-2 and 106.3 centimetres. G. W. T. Influence of the State of Aggregation of various Substances on their Eleotrical Resistance. By L. GRUNMACH (Ann. Phys. Chem.[2], 35, 764-772) .-Clausius has pointed out (Ann. Phys. Chem., 104, 650) that from Arndtsen’s researches on the electrical202 ABSTRACTS OF CHEMICAL PAYERS. resistance of metals, it follows that in the case of simple metals in the solid state, the resistance varies directly its the absolute temperature. Werner Siemens (ibid., 113, 91) has confirmed this conclusion, subject to the condition that it oiily holds when the metal is not near the melting point. I n the present paper, the author describes some obsemations of the resistance of mercury a t tpmperutnres ranging from -90" to + 20'. He obtains the value 0.00086 for the temperature-coefficient of liquid m('rcur'yv, which agrees fairly well on the one hand with the value 0.00095 given by Werner Siemens, and on the other hand with the value 0.000882 given by Mascart, Nerville, and Benoit.During lique- faction he finds that, the resistance undergoes a rapid increase up to about 1.5 times its original value, a much stnaller increase than that given by Cailletet and Bouty, and by C. L. Weber. He finds, moi-e- over, that the temperature-coefficient does not remain constant between the temperatures -40" and -go', but steadily diminishes with the temperature, as shown briefly in the table below :- Temperature. -40" to -50" -50 ,, -60 -60 ,, - r O -70 ,, -80 -80 ,, -90 Temperature-coefficie~t. 0 * 00226 0 00134 0 -001 11 0-00078 0.00037 These results show t h a t pure mercury, with regard to its resist- ance, behaves differently from other simple metals, not only in the liquid state but even.when solid, and a t temperatures much below the melting point. G. W. T. Electromotive Force of Selenium. By W. V. ULJANTN ( A m . Phys. Chem. [2], 35, 836).-Kalischer (this vol., p. 3 ) laid claim to a prior use of the method of preparing sensitir-e selenium a t a tempera- ture of 195". While quite willing to grant this, the author points out that in his paper (Abstr., 1883, 883) he had expressly stated that the method he had employed was that originally described by Sie- mens in 1877, which he had found much better than the one claimed by Kalischer. The writer quite agrees with Kalischer that Fritts's results have nothing to do with the E.M.F. of selenium. G. W. T. Theory of the Dissociation of Electrolytes. By J. H. VAN'T HOFF and L.T. REZCHER (Zeit. physikal. Chew., 2, 777--781).-The relation which Ostwald has deduced (Abstr., 1887, 1020, 1142) as expressing the behaviour of electrolytes on dilution, m2/( 1 - m)v =C, has been tested with a number of acids, and found t o hold good with remarkable accuracy. The aciils examined were acetic, butyric, benzoic, formic, and chloracetic. H. C. Electrcchemical Studies. By W. OSTWALD (ZeP't. p h y s i k d . Ch w., 2, 840-851) .--The conductivity of electrol~tes may accord- ing to Kohlrnusch be represented by p = u + 27, where u and v areGENERAL AND PHYSICAL CHEMISTRY. 203 the ionic velocities, but since in electrolysis only the dissociated portion of the electroiyte is active, the proportion K of the electi*olyte in the dissociated condition must be taken into account, and we get p = K(u + 21).Since u/v is known from Hittorf's measurements, and p may be observed with certain salts at maximum dilution, we have all the elements for calculating the values of u and w. The calculation of the velocities of a number of negative ions from observat,ioiis of their sodium salts shows that for these velocities certain definite relations cxist. Isomeric ions have the same velocity within l-ery narrow limits. The examination of homologous series of acids shows very distinctly that as the number of atoms in the ion increases its velocity decreases. The nature of the elements of which the ions are composed influences the velocity, but this is more marked in the case of simple than in that of complex ions. Thus the dif- ference between acetic acid and each of its chlorinated derivatives is very marked, whereas between benzoic and chloro- or brorno-berizoic acids it is hardly perceptible. If the number of atoms in the anion is greater than 12, the velocity depends aliuost solely on this number, the differences, as before observed, being smaller and smaller the greater this number is.Hence if the number of atoms, as abscisss, be plotted against t8he velocities as ordinates, a curve is obtained having its convex side towards the axis of abscissae, which it, approaches asymptotically, from which the velocity of any ion containing more than 12 atoms may be read off with an error of not more than 1 to 2 units. H. C. Specific Heat of Tellurium. By FABRE (Ann. Chim. Phys. [GI, 14, 10 1-103.Compare Regnault, Anw. Chim. Phys. [ 3 ] , 46, %30).- The specific heat of a sample of tellurium, precipitated by sulphurous acid, washed with water saturated with nitrogen, and dried in a stream of this gas, was found to he 0.05243 as the average of three experiments a t temperatures rauging from 98.01" t o 98.39". The specitic heat of the same sample, after having been distilled in a stream of sulphurous anhydride, was found to he 0.05177 as the average of three experiments a t 97-62", 97.7", and 97.9" respectively. The element as thus obtained differed in appearance from tellurium which has been distilled in hydrogen, and it did not clearly show a crystal1 ine fracture. Crystalline tellurium, prepared by decomposing alkaline tellurides, was washed with water saturated with nitrogen, distilled in a n atmosphere of hydrogen, and then melted and cooled very slowly.Its specific heat was found to be 0.048265 as a mean of t w o experiments at 98-22' and 98-13'. F. S , K. Estimation of the Value of a Degree in Thermometers of Short Range. By L. CALDERON (Bw., 21, 3303-3315).-The method described below was employed for ascertaining very accurately the value of the graduations of a, thermometer of short range by direct comparison with a standard thermometer. It is also suitable for determining the exact, value of the graduations of thermometer<, eudiometers, &c., or for accurately niessuring the height of the barometer, coeflioients of expansion, &c.204 ABSTRACTS OF CHEMICAL PAF'ERS. If the distance a between two consecutive graduationq n1 and n2 of a thermometer, between which the end of the mercury column stands, is measured in units sufficiently small, and if the distancep bdtween the lower graduation n' and the end of the mercnry column is also ascertained, the quotient p/a gives the fraction of the interval a occupied by the column of mercury.If q is the distance between the higher graduation n2 and the end of the column of mercury, then y = a - p , and whatever the value of a, p + q = a. The two expressions p / a and g/n, either of which can be employed to control the other, will then give the distances of the mercury column fibom the two consecutive graduations n1 and n2 respectively in fractioiis of the unit employed. The instrument employed for making the necessary measurements is a sort of cathetometer, a full dewription of which is given with the aid of a diagram. The author also describes in detail the modus operandi, and gives cxanil)les showing with what accurltcy the graduations can be controlled.In one experiment with a standard thermometer registering from -W5" t o 100*5", and divided into tenths of a degree, the distance between the graduations corresponding with 97%" and 97.cJ0, was equal to 96 divisioirs on the micrometer scale of the catheto- nieter. The tbermometer being placed in the vapour of boiling water, the distance from the end of the mercury column to the graduation 97.8" was T5 divisiorrs on the scale; the exact temperature shown by the thermometer was tlierefore 97.87812". In a second experiment, the thermometer being placed in melting ice, the distance between 0" and -0.1" was 102 divisions, and that between the end of the column of mercury aud the zero point 28 divisions ; so that the exact tempera- ture registered was -0*02745".The value of 1" of this thermo- meter, all corrections having been made, is therefore 0.999644". The following day a change of more than 6 mm. having taken p1ac.e in the height of the barometer, the temperatures registered by the same thermometer under the same conditions were 981632" and 0~06061". Thevalue of 1" after making all necessary corrections was therefore 0.999635". A series of 16 obserca,tions was made in which the thermometer referred to above was compared with an instrument graduated from -0.3" to 14", and divided into fifteenths of a degree ; the mean error of observation was only +0*004".F. S. K. Dilatation of Salt Solutions by Heat. By N. TSCHERNAY (J. Russ. Chem. Sec., 1888, 20, 430-448).-The author has determined the dilatation of several salt solutions by Mrtrignac's method, using dilatometers the constants of which had been accurately determined previously. The following nitrates were investigated, Vt being volume at to:- (1.) HNO3 + 50H20 Vt = 1 + O*O@O1595t + 0.00000S699t2. (2.) LiNO, + 50H20 1 + 0.0001471t + 0*00U003673t2. (5.) AgNO, + 5OH2Q 1 + 0.0001593t + U-000003.587t2. (6.) Ca(50J2 + 50H20 1 + 0.000171% + 0*000003531P. (%) NaNO, + 50H20 I + 0.0002144i + o . o o o o r ~ i ~ 4 t ~ . (4) KNO, + 50H20 1 + 0.0001746t + 0*01?00033i5t2.GEXERSL AND PI-IYSICXL CI-IEMIbTRT.205 He gires also the coefficients of dilatation d.r;]df, the equations for the change of molecular volume with the teniperature and the corre- sponding dilatation coefficients, &c. From a comparison of the different values, it is seen that the above solutions of nitrates have approximately the same dilatation coefficient a t temperatures higher than 30". The dilatation coefficients of molecular volumes are found not t o agree when the temperature rises to 5U0, and the difference hetween the numhers correqpoiidiqg with different salts diminishes very slowly with fallitig tempxature. Table of Vapour-tensions of Solutions of Potassium Hydr- oxide. By G. ERRERA (Gmzetta, 18, 225-231).-This is an elabo- rate table of vaponr-tensions of solutions of potassium hydroxide of various strengths, containing from 1 to 49 parts of the hydroxide to 100 of water.It is an extension of Wullner's table (Ann. Pkys. Chem., 110, 564) in which the values for the various lacunE in i t are calcu- lated and inserted : the f o r m u h used for temperatures below 52-84' being D = 0*0033201' - 0*0000@432'1'*, and for 52 84" to 100" 2, = 0.002863 ; in which D indicates the diminution of tension pro- duced by 1 part of the hydrate KH0,2H20 dissolved in 100 of water, and T the tension of water-vapour a t the given temperature. I?. B. C. E. G. Dissociation of Carbonic Anhydride. By H. LE CHATELIER (Zeit. physikal. Clzern. 2, 782-786) .-The author shows that by aid ,-,. - - 500 -?!- d T = const., of the formula log P + log the dissociation coefficient x of carbonic anhydride at the temperature J k XQ (2 + .c) (I - &)2 7' and pressure P may be calculated, L beiig the molecula; heat of lormation of carbonic anhydride.The results agree very well with the experiments of the author, Mallard, Crafts, and Deville. The value of L decreases with rising temperature, and at length becomes equal to zero, when the dissociation coefficient reaches a maximum. This maximum will be smaller the greater the pressure, a result which is in contradiction to tlhe ordinarv idea that a t a suffi- ciently high temperature all substances undergo &mplete dissociation. H. C. Rise of Salt Solutions in Capillary Tubes. By N. GOLDSTEIN ( J . RUM. Chem. Soc., 1888. 20, 408--415).-l'he author has found, as Valson did, that the heights of liquids in capillary tubes are in- versely proportional to their densities.so that htl = const. This rule, however, holds good only in the case of very dilute solutions, the value hd growing with increasing concentration. I n such a case, tlie capillary rise of the solution is found to be a function not only of the density, but also of the molecular weight of the salt dissolved. I n concentrated solutions containing one and the same percentage of different salts, the height of the column increases with a decreasing niolecular weight of the salt dissolved. Inversely. when two different solutions give columns of the same height, that salt, which is in smaller quantity, is sure to have a larger atomic weight. The difference in the height of the column corresponding with an equal difference of206 ABSTRACTS OF CHEMICAL PAPERS.percentages in solution will be nearly the same with salts of the same molecular weight, but larger with increasing molecular weight of the salt in solution. For exa.mple, with change of percentage of sodium chloride from 23.4 to 5.8 there is a diflermce of 2.6 mm. in the height of the column of liquid, whereas for the same change in a solution of potassium chloride the difference in the height of the column is 6.9 mm. The author propoqes to investigate in the same way solutions of carbon compounds, and especially solutions of salts containing water of cry stallisation. B. B. Catalytic Action of Metals on Oxyhydrogen Gas and the Occlusion of Hydrogen. By A. BERLINER (Anti. Phys.Chem. [Z], 35, 791- 810).-l’he term catalysis was first applied by Berzelius (Ann. Chim. Phys., 37, 66) t o the power shown by certain substances of causing decomposition or other chemical changes in other su0- stances without being themselves affected. Dulong and ThBnard have shown (Ann. Phys Chem., 76,81) that all metals and some earths can determine chemical union betoween oxygen and hydrogen at temperatures below the boiling point of mercury, and in the case of platinum, palladium, rhodium, and iridium, a t ordinary temperatures. Faraday has shown (Ann. Phyq. Chem., 33, 149) that t’he action of plntinuni on oxyhydrogen gas occurs a t ordinary tem- peratures, only when the surface of the metal is perfectly clean. Henry (Phil. Mag. [ 3 ] , 6, 354) and Turner (Amalen, 2, 210) have shown that copper and iron turnings, zinc-foil and wood-carbon have the same effect on oxyhydrogen gas, but only a t temperatures not f a r below thc boiling pointl of mercury, arid Loew ( J .pr. Chem. [Z], 11, 372) has shown that glass begins to act in the same way a t about, the same temperature. Berthelot (Abstr., 1882, 1022) pointed out the connection existing between catalytic action and occlusion of hydrogen, and the present paper contains an account of an extensive series of experiments directed to the further elucidation of the subject. The author arrives a t the conclusion that these catalytic actions are invariably due to the occlusion of hjdrogen, which when occluded always seems to act in the same way as when in the nascent state, as Graham (Phil.Mag. [4], 32, 503) showed conclusivelyin the case of palladium. The fact that when the metallic surface is not clean catalysis still takes place a t high temperatures is attributed by the author to the partial removal of the film of impurity M hen the teniperature is suficiently increased : this is in accordance with Graham’s observation that the largest amount of gas was occluded when the metal was first strongly heated and then allowed to cool in the gas forming the subject of experiment, Metallic Lustre. By W. SPRING (Bull. SOC. Chim., 50,218-261 ). -When finely powdered bismuth sulphide, copper sulphide, or manganese peroxide are corn pressed in cylinders, they acquire a metallic lustre, whilst zinc sulphide, mercury oxide, and copper car- honate acquire a vitreous lustre.A microscopic examination showed that the substances which take a metallic lustre form, without exception, opaque powders, and that the compounc’s hich have glazed surfaces G. W. T.IXORGANIC CHEJIISTRT. 207 are more or less transparent< when finely powdered. Between metallic and vitreous lustre there are ali degrees coiresponding with the various degrees of transparency and opaqueness. The metallic 1 ustre, there- fore, does not depend on the chemical but on the physical state of a subst,)nce (compare Dove, Ann. Phys. Chem., 83, lCi9 ; Brewster, F'ortschritte d. Phys., 8, 331 ; and Briickc, ibid., 17, 313). N. H. If. Apparatus for Fractional Distillation in a Vacuum. By. J. W. B R ~ ~ H L (Ber., 21,339-3342) .-The apparatus consists of a cy Iin- drical vessel, closed a t the bottom and provided at the lop with a ground flange, on to which fits a lid provided with a corresponding flange and two tubulures, one of which is placed in the centre of the lid.Through the centre tubulure, closed by an india-rubber cork, passes a rod by iiieans of which a circular rack containing test-tubes can be rotated in order to bring the tubes in turu immediately under the condenser-tube which passes through the second tubulure,also closed by an india-rubber cork. The cylindrical vessel is provided with st tubulure for connection to a pump. w. P. w. Ether Levels. By R. WEBER (Bey., 21, 3448--3451).-The crystalline figures frequently observed i n the ether levels attached tlo levelling instruments o r physical apparatus, are caused by the use of wet ether, and of glass which is readily attacked by water. Three kinds of glass having the compositioii- SO2.A1,03. CaO. K20. Na20. Total. Relatively hard . . . 69-00 0.89 12.21 18.52 - 100.62 Relatively soft . . . . 65.42 0.93 13.67 19-76 - 99-78 Ronsack glass . . . . 69.93 0.94 4.56 7-27 17-30 100.00 were experimented with, and it was found that tubes of Bonsack glass were attacked both by wet and dry ether, and gave crystalline bgures within a month of being filled ; that tubes of the softer potash glass were also readily attacked by wet ether, bnt showed only slight) indications of crystals after two years when filled with dry ether, whilst tubes of the harder potash glass were also attacked, although more slowly, by wet ether, but remained clear after the lapse of tmo yeais when filled w i t h dry ether.w. P. w.197General and P h y s i c a l Chemistry.Refractive Indices of Turbid Media. By A. HASCHEK(Afonatsh., 9, 900--902).--Solutions were made in alcohol of shellac,mastic and guaiacum, 8.9, 10.01,and 12.83 grams of each being takento 100 grams of alcohol. 20 grams of each solution was added to100 grams of water, and the refractive index then measured. Thesewere for the sodium and lithium lines, mastic 1.3454 and 1.3341,guaiacum 1.3429 and 1.3401, shellac 1.3461 and 1.3410. A solutionof water and alcohol alone, in the proportions in which each was pre-sent in the above liquids, gave 1.3365 and 1 3341.Nine square centirnetres of filter-pgper were boiled in 100 C.C.sul-phuric acid for half an bcur, and the refi-active index of the solutionfound to be 1.4320 and 1.4313, that of the acid alone being 1.4317and 1.4310. On again boiling for half an hour the solution gave1.4328 and 1.4320, and the acid 1.4318 and 1.4311.Since in each solution there has been an increase in the refractiveindex, due to the suspended particles, it must be assumed that theseparticles cause a retardation in the velocity of light, the more so asthib retardation appears to increase as the size of the particlesdecreases. H. C.Refraction of Liquids within wide Limits of Temperature.By E. KETTELER (Ann. Phys. Chem. [2], 35, 662-699).-1n formerpapers (Abstr., 1888,541), the author established, in the case of waterand alcohol, the two formulse (n2- l ) ( v -/3) = M, and M =C ( l + Of the four constants, p, C, a, k, occurring in theseformulae, p, 0, and k have to be determined by refraction observations,whilst C may be assumed to be known independently.In the present paper, the author describes an elaborate series ofexperiments on the refraction of carbon bisulphide, from the results ofwhich he deduces the following conclusions :-(1.) The coefficient p can be determined most accurately from theresults of Zehnder's and Quincke's pressure researches.(2.) The refraction of carbon bisulphide within the limits of tem-perature of the observations -20" to 160°, is approximately given bythe formula (n2 - l ) ( w - 6 ) = constant.( 3 .) The dispersion, given by the expression (nf - l ) / ( n ; - 1) - 1 ,diminislies with the density, the decrease being such as would beaccounted for by a change in the maximum absorption, proportioldto the change of density.(4.) Assuming these relations, the temperature-coefficient can bede terrriined for all temperatures and wave-lengths.Tables are given showing the indices of refraction for wave-lengthscorresponding with the iines A, C, D, F, G, and H of the solar spcctrumfor different temperatures, with the corresponding values of the tern-perature-coefficient, and the incorrectness of the principql olderformulae.G. W. 'l'.P VOL. LTI19s ABSTRACTS OF CHEMICAL PAPERS.Molecular Refraction of Furnaric, Maleic, Mesaconic,Citraconic, and Itaconic Acids, and of Thiophen.By C.KNOPS (Annulei,, 248, 175-231) .-The author has determined theindex of refraction of the methyl, ethyl, and propyl salts of fumaric:,maleic, mesaconic, citraconic, and itaconic acids. A comparison ofthe molecular refraction of these acids and their ethereal salts, leadsthe author to the conclusion that fumaric and maleic acids containonly one double-linked carbon-atom, and that fumaric acid stands inthe same relation to maleic acid that mesaconic acid does to citraconicacid (Abstr., 1885, 938). Briihl's theory is a t present incapable ofindicating in what points the constitution of fumaric and mesaconicacids differ respectively from the isomeric maleic and citraconicacids. According to Anschiitz (Abstr., 1887, 916 ; 1888, 448), ethylfumarate and mesaconate contain two double-linked oxygen-atoms,but the isomeric maleate and citraconate only contain one clouble-linked oxygen-atom.The molecular refraction of thiopheii indicates that this compoundcontains only one double-linked carbon-atom.Further investigationis required in order to decide whether the formula (1 1 >SCH-CHCH-CH w. c. vv. correctly represents the constitution of thiophen.Preparation of Phosphorescent Calcium and Strontium Sul-phides. By E. BECQUEREL (Compt. rend., 107, 892--894).-Whencalcium carbonate, as piire as possible, is calcined with sulphur, i tyields calcium sulphide which is only feebly phosphoresvent. If,however, traces of a sodium compound are added before calcination,the product shows a brilliant and persistent green phosphorescence.Manganese or bismuth alone has very little influence on the result,but, in presence of traces of sodium, the former produces a brilliantyellow and the latter a brilliant blue phosphorescence.Lithium is evenmore active than sodium, and the phosphorescence is green. Potas-sium, on the contrary, has very little effect. From these results, i tfollows that the simultaneous presence of an alkali is essential to theproduction of any phosphorescence by manganese or bismuth.Oyster shells and other shells, and aragonite and gypsum fromsomt- localities, contain sodium, and hence the phosphorescent pro-perties of the calcium sulphide prepared from these substances.If 0.1 part of rubidium carbonate is added to calcium carbonatewhich also contains a small quantity of sodium, and the mixture isheated with sulphur to a moderate temperature, the middle of themass has a red coJour, whilst t'he outer parts in contact with thecrucible show a green phosphorescence.When the product is re-calcined, the red disappears and only the green remains.Strontium sulphide shows similar phenomena, which, however, areless strongly marked ; if free from sodium, it shows a feeble, greenish-blue phosphorescence. I n presence of lithium, the phosphorescence isyellow. TVith rubidium, no red colour is observed. Pure strontiumoxide and pure sulphur yield a sulphide with a violet-blue phospliorGEKERAL AND PHYSICAL CHENISTRT. 199escence, which, in presence of sodium or lithium, becomes greenish o ryellowish in parts.C. H. B.Decomposition of the Halo'id Salts of Silver by the Actionof Light. By F. GRIVEAUX (Con@. rend., 107, 837-839).-Thtiauthor's experiments lead him to the conclusion that the decomposi-tion of the haloid salts of silver by the action of light is a phenomenonof dissociation similar to the decomposition of the same compoundswhen heated. This view is supported by the following phenomenawhich are especially well marked in the case of silver iodide. When aheam of light is allowed to fall on one of two silver plates coated withsilver iodide and immersed in a cell filled with liquid, an electro-motive force is developed, and attains a maximum after a certaintime.Tf iodine solutions of different concentrations are allowed tocirculate in the cell, the plates coated with silver iodide remaining thesame, the electromotive force diminishes as the concentration of theiodine increases, and at a particular concentration it becomes nil.If the distance between the cell and the source of light is graduallyincreased, the concentration of the iodine solution required to producezero E.M.F. gradually diminishes, and vice %,em&. If the cell isgradually moved to or from the light,, and finally placed a t a distanced. the E M.F. developed is the same as if the cell had been placed a td a t the beginning. When the concentration of the iodine solution inthe cell gradually varies, the E.M.F. also varies gradually, but, in theinverse direction.If when the E.M.F. has reached its maximumvalue the circulation of the iodine solution is stopped, the E.M.F.increases gradually and regularly, but when the circulation is restoredthe E.M.F. gradually sinks to its norlrial value for the particulardegree of concentration. This result ma-j- be ascribed to the decreasein the concentration of the solution, due to the action of the iodine onwater under the influence of light, a decomposition which is renderedevident by the decolorisation of the solution.Similar phenomena are observed with silver bromide and silverchloride, but the Concentration of the solution required to producezero E.M.F. varies with the nature of the halo'id. C. H. B.Decoloration and Recoloration of Litmus Solution by Light.By F.BELLAMP ( J . Plznrrn. [ S ] , 18, 493-43.5).-That litmus solutionloses its colonr when kept in a closed vessel, and regains it on ex1 osureto air, is well known. The author boiied 50 grams of litmus threetimes with three successive litres of water. Four flasks were filledwith the last solution and hermetically sealed, so as t o include o d y asmall bubble of air. The flasks were placed on a table near to awindow where, as a rule, only diffused light fell on them. BetweenAugust 24 and October 2 the four liquids became qiiite colourless. OnOctober 15, one of the flasks had become somew.h:~t coloured, a,nd thisgrew in intensity until November 12, when i t had reached its originalintensity ; the other three remained colourless.The coloured flask,placed alternately in darkness and light, became c~~lourless, aridrolonred four and three times respectively, finally the Bask was brokenby expansion of the liquid caused by the direct action of sunlight.P 200 ABSTRACTS OF CHEMICAL PAPERS.The author has only been able to repeat the experiment once, andthat less satisfactorily; he has not pet made out the cause of thechanges of colour, but is working at the question.Minimum-point of Change of Potential of a Voltaic Couple.By G. GORE (Proc. Ro!y. Soc., 44, 294--296).-The effect of dissolvedsubstances on the electromotive force of a magnesium-platinum couplein distilled water (this lol., p. 90) can be easily shown by balancingone couple against another through a galvanometer, the salts experi-mented with being added to one of the couples.The plates must becut from the same piece of metal, and immemed at the same time inseparate qcantities of the same water. The results are compared withthose obtained by means of a thermopile. The minimum-point ofchange depends on the couple and liquid used, temperature, andparticular galvanometer. The latter effect is probably dependent onthe inertia of the needle. The minimum-point is dependent on thefree chemical energy, and, with certain exceptions, on the chemicalheat of the substance dissolved.J. T.H. I(. T.Change of Potential of a Voltaic Couple. By G. GORE (23.0~.Roy. Soc , 44, 296--300).-The effect of potassium chlorate andchloride, hydrochloric acid, and bromine at different temperatures inincreasing the voltaic potential of a zinc-platinum couple is examined(see precedinq Abstract). The electromotive force increases moreor less regularly with increase of the strength of the solution ; in somecases (potahsium chlorate and chloride) it reaches a maximum beforethe saturation point is reached; in others (potassium chloride andbromine) a momentary decrease is observed ; in others the electro-motive force becomes constant for a time, and then again increases,The amount of salt required for minimuui change is greatest withpotaqsium chlorate, least with bromine.The total increase in elec-tromotive force is given. H. K. T.Influence of the Chemical Energy of Electrolytes on theMinimum-point and Change of Potential of a Voltaic Couple.By G.GORE (Proc. Roy. SOL, 44, 300--308).-A continuation ofexperiments on the " minimum-point " (see preceding Abstracts).The quantities of dissolved salt required for the minimum-point ofchange for the oxyhalogen salts of potassium are in the order chlo-rate, bromnte, iodate, beginning with the greatest; hence the morefeebly united the negative constituent, the smaller the proportion ofsalt required to disturb the voltaic balance. With the haloid salts, theminimum quantity was much smaller and in the order iodide, bromide,chloride ; hence the action is more powerful, and the order of activityreversed. With the halogens themselve4, the quantity required is stillless, the order remaining the same; hence the effect is greater thegreater the chemical energy of the substance and the greater thefreedom of that energy.At low potentials the rate of incwase of theelectromotive force per unit weight of substance is larger the greaterthe effect of the substance. The curve of variation of potential ischaracteristic for each substance. H. I(. TGEXU’EHXL -4XD PHYSICAL UHE3IISlKY. 201Effects of different Positive Metals on the Change of Poten-tial of a Voltaic Couple. By G. GORE (PYOC. Boy. SUC., 44, 368-377) .-A continuation of the above experiments, in which the metalsand form of galvanometer are varied. The more easily the positiveplate, or the less easily tlie negative plate is corroded, the smallerthe quantity of dissolved substance required to disturb the balance.With chlorine and bromine, the quantities vary directly as the atomicweights of the positive metals in the couples magnesium-platinum,zinc-platinum, cadmium -platinum.Aq the smallness of the quantityof substance required to disturb the balance depends both on thesensitiveness of the galvanometer and on the chemical energy of thesubstance, it is probable that the effect really begins with the firstaddition of substance, but is too small to detect. H. K, T.Certain Generic Electrical Relations of the Alloys ofPlatinum. By C. BARUS (Amer. ,T Sci., 36, 427--44d).-Measure-i~ients of the conductivity of a large number of alloys of platinumuith other metals are given, and also the observed temperature-coefficient for ett ch alloy. P 1 o t t iri g the temperature- coefficien tsagainst the specific resistance, it appeam that the effect of alloyingplatinum with less than 10 per cent. of any other met,al is to producea variation in the temperature-coefficient which is quite independentG f the special ingredients, and depends only on the resistance of thealloy.Also, although the resistance of the alloys examined variedfrom 10 t o 65 microhms. per c.c., throughout the whole of this enor-mous variation the temperature-coefficient was found to vary as alinear function of the conductivity. The author shows that a similarrelation holds good in the case of alloys of other metals. H. C.Electrical Resistance of Mercury. By F. KOHLRAUSCH (Ann.Phys. Chew. [2], 35, 700--764).-This paper contains a very fullaccount of a determination of the absolute resistance of mercurycarried out by Weber’s method of damping with some modificationsof Darn’s.The result of the determination gives 94060 centimetre-seconds as the resistance of ft cubic centimctre of mercury a t 0”.Glazebrook has compared one of the author’s mercury standards withthe B.A. unit in the Cavendish Laboratory, and the result of the com-parison gives one B.A. unit = 0 9866 ohm.It will be remembered that at tke Paris Conference it was deter-mined t h a t the legal ohm should be the resistance of a column ofmercury 1 square centimetre in sectional area, and 106 centimetresin length a t 0”. It was considered practically certain a t the time thatthis length was a, little too short, but as the amount of the excess wasdoubtful it was considered advisabl3 to adopt the whole number.According to the author the true value lies between 106-2 and106.3 centimetres.G. W. T.Influence of the State of Aggregation of various Substanceson their Eleotrical Resistance. By L. GRUNMACH (Ann. Phys.Chem. [2], 35, 764-772) .-Clausius has pointed out (Ann. Phys.Chem., 104, 650) that from Arndtsen’s researches on the electrica202 ABSTRACTS OF CHEMICAL PAYERS.resistance of metals, it follows that in the case of simple metals in thesolid state, the resistance varies directly its the absolute temperature.Werner Siemens (ibid., 113, 91) has confirmed this conclusion, subjectto the condition that it oiily holds when the metal is not near themelting point.I n the present paper, the author describes some obsemations of theresistance of mercury a t tpmperutnres ranging from -90" to + 20'.He obtains the value 0.00086 for the temperature-coefficient of liquidm('rcur'yv, which agrees fairly well on the one hand with the value0.00095 given by Werner Siemens, and on the other hand with thevalue 0.000882 given by Mascart, Nerville, and Benoit.During lique-faction he finds that, the resistance undergoes a rapid increase up toabout 1.5 times its original value, a much stnaller increase than thatgiven by Cailletet and Bouty, and by C. L. Weber. He finds, moi-e-over, that the temperature-coefficient does not remain constantbetween the temperatures -40" and -go', but steadily diminisheswith the temperature, as shown briefly in the table below :-Temperature.-40" to -50"-50 ,, -60-60 ,, - r O-70 ,, -80-80 ,, -90Temperature-coefficie~t.0 * 002260 001340 -001 110-000780.00037These results show t h a t pure mercury, with regard to its resist-ance, behaves differently from other simple metals, not only in theliquid state but even.when solid, and a t temperatures much belowthe melting point. G. W. T.Electromotive Force of Selenium. By W. V. ULJANTN ( A m .Phys. Chem. [2], 35, 836).-Kalischer (this vol., p. 3 ) laid claim to aprior use of the method of preparing sensitir-e selenium a t a tempera-ture of 195". While quite willing to grant this, the author pointsout that in his paper (Abstr., 1883, 883) he had expressly stated thatthe method he had employed was that originally described by Sie-mens in 1877, which he had found much better than the one claimedby Kalischer.The writer quite agrees with Kalischer that Fritts'sresults have nothing to do with the E.M.F. of selenium.G. W. T.Theory of the Dissociation of Electrolytes. By J. H. VAN'THOFF and L. T. REZCHER (Zeit. physikal. Chew., 2, 777--781).-Therelation which Ostwald has deduced (Abstr., 1887, 1020, 1142) asexpressing the behaviour of electrolytes on dilution, m2/( 1 - m)v =C,has been tested with a number of acids, and found t o hold good withremarkable accuracy. The aciils examined were acetic, butyric,benzoic, formic, and chloracetic. H. C.Electrcchemical Studies.By W. OSTWALD (ZeP't. p h y s i k d .Ch w., 2, 840-851) .--The conductivity of electrol~tes may accord-ing to Kohlrnusch be represented by p = u + 27, where u and v arGENERAL AND PHYSICAL CHEMISTRY. 203the ionic velocities, but since in electrolysis only the dissociatedportion of the electroiyte is active, the proportion K of the electi*olytein the dissociated condition must be taken into account, and we getp = K(u + 21). Since u/v is known from Hittorf's measurements,and p may be observed with certain salts at maximum dilution, wehave all the elements for calculating the values of u and w.The calculation of the velocities of a number of negative ions fromobservat,ioiis of their sodium salts shows that for these velocitiescertain definite relations cxist.Isomeric ions have the same velocitywithin l-ery narrow limits. The examination of homologous series ofacids shows very distinctly that as the number of atoms in the ionincreases its velocity decreases. The nature of the elements of whichthe ions are composed influences the velocity, but this is more markedin the case of simple than in that of complex ions. Thus the dif-ference between acetic acid and each of its chlorinated derivatives isvery marked, whereas between benzoic and chloro- or brorno-berizoicacids it is hardly perceptible.If the number of atoms in the anion is greater than 12, the velocitydepends aliuost solely on this number, the differences, as beforeobserved, being smaller and smaller the greater this number is.Hence if the number of atoms, as abscisss, be plotted against t8hevelocities as ordinates, a curve is obtained having its convex sidetowards the axis of abscissae, which it, approaches asymptotically,from which the velocity of any ion containing more than 12 atomsmay be read off with an error of not more than 1 to 2 units.H.C.Specific Heat of Tellurium. By FABRE (Ann. Chim. Phys. [GI,14, 10 1-103. Compare Regnault, Anw. Chim. Phys. [ 3 ] , 46, %30).-The specific heat of a sample of tellurium, precipitated by sulphurousacid, washed with water saturated with nitrogen, and dried in astream of this gas, was found to he 0.05243 as the average of threeexperiments a t temperatures rauging from 98.01" t o 98.39". Thespecitic heat of the same sample, after having been distilled in astream of sulphurous anhydride, was found to he 0.05177 as theaverage of three experiments a t 97-62", 97.7", and 97.9" respectively.The element as thus obtained differed in appearance from telluriumwhich has been distilled in hydrogen, and it did not clearly show acrystal1 ine fracture.Crystalline tellurium, prepared by decomposingalkaline tellurides, was washed with water saturated with nitrogen,distilled in a n atmosphere of hydrogen, and then melted and cooledvery slowly. Its specific heat was found to be 0.048265 as a meanof t w o experiments at 98-22' and 98-13'. F. S , K.Estimation of the Value of a Degree in Thermometers ofShort Range. By L. CALDERON (Bw., 21, 3303-3315).-Themethod described below was employed for ascertaining very accuratelythe value of the graduations of a, thermometer of short range bydirect comparison with a standard thermometer.It is also suitablefor determining the exact, value of the graduations of thermometer<,eudiometers, &c., or for accurately niessuring the height of thebarometer, coeflioients of expansion, &c204 ABSTRACTS OF CHEMICAL PAF'ERS.If the distance a between two consecutive graduationq n1 and n2 ofa thermometer, between which the end of the mercury columnstands, is measured in units sufficiently small, and if the distancepbdtween the lower graduation n' and the end of the mercnry columnis also ascertained, the quotient p/a gives the fraction of the intervala occupied by the column of mercury.If q is the distance betweenthe higher graduation n2 and the end of the column of mercury, theny = a - p , and whatever the value of a, p + q = a. The twoexpressions p / a and g/n, either of which can be employed to controlthe other, will then give the distances of the mercury column fibomthe two consecutive graduations n1 and n2 respectively in fractioiis ofthe unit employed.The instrument employed for making the necessary measurements isa sort of cathetometer, a full dewription of which is given with the aidof a diagram. The author also describes in detail the modus operandi,and gives cxanil)les showing with what accurltcy the graduationscan be controlled. In one experiment with a standard thermometerregistering from -W5" t o 100*5", and divided into tenths of a degree,the distance between the graduations corresponding with 97%" and97.cJ0, was equal to 96 divisioirs on the micrometer scale of the catheto-nieter.The tbermometer being placed in the vapour of boiling water,the distance from the end of the mercury column to the graduation 97.8"was T5 divisiorrs on the scale; the exact temperature shown by thethermometer was tlierefore 97.87812". In a second experiment, thethermometer being placed in melting ice, the distance between 0" and-0.1" was 102 divisions, and that between the end of the column ofmercury aud the zero point 28 divisions ; so that the exact tempera-ture registered was -0*02745". The value of 1" of this thermo-meter, all corrections having been made, is therefore 0.999644".The following day a change of more than 6 mm.having taken p1ac.ein the height of the barometer, the temperatures registered by thesame thermometer under the same conditions were 981632" and0~06061". Thevalue of 1" after making all necessary corrections wastherefore 0.999635". A series of 16 obserca,tions was made in whichthe thermometer referred to above was compared with an instrumentgraduated from -0.3" to 14", and divided into fifteenths of a degree ;the mean error of observation was only +0*004". F. S. K.Dilatation of Salt Solutions by Heat. By N. TSCHERNAY (J.Russ. Chem. Sec., 1888, 20, 430-448).-The author has determinedthe dilatation of several salt solutions by Mrtrignac's method, usingdilatometers the constants of which had been accurately determinedpreviously.The following nitrates were investigated, Vt being volumeat to:-(1.) HNO3 + 50H20 Vt = 1 + O*O@O1595t + 0.00000S699t2.(2.) LiNO, + 50H20 1 + 0.0001471t + 0*00U003673t2.(5.) AgNO, + 5OH2Q 1 + 0.0001593t + U-000003.587t2.(6.) Ca(50J2 + 50H20 1 + 0.000171% + 0*000003531P.(%) NaNO, + 50H20 I + 0.0002144i + o . o o o o r ~ i ~ 4 t ~ .(4) KNO, + 50H20 1 + 0.0001746t + 0*01?00033i5t2GEXERSL AND PI-IYSICXL CI-IEMIbTRT. 205He gires also the coefficients of dilatation d.r;]df, the equations forthe change of molecular volume with the teniperature and the corre-sponding dilatation coefficients, &c. From a comparison of thedifferent values, it is seen that the above solutions of nitrates haveapproximately the same dilatation coefficient a t temperatures higherthan 30".The dilatation coefficients of molecular volumes are foundnot t o agree when the temperature rises to 5U0, and the differencehetween the numhers correqpoiidiqg with different salts diminishesvery slowly with fallitig tempxature.Table of Vapour-tensions of Solutions of Potassium Hydr-oxide. By G. ERRERA (Gmzetta, 18, 225-231).-This is an elabo-rate table of vaponr-tensions of solutions of potassium hydroxide ofvarious strengths, containing from 1 to 49 parts of the hydroxide to100 of water. It is an extension of Wullner's table (Ann. Pkys. Chem.,110, 564) in which the values for the various lacunE in i t are calcu-lated and inserted : the f o r m u h used for temperatures below 52-84'being D = 0*0033201' - 0*0000@432'1'*, and for 52 84" to 100"2, = 0.002863 ; in which D indicates the diminution of tension pro-duced by 1 part of the hydrate KH0,2H20 dissolved in 100 of water,and T the tension of water-vapour a t the given temperature.I?.B.C. E. G.Dissociation of Carbonic Anhydride. By H. LE CHATELIER(Zeit. physikal. Clzern. 2, 782-786) .-The author shows that by aid ,-,. -- 500 -?!- d T = const., of the formula log P + logthe dissociation coefficient x of carbonic anhydride at the temperature J k XQ(2 + .c) (I - &)27' and pressure P may be calculated, L beiig the molecula; heat oflormation of carbonic anhydride. The results agree very well withthe experiments of the author, Mallard, Crafts, and Deville.The value of L decreases with rising temperature, and at lengthbecomes equal to zero, when the dissociation coefficient reaches amaximum.This maximum will be smaller the greater the pressure,a result which is in contradiction to tlhe ordinarv idea that a t a suffi-ciently high temperature all substances undergo &mplete dissociation.H. C.Rise of Salt Solutions in Capillary Tubes. By N. GOLDSTEIN( J . RUM. Chem. Soc., 1888. 20, 408--415).-l'he author has found,as Valson did, that the heights of liquids in capillary tubes are in-versely proportional to their densities. so that htl = const. This rule,however, holds good only in the case of very dilute solutions, thevalue hd growing with increasing concentration.I n such a case, tliecapillary rise of the solution is found to be a function not only of thedensity, but also of the molecular weight of the salt dissolved. I nconcentrated solutions containing one and the same percentage ofdifferent salts, the height of the column increases with a decreasingniolecular weight of the salt dissolved. Inversely. when two differentsolutions give columns of the same height, that salt, which is in smallerquantity, is sure to have a larger atomic weight. The difference inthe height of the column corresponding with an equal difference o206 ABSTRACTS OF CHEMICAL PAPERS.percentages in solution will be nearly the same with salts of the samemolecular weight, but larger with increasing molecular weight of thesalt in solution.For exa.mple, with change of percentage of sodiumchloride from 23.4 to 5.8 there is a diflermce of 2.6 mm. in the heightof the column of liquid, whereas for the same change in a solutionof potassium chloride the difference in the height of the column is6.9 mm. The author propoqes to investigate in the same way solutionsof carbon compounds, and especially solutions of salts containingwater of cry stallisation. B. B.Catalytic Action of Metals on Oxyhydrogen Gas and theOcclusion of Hydrogen. By A. BERLINER (Anti. Phys. Chem. [Z],35, 791- 810).-l’he term catalysis was first applied by Berzelius(Ann. Chim. Phys., 37, 66) t o the power shown by certain substancesof causing decomposition or other chemical changes in other su0-stances without being themselves affected.Dulong and ThBnard have shown (Ann.Phys Chem., 76,81) that allmetals and some earths can determine chemical union betoween oxygenand hydrogen at temperatures below the boiling point of mercury, andin the case of platinum, palladium, rhodium, and iridium, a t ordinarytemperatures. Faraday has shown (Ann. Phyq. Chem., 33, 149) thatt’he action of plntinuni on oxyhydrogen gas occurs a t ordinary tem-peratures, only when the surface of the metal is perfectly clean.Henry (Phil. Mag. [ 3 ] , 6, 354) and Turner (Amalen, 2, 210) haveshown that copper and iron turnings, zinc-foil and wood-carbon havethe same effect on oxyhydrogen gas, but only a t temperatures not f a rbelow thc boiling pointl of mercury, arid Loew ( J .pr. Chem. [Z], 11,372) has shown that glass begins to act in the same way a t about,the same temperature.Berthelot (Abstr., 1882, 1022) pointed out the connection existingbetween catalytic action and occlusion of hydrogen, and the presentpaper contains an account of an extensive series of experimentsdirected to the further elucidation of the subject. The author arrivesa t the conclusion that these catalytic actions are invariably due to theocclusion of hjdrogen, which when occluded always seems to act inthe same way as when in the nascent state, as Graham (Phil. Mag. [4],32, 503) showed conclusivelyin the case of palladium. The fact thatwhen the metallic surface is not clean catalysis still takes place a thigh temperatures is attributed by the author to the partial removalof the film of impurity M hen the teniperature is suficiently increased :this is in accordance with Graham’s observation that the largestamount of gas was occluded when the metal was first strongly heatedand then allowed to cool in the gas forming the subject of experiment,Metallic Lustre. By W. SPRING (Bull. SOC. Chim., 50,218-261 ).-When finely powdered bismuth sulphide, copper sulphide, ormanganese peroxide are corn pressed in cylinders, they acquire ametallic lustre, whilst zinc sulphide, mercury oxide, and copper car-honate acquire a vitreous lustre. A microscopic examination showedthat the substances which take a metallic lustre form, without exception,opaque powders, and that the compounc’s hich have glazed surfacesG. W. TIXORGANIC CHEJIISTRT. 207are more or less transparent< when finely powdered. Between metallicand vitreous lustre there are ali degrees coiresponding with the variousdegrees of transparency and opaqueness. The metallic 1 ustre, there-fore, does not depend on the chemical but on the physical state of asubst,)nce (compare Dove, Ann. Phys. Chem., 83, lCi9 ; Brewster,F'ortschritte d. Phys., 8, 331 ; and Briickc, ibid., 17, 313).N. H. If.Apparatus for Fractional Distillation in a Vacuum. By. J.W. B R ~ ~ H L (Ber., 21,339-3342) .-The apparatus consists of a cy Iin-drical vessel, closed a t the bottom and provided at the lop with a groundflange, on to which fits a lid provided with a corresponding flange andtwo tubulures, one of which is placed in the centre of the lid. Throughthe centre tubulure, closed by an india-rubber cork, passes a rod byiiieans of which a circular rack containing test-tubes can be rotated inorder to bring the tubes in turu immediately under the condenser-tubewhich passes through the second tubulure,also closed by an india-rubbercork. The cylindrical vessel is provided with st tubulure for connectionto a pump. w. P. w.Ether Levels. By R. WEBER (Bey., 21, 3448--3451).-Thecrystalline figures frequently observed i n the ether levels attached tlolevelling instruments o r physical apparatus, are caused by the use ofwet ether, and of glass which is readily attacked by water. Threekinds of glass having the compositioii-SO2. A1,03. CaO. K20. Na20. Total.Relatively hard . . . 69-00 0.89 12.21 18.52 - 100.62Relatively soft . . . . 65.42 0.93 13.67 19-76 - 99-78Ronsack glass . . . . 69.93 0.94 4.56 7-27 17-30 100.00were experimented with, and it was found that tubes of Bonsackglass were attacked both by wet and dry ether, and gave crystallinebgures within a month of being filled ; that tubes of the softer potashglass were also readily attacked by wet ether, bnt showed only slight)indications of crystals after two years when filled with dry ether,whilst tubes of the harder potash glass were also attacked, althoughmore slowly, by wet ether, but remained clear after the lapse of tmoyeais when filled w i t h dry ether. w. P. w

ISSN:0368-1769    

DOI:10.1039/CA8895600197

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

IXORGANIC CHEJIISTRT. In o r g a n i c C h e m i s t r y. 207 Oxidation of Hydrogen Iodide by Oxy-aeids. By 0. BURCHARD (Zeit. physikab. Clzenz., 2, 796-8;39).-This paper contains the details of st large number of experiments on the action of chloric, bromic, and iodic acids on hydrogen iodide, with varying concentrations of the solutions, and also in the presence of other acids. Of the above three208 ARSTHXCTS OF CHEMICAL PAPERS. acids, iodic acid is the one which acts most readily on hydrogen iodide and chloric acid the least. With dilute solutions of iodic acid and hydrogen iodide, a certain period elapses before t,he reaction sets in, this period increasing, of course, with the dilution and also with the temperature. It was necessary in studying the reaction, as a time reaction, t o neutralise the mixture o€ both acids at a given moment, without affecting in any way the liberated iodine.This it was found could be done by the addition of acid sodium crtrbonate to the solution. The carbonate, which is thus introduced in excess, interferes, however, with the estimation of the iodine by means of thiosulphate, but for thc latter, sodium hydrogen sulphite may be substituted, the action of which on iodine in solution is represented by NaHS03 + H20 + I, = NaHS04 + 2H1, and is not affected by the preseiice of the carhonate. The action of iodic acid on hydrogen iodide is representcd by 5HI + HIO, = 3H20 + 31,. For the action of bromic acid, solutions of at least dDC normal concentration are required, and the action takes place in three stages : (1) HBrO, + 5HI = 3H,O + Br + 51; (2) Br + HI = HBr + I; ( 3 ) HBrO, + 5HBr = 3H20 + 3Br2.Hence, if there are less than six equivalents of hydrogen iodide to each equivalent of bromic acid present, bromine will be found in the solution a t the end of the reaction. For the action of chloric acid, the solutions miist be so concentrated, and the time required is so long, that a decomposition of the hydrogen iodide itself occurs, and thus the exact nature of the reactlion carinot be ascertained. None of the ordinary equations satisfy the conditions of the above changes studied as time reactions. The author finds, however, that the time required for the oxidation of a given quantity of hydrogen iodide depends in a similar manner on the concentration, as the action of sulphurous on iodic acid studied by Landolt (Abstr., 1886, 658).An excess of either acid above the equivalent quantities produces an acceleration of the reaction. The presence of other acids, both those which take part in the reaction and tliose which do not, also causes an acceleration, which in the case of the latter is in proportion to their avidities. H. c'. Action of Incandescent Platinum on Gases and Vapours. By W. R. HODGKINSON and F. K. S. LOWNDES (Chew,. News, 58, 223- 2'24 ; compare Abstr., 1889, 20).--It is now shown t,hat iodine mono- chloride or trichloride, or chlorine in the presence of iodine or iodine bromides, when vaporised and submitted to the action of incandescent platinum wire, in the manner already described, give rise to flames, to mixtures of platinous chloride or bromide and iodide, and in the presence of chlorine to the deposition of crystals of platinum on the hottest part of the wire. I n similar experiments with carbon tetra- chloride, there is no flame, chlorine is liberated and carbon and carbon sesquichloride are deposited ; with phosphorus pentachloride there is flame, but the wire soon becomes alloyed with liberat,ed phosphorus, and, consequently, melts ; with hydrochloric acid, platinons chloride is formed ; hydrogen fluoride yields a soluble platinum salt ; mercurous chloride gives platinons chloride and mercury ; phosphorus or arsenicINORGANIC CHEMISTRY.209 vapour destroys the wire at once, whilst there is no apparent action with mercury, sulphur, nilrogen oxides, or sulphurous anhydride. D.A. L. Analysis of Atmospheric Air. By UFFELMANN (Chen?. Cmt~., 1888, 1324-1325, from Archiv. f. Hygiene, 8, 262--350).-The carbonic anhydride was deterniined in a flask of about 24 to 4 litres capacity. After filling with water, the flask was completely filled with the air under investigation, by running out the water again and allowing it to drain for 10 minutes. 50 c c. of baryta-water (7 : 1000) was next added, the flask closed with a tight stopper with india- rubber cap, and after shaking for one minute, allowed to remain by itself for 24 hours. The stopper was now replaced by a double-bored one, 60 C.C. of freshly boiled water added to wash down the sides of the flask, and the excess of baryta titrated with oxalic acid from a burette with a very long nozzle, reaching through the stopper down to the liquid at the bottom of the flask. (The oxalic acid = 2.8636 grams per litre.) The determination of the organic matters of the atmosphere was made by passing a definite quaiitity of the air through a solution of potassium permanganate, of which 1 C.C.= 0.395 gram KMn04 (= 0.1 mgrm. = 0.07 C.C. 0 = 0 7875 mgrm. oxalic acid) and the excess of permanganate determined by oxalic acid. The dust was collected on an asbestos filter and titrated with permanganate accord- ing to the method above mentioned. The micro-organisms were determined, after collecting in sterilised water, according to Esniarch's method. The ammonia was determined by projecting a spray of water against a slanting glrtps plate at the distance of 1 metre, and titrating with Nessler's reagent.The principal results of a long series of examinations of the atmo- sphere in the neighbourhood of Rostock are as follows :-(1,) The carbonic anhydride amounted to 3.18 in 10,000 in the open field ; the amount increased with land-winds or fog. (2.) The organic matters were equivalent to 2.71 C.C. oxygen per 1,000,000 vols. of air in the open field ; this amount varied very greatly, i t being decidedly less after continued rain. (3.) The amount of organic matter in the air at the sea-coast was found to be but one-third of that found 12 kilo- metres inland. (4.) The air of the Rostock University yard contained one-tenth more carbonic anhydride and one-third more organic matter than the air of the open fields.(5.) The air in the open fields near Rostock contained, on the average, 250 micro-organisms per cubic metre, that of the university yard 450, whilst the air on the sea-coast contained but 100 per cubic metre ; these quantities being less after continued rain and greater during fog. (6.) The amount of carbonic anhydride in cellars depends greatly on the barometric pressure, and varies inversely as the height of the barometer. (7.) The air of cellars contained spores of fungi. (8.) The air of house sewers was found to be but little richer in organic matter than that of well ventilated rooms, and coutained but few germs. (9.) Atmospheric air may be considered impure when it contains so much210 ARSTRACTS OF CHEMICAL PAPERS. oxidisable organic matters that in 1,000,000 vols.12 or more vols. of oxygen are required in the permanganate test. J. W. L. Hydrogen Telluride. By BERTHELOT and FABRE (Ann. Chim. Pkys. [GI, 14, 103--106).-Pure hydrogen telluride (compare Bineau, Aim. Chin?. Phys. [2], 47, 232) can be prepared by treating maqne- fiium telluride with very dilute hydrochloric acid in an atmosphere of nitrogen. The gas thus obtained is completely and rapidly absorbed b r a1 kalis, yielding white or colourless, crystalline tellurides which dissolve in pure water, forming colourless solutions ; if, however, a trace of oxygen is present, violet or purple solutions are produced, and, with a large excess of oxygen, metallic tellurium is immediately precipitated. It is very unstablc ; when kept over dry mercury, it de- composes in a few hours, even in the dark, but in presence of moist air tlecomposition is instantaneous.The smell of hydrogen telluride differs considerably from that of hydrogen sulphide or selenide, and when the gas is inhaled the effects produced are far less disagreeable than i n the case of the latter. The magnesium telluride referred to aI)ove is prepared by the action of excess of tellurium vapour on heated magnesium in an atmosphere of pure, dry hydrogen. It is a white substance, which quickly darkens on exposure to the air, and dissolves in water, forming a blackish-purple solution, owing to the presence of oxygen ; it dissolves in water saturated with nitrogen, yielding an almost colourless solution. F. S. I(. Amides of Phosphorus and Sulphur.By A . MENTE (Annalen, 248, 232--869).-GGladstone (this Journal, 1864, 225 ; 1866, 1 and 290 ; 1868, 64 and 261, and 1869, 55) obtained a series of compounds by the action of gaseous ammonia on phosphorus oxychloride, which he regarded as amic acids of pyrophosphoric or tetraphosphoric acid. The author considers t h a t these compounds are imido-acids. Imidodi- ph~~phoric acid, NH<potoH)>O PO(0H) (Gladstone's ppophosphamic acid), \ I can be prepared by the action of ammonium cerbamate on phosphorus oxychloride. The product is dissolved in water containing hydro- chloric acid, and the acid is precipitated in the form of the barium or iron salt by the addition of barium or ferric chloride. The barium salt contains 1 mol. H20. Di-imidodbhosphoric acid, NH<pOIOH)>NH7 PO(0H) is best prepared by .I adding phosphorus oxychloride diluted with 10 times its volume of benzene to excess of ammonium carbarnate. The barium salt is sparingly soluble in water and is anhydrous. A basic sodium salt, NaN:P,O,(ONa)?:NH, is known. Di-in, idod ip ho'sphormonamk acid ( pyrophospho triamic acid), N"<pocoH) PO(NH2) >NH, is an insoluble, white powder, obtained by \ I saturating phosphorus oxychloride with ammonia a t loo", and was11- ing the product with water. The acid is decomposed by boiling with sodium hjdroxide, yielding the basic sodium salt of di-irnidodiphos-INdRGANIC CHEMISTRY. 21 1 phoric acid. Silver nitrate gives. with neutral solutions of the acid, the monobasic silver salt, P,O,(NH),(NH,)*OAg, with ammonincal solutions a salt of the formula NAg:P,O,(NAg),(NH,)-OAg.The salts of this acid have already been described by Gladstone (loc. cit.). ing imidodiphosphoric chloride, NH( POCl,),, at 290", yields an insoluble barium salt, NP307Ba + H20. The cnlcium and ferric salts are insoluble, even in strong acid. Most of the metallic salts are insoluble in water but dissolve in acids. Neither the acid itself nor the salts of the alkali metals have been obtained in a crystslline form. Am?nonium imidosulphonate, NH( S0,*ONH4),, is formed by +he action nf ammonium cai*bamate on sulphuryl chloride, pyrosulphuryl chloride, or sulphuric monochlorhydrin. Amnionium chloride is removed by digesting with alcohol, and tlie residue is recrystallised from water. The compound crystallises in the monoclinic system, :ind its sp.gr. is 1.965. Imi~oszcZphuryZnmide, NH(SO,NH,),, is tlie first product of the action of ammonium carbamate on pyrosulphuryl chloride. I t is decomposed by water, yielding ammonium imidosul- phonate. The amide forms beautiful crystals, and is freely soluble i n water. IV. c. w. Allotropic Arsenic. Reply to Geuther. By ENGEL (BUZZ. XOC. Chinz., 50, 194--1'37).-Several new determinations of the specific gravity of allotropic arsenic gave the mean 4.6, which is the same number as that previously obtained (compare Geuther, Abstr., 1887, 888). The ratio of the densities of crystalline and allotropic arsenic is 1.245, and is practically the same as the ratio of white and red phosphorus = 1.244. The molecular constitution of the two modi- fications of arsenic seems to be the same as that of the corresponding modifications of phosphorus.Action of Ammonia and Amines on Arsenious Bromide. By W. LANDAU (Cheltz. Centr., 1888, 135&1355).--By passing dry ammonia into a solution of arsenious bromide and benzene, the compound 2AsBr3,7NH3 was formed. Ethylamine forms the com- pound AsBrj,4NH,Et + H,O, melting at 152". DipvopyZavuine forms with it the componnd AsBr3,4NHPr2 + H20, melting a t 258". The trimethylamine-derivative, AsBr3,3NMe3, melts at 235". 'The com- pound from triethylamine, AsBr,,3NEt3, melts a t 242". The aniliiLe compound, AsBr,,SNH,Ph + H,O, becomes changed into AsBrJ,4NH,Ph + H,O, by treatment with absolute alcohol or glacid acetic acid. Diphenylnmine arsenious bromide, AsBr3,3NHPh, + H,O, melts at 140°, and becomes changed, like the aniline compound, by the actiou of alcohol or acetic acid into a compound melting a t 230".The quinoline corn pound, As Rr3, C9NH7, HBr, melts at 13 7". The tyiethy Zp hosp hine- derivative, AsBr,,PEt,,HBr, melts a t 6Fj". J. W. L. N. H. M. Preparation of Boron and Silicon. By S . G. RAWSON (Chem. News, 58, 283).-A mixture of 3.5 grams of boric anhydride and212 ABSTRACTS OF OHEMTCAL PAPERS. 11 grams of calcium fluoride, is gently heated with concentrated sul- phuric acid ; the boron fluoride evolved is passed over heated potis- sium contained in a series of bulbs. Potassium fluoride and boroii arc formed, and are easily separated by washing with water. Amorphous silicon may be prepared in a similar manner, D.A. L. Preparation of Silicon. By H. N. WARREN (Chem. News, 58, 215-216) .-The author prepares amorphous silicoii by passing silicon fluoride over metallic magnesium heated in a combustion tube. Among the other products of the reaction is a magnesium silicide, and by the action of concentrated acids on this, a gas is evolved, which takes fire spontaneously in the air with explosive violence ; with feeble acids the gas is not spontaneously inflammable. Owing to the difflculty of eliminating free hydrogen from this gas, its exact composition could not be ascertained : it, however, appears t o he a mixture of solid, liquid, and gaseous silicon hydride. D. A. L. Effect of High Temperature and Pressure on Carbon. By C. A. PARSONS (Proc. Roy. Soc., 44, 320--323).-Carbon rods were snrrounded by benzene, paraffin, treacle, chloride o r bisulphide of car.hon, and submitted to great pressure in a hydraulic press, the rods being meantime heated by passing an electric current through them.In some cases a considerable amount of gas was evolved, and a soft friable deposit of carbon produced. In no case was the density of the carbon increased. When the rod was surrounded with silica, the latter fused, and the rod was largely conrerted into graphite ; the Rame occurred with hydrated alumina in lime or magnesia, the rod being rapidly destroyed with evolution of gas. With layers of coke, lime, and silica, the rod was rapidly corroded, and was found after the experiment to be coated with a coke-like layer of great hardness, sufh’cient to scratch rock-crystal and ruby, and to wear down the cut facets of a diamond.It resists the action of a mixture of hpdrofluoric and nitric acids. The conditions of temperature and pressure with presence of moisture, lime, and silica, resemble those which appear to have existed in the craters of the Cape diamond mines. The part played by the lime and silica is not clear. Formation of Carbon Oxysulphide by the Action of Carbon Bisulphide on Clay. By A. GAUTTER (Comyt. rend., 107, 911- 913).-K;lolin previously heated to incipient redness is packed into a ia1-g.e porcelain tube, which is then heated to bright redness, whilst car+on bisulphide vapour is passed through it. The gas which issues from the tube contains 60-64 per cent. of carbon oxysulphide, 35-39 per cent.of carbonic oxide, about 1 per cent. of carbonic anhydride, find traces of hydrogen sulphide, mixed of course with excess of carbon bisulphide vapour. The proportion of carbonic oxide is lower, and the proportion of oxysulphide higher the higher the temperature. The products are passed into a flask half filled with ice-cold water, which condenses the greater part of the bisulphide ; then through potaBsium hydroxide, which absorbs hydrogen sulphide and carbonic anhjdride ; then though acidified cuprous chloride, which absorbs car- H. K. T.INORGANIC CHEMISTRY. 213 bonic oxide, and finally through a 12 per cent. solution of aniline in alcohol, and over pumice and sulphuric acid. Alcoholic aniline has no action on carbon oxysulphide, but readily absorbs carbon bisul- phide.The properties of pure carbon oxysulphide agree mainly with the ordinary description. It has a very faint, somewhat et'hereal alliaceous odour. Carbon oxysulphide, as Berthelot observed, combines slowly with ammonia, forming yellow crystals of ammonium oxythiocarba- mate, which is decomposed by water. Sodium hydroxide slowly absorbs the gas, and a 35 per cent. solution in contact with excess of the gas yields pale-yellow tabular and acicular crystals of a thiocar- bonate, which is decomposed by water, as indicated by the equation 2NaHCS0, + H,O = NaHC03 + NaRS + CO, + H2S. When carbon oxysulphide is prepared by the action of carbon bisulphide 011 an oxide, alumina gives the best results, but it becomes too finely divided, and is difficult to manage.It mnst be heated to a white heat, since even a t a cherry-red heat the yield is small. If, however, sulphur vapour is passed over a mixture of alumina and carbon heated to bright, redness, almost pure carbon oxysulphide is obtained. Fremy observed that when carbon bisulphide is passed over heated oxides of lead, zinc, iron, and copper, crystalline sulphides are formed. The author finds that only in the case of zinc oxide is any notable quantity of carbon oxysulphide obtained. After carbon bisulphide has been passed over kaolin, the tube contains brilliant, acicular crystals of silicon sulphide, and somewhat large, hard, lozenge-shaped crystals, which evolve hydrogen sulphide when moistened, and are slowly decomposed by water into alumina and gelatinous silica,.They consist of a kind of thiosilicate, some of the oxygen in the kaolin having been replaced by sulphur, whilst some of the silicon has been removed in the form of sulphide. Alkaline Aluminates. By K. J. BAYER (Chem. %it., 12, 1209- 1210).-When the product of the ignition of alumina and soda in the molecular proportions 1 : 1 is treated with water, pure hydrated alumina, A1,o3,3H,0, is spontaneously and continuously deposited until the solution contains alumina and sodium hydroxide in t'he proportions of 1 mol. of the former to 6 mols. of the latter; the decomposition t,hen proceeds no further, and the solution remains clear. If instead of water a solution of sodium hydroxide, containing as much sodium as is already present in the ignited mixture is employed, then the solution remains quite clear, whether warm or cold, or a t rest or in motion, provided it is protected from carbonic anhydride ; but in the presence of this gas, or of spontaneously depo- sited hydrated alumina, this solution behaves in the manner already described.Neither pulverised glass, nor sand, nor granite powder, nor even ordinary gelatinous a,lumina can initiate this decomposition. If the Eolntions contain sodium salts with alkaline reaction, the podium determined by titration is somewhat higher, but the preci- pitated alumina is always pure. Potassium aluminate behaves in a similar manner. In explanation of these results, the author suggests that the A1,0,,2Na20 and A120,,6Na20 are really chemical compounds. C. H. B. Y VOL. LVI.214 ABSTRACTS OF CHEMICAL PAPERS.and therefore with the compounds A1203,Na20 and A1,03,3Na20 would indicate the existence of four different alkaline aluminates. D. A. L. Porcelain Glazes. By C. LAUTH and G. DUTAILLY (Bull. Soc. Chiw., 50, 221--251).-The first part of the paper contains the re5ults of experiments made with colourless glazes, which are divided into three classes :-(1.) Silicates of a single base associated with silica and alumina. (2.) Silicates of two bases, associated with silica and alumina. ( 3 . ) Silicates of several bases together, associated with silica and alumina. In the second part of the paper, experiments wit’h various coloured glazes are described. N. H. M. Cause of Rails Rusting less Quickly when in Use than when not. By W. SPRING (BUZZ.SOC. Chirrh., 50, 215-218).--The preservation of rails, when in use, from rust is not the result of vibratory movement, or of an electric action due to the passage of trains, but is due t o the superficial fovmation of the magnetic oxide produced by the compressign of the rust on the metal. - N. H. M. A Crystalline Subsulphide of Iron and Nickel. By J. B. MACKINTOSH (Chem. Neu-s, 58, 200).-A compound approximating in composition to the formula Fe4Ni2S, has been found in fern-like aggregations of srnall cnbical crystals in the cavities in the concre- tions in the hearth of a shaft furllace used for smelting roasted nickeliferous pyrrhotite. The author’s analytical numbers are : Cu 2.20 ; Ni,Co 26.16 ; Fe 61.685 ; S 8.305 ; SiO, 0.56 ; total, 98.91 ; deficiency and silica being due to adherent slag.D. A. L. New Fluorine Compounds of Vanadium. By A. PIccIx-r and G. GIORGIS (Gazzetta, 18, 186--194).-On dissolving ammonium metavanadate in aqueous hydrofluoric acid and treating the hot liquid with sulphurous anhydride, a blue liquid is obtained, which on neutralising with ammonia and adding ammonium fluoride, yields a bluish, crystalline precipitate This is collected, washed with a little water, and recrystallised from water; a t first monoclinic prisms having the composition of Baker’s salt (Trans., 1879, 760) separate, and then srnall, blue, lustrous crystals; these are mono- metric octahedra, which dissolve easily in water, yielding a blue solu- tion, from which the salt separates again on the addition of ammonium fluoride.On analysis, it gave results correbponding with the formula VOF,,SNH,F. The author calls it octahedral ammonium hydrqjluorozy- varbadats. When dissolved in concentrated hy drofluoric acid and allowed to remain for some days, it deposits crystals of Baker’s salt, VOF,,2NH4F + H,O. The new salt is also formed a t the negative pole, when a solution of ammonium metavanadate, acidified with hydrofluoric acid and mixed with ammonium fluoride, is submitted to electrolysis ; or when the mixture is reduced by alcohol. I n the latter case, how- ever, the mother-liquors, if exposed to the air after the hydrofluoroxy- vanadate has been deposited, yield yellow, octahedral crystals of t h e composition V02F,YNH4F. These can be obtained more easily byMINERALOGCICAL CHEMISTRY.215 dissolring vanadic acid in excess of hydrofluoric acid, and carefully neutralising w i t h ammonia while the liquid is still warm. On cooling, an abundant deposit of the crystals is obtained ; care must be taken not to add any great excess of ammonia, otherwise colourless crystals of ammonium vanadate alone will separate. By adding potassium hydrogen fluoride to a solution of ammonium metavanndate reduced by sulphurous anhydride, and evaporating the blue solution, the author obtained sky-blue, crystalline crusts, of the composition VOF2,2KC1. The remainder of the paper is devoted to theoretical consideration of the crystallographic connection of various isomorphous fluorides, the author drawing especial attention to the fact that the four com- pounds V0,F,3NH4F’, VOF,,SNH,F, FeF,,3NH4F, and CrF3,3NH4F, all crpstallise in the monometric system in cubes or octahedra, and all contain the same number of atoms.C. E. G.IXORGANIC CHEJIISTRT.In o r g a n i c C h e m i s t r y.207Oxidation of Hydrogen Iodide by Oxy-aeids. By 0. BURCHARD(Zeit. physikab. Clzenz., 2, 796-8;39).-This paper contains the detailsof st large number of experiments on the action of chloric, bromic, andiodic acids on hydrogen iodide, with varying concentrations of thesolutions, and also in the presence of other acids. Of the above thre208 ARSTHXCTS OF CHEMICAL PAPERS.acids, iodic acid is the one which acts most readily on hydrogen iodideand chloric acid the least. With dilute solutions of iodic acid andhydrogen iodide, a certain period elapses before t,he reaction sets in,this period increasing, of course, with the dilution and also with thetemperature.It was necessary in studying the reaction, as a time reaction, t oneutralise the mixture o€ both acids at a given moment, withoutaffecting in any way the liberated iodine.This it was found could bedone by the addition of acid sodium crtrbonate to the solution. Thecarbonate, which is thus introduced in excess, interferes, however,with the estimation of the iodine by means of thiosulphate, but forthc latter, sodium hydrogen sulphite may be substituted, the action ofwhich on iodine in solution is represented by NaHS03 + H20 + I, =NaHS04 + 2H1, and is not affected by the preseiice of the carhonate.The action of iodic acid on hydrogen iodide is representcd by5HI + HIO, = 3H20 + 31,.For the action of bromic acid, solutionsof at least dDC normal concentration are required, and the actiontakes place in three stages : (1) HBrO, + 5HI = 3H,O + Br + 51;(2) Br + HI = HBr + I; ( 3 ) HBrO, + 5HBr = 3H20 + 3Br2.Hence, if there are less than six equivalents of hydrogen iodide toeach equivalent of bromic acid present, bromine will be found in thesolution a t the end of the reaction. For the action of chloric acid, thesolutions miist be so concentrated, and the time required is so long,that a decomposition of the hydrogen iodide itself occurs, and thus theexact nature of the reactlion carinot be ascertained.None of the ordinary equations satisfy the conditions of the abovechanges studied as time reactions. The author finds, however, thatthe time required for the oxidation of a given quantity of hydrogeniodide depends in a similar manner on the concentration, as the actionof sulphurous on iodic acid studied by Landolt (Abstr., 1886, 658).An excess of either acid above the equivalent quantities produces anacceleration of the reaction.The presence of other acids, both thosewhich take part in the reaction and tliose which do not, also causes anacceleration, which in the case of the latter is in proportion to theiravidities. H. c'.Action of Incandescent Platinum on Gases and Vapours.By W. R. HODGKINSON and F. K. S. LOWNDES (Chew,. News, 58, 223-2'24 ; compare Abstr., 1889, 20).--It is now shown t,hat iodine mono-chloride or trichloride, or chlorine in the presence of iodine or iodinebromides, when vaporised and submitted to the action of incandescentplatinum wire, in the manner already described, give rise to flames,to mixtures of platinous chloride or bromide and iodide, and in thepresence of chlorine to the deposition of crystals of platinum on thehottest part of the wire.I n similar experiments with carbon tetra-chloride, there is no flame, chlorine is liberated and carbon and carbonsesquichloride are deposited ; with phosphorus pentachloride there isflame, but the wire soon becomes alloyed with liberat,ed phosphorus,and, consequently, melts ; with hydrochloric acid, platinons chlorideis formed ; hydrogen fluoride yields a soluble platinum salt ; mercurouschloride gives platinons chloride and mercury ; phosphorus or arseniINORGANIC CHEMISTRY.209vapour destroys the wire at once, whilst there is no apparent actionwith mercury, sulphur, nilrogen oxides, or sulphurous anhydride.D. A. L.Analysis of Atmospheric Air. By UFFELMANN (Chen?. Cmt~.,1888, 1324-1325, from Archiv. f. Hygiene, 8, 262--350).-Thecarbonic anhydride was deterniined in a flask of about 24 to 4 litrescapacity. After filling with water, the flask was completely filled withthe air under investigation, by running out the water again andallowing it to drain for 10 minutes. 50 c c. of baryta-water (7 : 1000)was next added, the flask closed with a tight stopper with india-rubber cap, and after shaking for one minute, allowed to remain byitself for 24 hours.The stopper was now replaced by a double-boredone, 60 C.C. of freshly boiled water added to wash down the sides ofthe flask, and the excess of baryta titrated with oxalic acid from aburette with a very long nozzle, reaching through the stopper downto the liquid at the bottom of the flask. (The oxalic acid =2.8636 grams per litre.)The determination of the organic matters of the atmosphere wasmade by passing a definite quaiitity of the air through a solution ofpotassium permanganate, of which 1 C.C. = 0.395 gram KMn04(= 0.1 mgrm. = 0.07 C.C. 0 = 0 7875 mgrm. oxalic acid) and theexcess of permanganate determined by oxalic acid. The dust wascollected on an asbestos filter and titrated with permanganate accord-ing to the method above mentioned.The micro-organisms weredetermined, after collecting in sterilised water, according to Esniarch'smethod.The ammonia was determined by projecting a spray of water againsta slanting glrtps plate at the distance of 1 metre, and titrating withNessler's reagent.The principal results of a long series of examinations of the atmo-sphere in the neighbourhood of Rostock are as follows :-(1,) Thecarbonic anhydride amounted to 3.18 in 10,000 in the open field ; theamount increased with land-winds or fog. (2.) The organic matterswere equivalent to 2.71 C.C. oxygen per 1,000,000 vols. of air in theopen field ; this amount varied very greatly, i t being decidedly less aftercontinued rain.(3.) The amount of organic matter in the air atthe sea-coast was found to be but one-third of that found 12 kilo-metres inland. (4.) The air of the Rostock University yard containedone-tenth more carbonic anhydride and one-third more organic matterthan the air of the open fields. (5.) The air in the open fields nearRostock contained, on the average, 250 micro-organisms per cubicmetre, that of the university yard 450, whilst the air on the sea-coastcontained but 100 per cubic metre ; these quantities being less aftercontinued rain and greater during fog. (6.) The amount ofcarbonic anhydride in cellars depends greatly on the barometricpressure, and varies inversely as the height of the barometer.(7.) The air of cellars contained spores of fungi.(8.) The air ofhouse sewers was found to be but little richer in organic matter thanthat of well ventilated rooms, and coutained but few germs. (9.)Atmospheric air may be considered impure when it contains so muc210 ARSTRACTS OF CHEMICAL PAPERS.oxidisable organic matters that in 1,000,000 vols. 12 or more vols. ofoxygen are required in the permanganate test. J. W. L.Hydrogen Telluride. By BERTHELOT and FABRE (Ann. Chim.Pkys. [GI, 14, 103--106).-Pure hydrogen telluride (compare Bineau,Aim. Chin?. Phys. [2], 47, 232) can be prepared by treating maqne-fiium telluride with very dilute hydrochloric acid in an atmosphere ofnitrogen. The gas thus obtained is completely and rapidly absorbedb r a1 kalis, yielding white or colourless, crystalline tellurides whichdissolve in pure water, forming colourless solutions ; if, however, atrace of oxygen is present, violet or purple solutions are produced,and, with a large excess of oxygen, metallic tellurium is immediatelyprecipitated.It is very unstablc ; when kept over dry mercury, it de-composes in a few hours, even in the dark, but in presence of moist airtlecomposition is instantaneous. The smell of hydrogen telluridediffers considerably from that of hydrogen sulphide or selenide, andwhen the gas is inhaled the effects produced are far less disagreeablethan i n the case of the latter. The magnesium telluride referred toaI)ove is prepared by the action of excess of tellurium vapour onheated magnesium in an atmosphere of pure, dry hydrogen.It is awhite substance, which quickly darkens on exposure to the air, anddissolves in water, forming a blackish-purple solution, owing to thepresence of oxygen ; it dissolves in water saturated with nitrogen,yielding an almost colourless solution. F. S. I(.Amides of Phosphorus and Sulphur. By A . MENTE (Annalen,248, 232--869).-GGladstone (this Journal, 1864, 225 ; 1866, 1 and290 ; 1868, 64 and 261, and 1869, 55) obtained a series of compoundsby the action of gaseous ammonia on phosphorus oxychloride, whichhe regarded as amic acids of pyrophosphoric or tetraphosphoric acid.The author considers t h a t these compounds are imido-acids. Imidodi-ph~~phoric acid, NH<potoH)>O PO(0H) (Gladstone's ppophosphamic acid),\ I can be prepared by the action of ammonium cerbamate on phosphorusoxychloride. The product is dissolved in water containing hydro-chloric acid, and the acid is precipitated in the form of the barium oriron salt by the addition of barium or ferric chloride.The bariumsalt contains 1 mol. H20.Di-imidodbhosphoric acid, NH<pOIOH)>NH7 PO(0H) is best prepared by. I adding phosphorus oxychloride diluted with 10 times its volume ofbenzene to excess of ammonium carbarnate. The barium salt issparingly soluble in water and is anhydrous. A basic sodium salt,NaN:P,O,(ONa)?:NH, is known.Di-in, idod ip ho'sphormonamk acid ( pyrophospho triamic acid),N"<pocoH) PO(NH2) >NH, is an insoluble, white powder, obtained by\ I saturating phosphorus oxychloride with ammonia a t loo", and was11-ing the product with water. The acid is decomposed by boiling withsodium hjdroxide, yielding the basic sodium salt of di-irnidodiphosINdRGANIC CHEMISTRY.21 1phoric acid. Silver nitrate gives. with neutral solutions of the acid,the monobasic silver salt, P,O,(NH),(NH,)*OAg, with ammonincalsolutions a salt of the formula NAg:P,O,(NAg),(NH,)-OAg. Thesalts of this acid have already been described by Gladstone (loc. cit.).ing imidodiphosphoric chloride, NH( POCl,),, at 290", yields aninsoluble barium salt, NP307Ba + H20. The cnlcium and ferric saltsare insoluble, even in strong acid. Most of the metallic salts areinsoluble in water but dissolve in acids. Neither the acid itself northe salts of the alkali metals have been obtained in a crystslline form.Am?nonium imidosulphonate, NH( S0,*ONH4),, is formed by +he actionnf ammonium cai*bamate on sulphuryl chloride, pyrosulphurylchloride, or sulphuric monochlorhydrin.Amnionium chloride isremoved by digesting with alcohol, and tlie residue is recrystallisedfrom water. The compound crystallises in the monoclinic system,:ind its sp. gr. is 1.965. Imi~oszcZphuryZnmide, NH(SO,NH,),, is tliefirst product of the action of ammonium carbamate on pyrosulphurylchloride. I t is decomposed by water, yielding ammonium imidosul-phonate. The amide forms beautiful crystals, and is freely soluble i nwater. IV. c. w.Allotropic Arsenic. Reply to Geuther. By ENGEL (BUZZ. XOC.Chinz., 50, 194--1'37).-Several new determinations of the specificgravity of allotropic arsenic gave the mean 4.6, which is the samenumber as that previously obtained (compare Geuther, Abstr., 1887,888).The ratio of the densities of crystalline and allotropic arsenicis 1.245, and is practically the same as the ratio of white and redphosphorus = 1.244. The molecular constitution of the two modi-fications of arsenic seems to be the same as that of the correspondingmodifications of phosphorus.Action of Ammonia and Amines on Arsenious Bromide.By W. LANDAU (Cheltz. Centr., 1888, 135&1355).--By passing dryammonia into a solution of arsenious bromide and benzene, thecompound 2AsBr3,7NH3 was formed. Ethylamine forms the com-pound AsBrj,4NH,Et + H,O, melting at 152". DipvopyZavuine formswith it the componnd AsBr3,4NHPr2 + H20, melting a t 258".Thetrimethylamine-derivative, AsBr3,3NMe3, melts at 235". 'The com-pound from triethylamine, AsBr,,3NEt3, melts a t 242". The aniliiLecompound, AsBr,,SNH,Ph + H,O, becomes changed into AsBrJ,4NH,Ph + H,O, by treatment with absolute alcohol or glacid acetic acid.Diphenylnmine arsenious bromide, AsBr3,3NHPh, + H,O, melts at 140°,and becomes changed, like the aniline compound, by the actiou ofalcohol or acetic acid into a compound melting a t 230". The quinolinecorn pound, As Rr3, C9NH7, HBr, melts at 13 7". The tyiethy Zp hosp hine-derivative, AsBr,,PEt,,HBr, melts a t 6Fj". J. W. L.N. H. M.Preparation of Boron and Silicon. By S . G. RAWSON (Chem.News, 58, 283).-A mixture of 3.5 grams of boric anhydride an212 ABSTRACTS OF OHEMTCAL PAPERS.11 grams of calcium fluoride, is gently heated with concentrated sul-phuric acid ; the boron fluoride evolved is passed over heated potis-sium contained in a series of bulbs.Potassium fluoride and boroii arcformed, and are easily separated by washing with water. Amorphoussilicon may be prepared in a similar manner, D. A. L.Preparation of Silicon. By H. N. WARREN (Chem. News, 58,215-216) .-The author prepares amorphous silicoii by passing siliconfluoride over metallic magnesium heated in a combustion tube.Among the other products of the reaction is a magnesium silicide,and by the action of concentrated acids on this, a gas is evolved,which takes fire spontaneously in the air with explosive violence ;with feeble acids the gas is not spontaneously inflammable.Owing tothe difflculty of eliminating free hydrogen from this gas, its exactcomposition could not be ascertained : it, however, appears t o he amixture of solid, liquid, and gaseous silicon hydride. D. A. L.Effect of High Temperature and Pressure on Carbon. ByC. A. PARSONS (Proc. Roy. Soc., 44, 320--323).-Carbon rods weresnrrounded by benzene, paraffin, treacle, chloride o r bisulphide ofcar.hon, and submitted to great pressure in a hydraulic press, the rodsbeing meantime heated by passing an electric current through them.In some cases a considerable amount of gas was evolved, and a softfriable deposit of carbon produced. In no case was the density ofthe carbon increased.When the rod was surrounded with silica, thelatter fused, and the rod was largely conrerted into graphite ; theRame occurred with hydrated alumina in lime or magnesia, the rodbeing rapidly destroyed with evolution of gas. With layers of coke,lime, and silica, the rod was rapidly corroded, and was found afterthe experiment to be coated with a coke-like layer of great hardness,sufh’cient to scratch rock-crystal and ruby, and to wear down the cutfacets of a diamond. It resists the action of a mixture of hpdrofluoricand nitric acids. The conditions of temperature and pressure withpresence of moisture, lime, and silica, resemble those which appearto have existed in the craters of the Cape diamond mines. The partplayed by the lime and silica is not clear.Formation of Carbon Oxysulphide by the Action of CarbonBisulphide on Clay.By A. GAUTTER (Comyt. rend., 107, 911-913).-K;lolin previously heated to incipient redness is packed into aia1-g.e porcelain tube, which is then heated to bright redness, whilstcar+on bisulphide vapour is passed through it. The gas which issuesfrom the tube contains 60-64 per cent. of carbon oxysulphide, 35-39per cent. of carbonic oxide, about 1 per cent. of carbonic anhydride,find traces of hydrogen sulphide, mixed of course with excess of carbonbisulphide vapour. The proportion of carbonic oxide is lower, andthe proportion of oxysulphide higher the higher the temperature.The products are passed into a flask half filled with ice-cold water,which condenses the greater part of the bisulphide ; then throughpotaBsium hydroxide, which absorbs hydrogen sulphide and carbonicanhjdride ; then though acidified cuprous chloride, which absorbs car-H. K.TINORGANIC CHEMISTRY. 213bonic oxide, and finally through a 12 per cent. solution of aniline inalcohol, and over pumice and sulphuric acid. Alcoholic aniline hasno action on carbon oxysulphide, but readily absorbs carbon bisul-phide.The properties of pure carbon oxysulphide agree mainly with theordinary description. It has a very faint, somewhat et'hereal alliaceousodour. Carbon oxysulphide, as Berthelot observed, combines slowlywith ammonia, forming yellow crystals of ammonium oxythiocarba-mate, which is decomposed by water. Sodium hydroxide slowlyabsorbs the gas, and a 35 per cent. solution in contact with excess ofthe gas yields pale-yellow tabular and acicular crystals of a thiocar-bonate, which is decomposed by water, as indicated by the equation2NaHCS0, + H,O = NaHC03 + NaRS + CO, + H2S.When carbon oxysulphide is prepared by the action of carbonbisulphide 011 an oxide, alumina gives the best results, but it becomestoo finely divided, and is difficult to manage.It mnst be heated to awhite heat, since even a t a cherry-red heat the yield is small. If,however, sulphur vapour is passed over a mixture of alumina and carbonheated to bright, redness, almost pure carbon oxysulphide is obtained.Fremy observed that when carbon bisulphide is passed over heatedoxides of lead, zinc, iron, and copper, crystalline sulphides are formed.The author finds that only in the case of zinc oxide is any notablequantity of carbon oxysulphide obtained.After carbon bisulphide has been passed over kaolin, the tubecontains brilliant, acicular crystals of silicon sulphide, and somewhatlarge, hard, lozenge-shaped crystals, which evolve hydrogen sulphidewhen moistened, and are slowly decomposed by water into aluminaand gelatinous silica,.They consist of a kind of thiosilicate, some ofthe oxygen in the kaolin having been replaced by sulphur, whilstsome of the silicon has been removed in the form of sulphide.Alkaline Aluminates. By K. J. BAYER (Chem. %it., 12, 1209-1210).-When the product of the ignition of alumina and sodain the molecular proportions 1 : 1 is treated with water, purehydrated alumina, A1,o3,3H,0, is spontaneously and continuouslydeposited until the solution contains alumina and sodium hydroxidein t'he proportions of 1 mol.of the former to 6 mols. of the latter;the decomposition t,hen proceeds no further, and the solution remainsclear. If instead of water a solution of sodium hydroxide, containingas much sodium as is already present in the ignited mixture isemployed, then the solution remains quite clear, whether warm orcold, or a t rest or in motion, provided it is protected from carbonicanhydride ; but in the presence of this gas, or of spontaneously depo-sited hydrated alumina, this solution behaves in the manner alreadydescribed. Neither pulverised glass, nor sand, nor granite powder,nor even ordinary gelatinous a,lumina can initiate this decomposition.If the Eolntions contain sodium salts with alkaline reaction, thepodium determined by titration is somewhat higher, but the preci-pitated alumina is always pure.Potassium aluminate behaves in asimilar manner. In explanation of these results, the author suggeststhat the A1,0,,2Na20 and A120,,6Na20 are really chemical compounds.C. H. B.Y VOL. LVI214 ABSTRACTS OF CHEMICAL PAPERS.and therefore with the compounds A1203,Na20 and A1,03,3Na20 wouldindicate the existence of four different alkaline aluminates.D. A. L.Porcelain Glazes. By C. LAUTH and G. DUTAILLY (Bull. Soc.Chiw., 50, 221--251).-The first part of the paper contains there5ults of experiments made with colourless glazes, which are dividedinto three classes :-(1.) Silicates of a single base associated withsilica and alumina. (2.) Silicates of two bases, associated with silicaand alumina.( 3 . ) Silicates of several bases together, associated withsilica and alumina. In the second part of the paper, experimentswit’h various coloured glazes are described. N. H. M.Cause of Rails Rusting less Quickly when in Use thanwhen not. By W. SPRING (BUZZ. SOC. Chirrh., 50, 215-218).--Thepreservation of rails, when in use, from rust is not the result ofvibratory movement, or of an electric action due to the passage oftrains, but is due t o the superficial fovmation of the magnetic oxideproduced by the compressign of the rust on the metal.-N. H. M.A Crystalline Subsulphide of Iron and Nickel. By J. B.MACKINTOSH (Chem. Neu-s, 58, 200).-A compound approximating incomposition to the formula Fe4Ni2S, has been found in fern-likeaggregations of srnall cnbical crystals in the cavities in the concre-tions in the hearth of a shaft furllace used for smelting roastednickeliferous pyrrhotite. The author’s analytical numbers are :Cu 2.20 ; Ni,Co 26.16 ; Fe 61.685 ; S 8.305 ; SiO, 0.56 ; total, 98.91 ;deficiency and silica being due to adherent slag. D. A. L.New Fluorine Compounds of Vanadium. By A. PIccIx-r andG. GIORGIS (Gazzetta, 18, 186--194).-On dissolving ammoniummetavanadate in aqueous hydrofluoric acid and treating the hotliquid with sulphurous anhydride, a blue liquid is obtained, whichon neutralising with ammonia and adding ammonium fluoride, yieldsa bluish, crystalline precipitate This is collected, washed witha little water, and recrystallised from water; a t first monoclinicprisms having the composition of Baker’s salt (Trans., 1879, 760)separate, and then srnall, blue, lustrous crystals; these are mono-metric octahedra, which dissolve easily in water, yielding a blue solu-tion, from which the salt separates again on the addition of ammoniumfluoride. On analysis, it gave results correbponding with the formulaVOF,,SNH,F. The author calls it octahedral ammonium hydrqjluorozy-varbadats. When dissolved in concentrated hy drofluoric acid and allowedto remain for some days, it deposits crystals of Baker’s salt, VOF,,2NH4F + H,O. The new salt is also formed a t the negative pole, whena solution of ammonium metavanadate, acidified with hydrofluoricacid and mixed with ammonium fluoride, is submitted to electrolysis ;or when the mixture is reduced by alcohol. I n the latter case, how-ever, the mother-liquors, if exposed to the air after the hydrofluoroxy-vanadate has been deposited, yield yellow, octahedral crystals of t h ecomposition V02F,YNH4F. These can be obtained more easily bMINERALOGCICAL CHEMISTRY. 215dissolring vanadic acid in excess of hydrofluoric acid, and carefullyneutralising w i t h ammonia while the liquid is still warm. On cooling,an abundant deposit of the crystals is obtained ; care must be takennot to add any great excess of ammonia, otherwise colourless crystalsof ammonium vanadate alone will separate.By adding potassium hydrogen fluoride to a solution of ammoniummetavanndate reduced by sulphurous anhydride, and evaporating theblue solution, the author obtained sky-blue, crystalline crusts, of thecomposition VOF2,2KC1.The remainder of the paper is devoted to theoretical considerationof the crystallographic connection of various isomorphous fluorides,the author drawing especial attention to the fact that the four com-pounds V0,F,3NH4F’, VOF,,SNH,F, FeF,,3NH4F, and CrF3,3NH4F,all crpstallise in the monometric system in cubes or octahedra, and allcontain the same number of atoms. C. E. G

ISSN:0368-1769    

DOI:10.1039/CA8895600207

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

MINERALOGCICAL CHEMISTRY. 215 Mine r a l o g i c a 1 C h em i s t ry. A Remarkable Bed of Sulphur. By PREUSSNER (Chem. Centr., 1888, 1339-1340, from Zeit. deut. geol. Gess., 40, 184--187).-1n 1869, when oil was being bored for, an unusually large bed of sulphur was found in Louisiana, onz mile from t h e South Pacific Coast, eight miles from Calcasieu River. Siuce 1886 four borings have been made, all close together, arid with very similar results. The following structure was met with during the first of these : - Thickness of bed. Depth. feet. feet. Yellow and blue clay.. .............. 160 160 Grey and yellow sand ............... 173 233 Blue sandy limestone.. .............. 48 383 Pure sulphur ...................... 108 551 Sulphur accompanying gypsum. ...... 99 650 Pure sulphur ......................6 656 Sulphur accompanying gypsum ...... 24 680 Gypsum rich i n sulphur. ............ 440 11 30 Sulphur accompanying gypsum ...... 100 1230 Rock ............................. 2 235 White soft limestone. ............... 60 443 J. W. L. Arsenopyrite from Servia. By J. LOCZKA (Zeit. Kryst. Min., 15, 40-41).-The crystals analysed by the author had the following percentage composition :- s. Sb. AS. Fe. Zn. Insoluble. Total. 21.72 0.14 42-33 34.58 0.46 0.22 99 49 9 2216 ABSTRACTS OF CHEMICAL PAPERS. The insoluble residue consists of silica with a trace of calcium. The sp. gr. of the mineral is 6.0394. Constitution of Arsenopyrite. By J. LOCZKA (Zeit. Rryst. Min,., 15, 41--42).--When heated without access of air, arsenopyrite loses much of its arsenic, the loss amounting to 4055 per cent.The author has made a series of experiments to ascertain the chemical changes that take place when arsenopyrite is heated, and concludes that in this mineral an iron sulphide must be present, which loses when heated a portion of its sulphur. The latter then renders the arsenic free by combining as iron sulphide with the iron that was present in combination with arsenic. As analysis shows the composition of arsenopyrite to correspond with the ratio 1Pe : 2S,lFe : AS, it must be supposed that this iron sulphide is FeS2, and consequently that arsenopyrite consists of FeAs2 and FeS2. The decomposition brought about by the action of heat may be illustrated by the following equations:-(l.) FeAs, + FeS2 = FeS + S + FeAs2. (2.) FeAsz +.S = FeS + 2As. B. H. B. (3.) FeAs, + FeS, = 2FeS + 2As. B. H. B. Periclase from Nordmarken. By A. SJOGREN (Zeit. K ~ y s t . M i n ., 15, 106, from Geol. Form. Forh., 9, 527).-Periclase occurs with haiismannite in large and small grains in a bed of limestone in a manganese mine in Nordmarken. The mineral is colourless and transparent, but is usually coloured green by admixed minerals. Analysis gave the following results :- MgO. MnO. ZnO. FeO. Total. 87-38 9.00 2.52 0.19 99-09 B. H. B. Psilomelane. By G. LANGHAUS (Jnhrb. f. Niin., i, Ref., 16-17).- The author has analysed three varieties of psilomelane with the fol- lowing results :- BaO. CaO. MgO. K20. Na20. H20. A1203. Fe,O,. I. 0.61 1.18 0.52 2.59 0.18 3-06 1.16 0.37 111. 6-43 1.33 0.21 1-89 0.69 3.10 1-10 0.50 XnO.0. SiO,. Insoluble. 74.!,7 15-06 O.:% 0.21 69.76 13.93 2.72 024 67.29 12.19 3-12 2.47 11. Ci.')O 0.52 0.66 2.17 0.76 3.90 0.87 ci.49 Traces of COO, NiO, CuO. PbO were also observed in each ease, and of Li20 in 11 and 111. The varieties analysed were obtained (I) from the Volle Rose mine, Mittelberg, in the Duchy of Gotha, (11) from the Heinrichsgliiuk mine, Rumpelsberg, Gotha, and (111) from Eisenbach, near Neustadt, in the Black Forest. Qualitative analyses of psilomelane from other mines in the Duchy of Gotlia led t o similar results. The author calculates the formula of psilomelane to be HJVIXlO6. B. H. B.MIXERALOQICAL CHEMISTRY. 21 7 Analyses of Monazite an.d Xenotime. By C. W. BLOMYTRAND ( Z e d . Kryst. Min., 15, 99-103, from Geol.Foren. B’orh., 9, 160).- The author gives the results of the analyses of nine specimens of monazite from Norway. The localities from which the specimens were derived were MOSS, Dillingso, Liinneby, Arendal, Naresto, and Hvalo. The analyses show that monazites are normal salts of tribasic phosphoric acid. There is, however, an excess of bases, which appear to be in combination with silica. The general formula of these minerals is therefore rn(3R0,P205) + 2R0,SiOz + pH,O, in which rn is between 5 and 80, and p usually less than 1. The author’s conclusion is that monazites are normal cerium and thorium phosphates, in which a portion of the phosphoric acid is replaced by silica. This view is not in accord with that of Penfield, who regards monazites as cerium phosphates with mechanically admixed thorite.In an appendix, the author gives two auxlyses of xenotime from Hvalo and Naresto, and concludes that the composition of this mineral is similar to that of monazite. B. El. B. Sulphohalite, a New Sodium Sulphato-chloride. By W. E. HIDDEN and J. B. MACKINTOSH ( A m e r . J . Sci., 36, 463--464).--This mirieral belongs to the regular system, and occurs in rhombic dodeca- hedra. Its sp. gr. is 2.489, and its hardness 3.5. Analysis yielded the followiiig results :- 13-12 42.48 1-77 It is transparent, with a faint yellow colour. c1. so,. Ntt2C03. The formula is 3Na$3O4,2NaCl. Excepting the very rare Cornish mineral connellite, no other species is known of analogous com- position. The mineral was found with hanksite at Borax Lake, San Bernardino Go., California. Only three examples are known, arid two of these are in the collection of C.S. Bement, of Philw- delphia. The authors propose for this new mineral the name of sulphohalite as indicating its remarkable composition. B. El. B. Allactite from Lhgban. By A. SJOGREN (Zeit. Kryst. Min., 15, 106-1 07, from fifvers. Vet. Akad. Forh., 1887, 107).-This mineral occurs, with a manganiferons barytes, calcite, and a mineral resembling aphrodite, at the Collegii mine at LHngban. It resembles the allactite found at Nordmarken. On analysis, it gave the following results :- A S , ~ ~ . MnO. CaO. MgO. H20. Total. 29.00 58.87 1.77 1.35 9.00 99.99 B. H. B. Pyrrhoarsenite and Berzeliite. By A. G. H~GBOM (Zeit. RrY5t. Jfin., 15, 105-106, from Geol.Foren. Forh., 9,397) .-Two specimens of pyrrhonrsenite were analysed ; one being the usual orange variety (l), and the other a purer yellow, transparent variety (11) having a sp. gr. of 4 01. The Both contained admixed barjtes and calcite.218 ABSTRAUTS OF CEEMICAL PAPERS. berzeliite (111) examined was a honey-yellow isotropic variety from Llngban. C 0 2 . BaSO,. FeO. MnO. CaO. MgO. As205. Sb20,. Total. I. 1-27 3.96 trace 19.18 18.35 3.50 50.92 2.60 99.78 11. 1.58 1.36 - 14.12 18.54 7.53 53.39 2.90 99.42 111. - 0.49 - 5-68 19.97 16.12 57-59 - 99-85 B. H. B. Pyrrhoarsenite and other Swedish Antimoniates. By L. J. IGELsTRobf (Jahrb. f. k f i t b . , 1888, i, Mem., 48-53).-The bright straw- yellow anhydrous arsenate from the Sjo mine, in the parish of Grtbyttnn, Orebro, Sweden, is undoubtedly pyrrhosrsenite, but with double the amount of antimonic acid contained in the jellow variety (Analysis 11) discovered by Hogbom in 1885.The analysis gave the following results (I) :- AS~~,. Sb206. CaO. MnO. MgO. Total. I. 53-83 6.54 20.21 10.82 9.20 100.00 11. 56-40 3-07 17-50 15.03 8-00 100.00 The author considers the formuls of the antimoniates and Pyrrhoarsenite (type I, analysed by Hogbom), ZO( Ca,Mg,Mn)3As,08 Pyrrhoarsenite (type 11, analysed by the author), lO(Ca,Mg,Mn),As,O, Polyarsenite (Abstr., 1887, 347), 40H,Mn4Asz010 + (Cs,Mg),Sb,07. Xamthoarsenite (Abstr., 1886, 25), 1G(Mn,Mg,Fe,Ca,H2)l&sLO16 + Manganostibiite, 2(Mn,Fe,Ca,Mg),AsZO8 + 5 ( Mn,Fe,Mg)loSb,Olo. Hmmatostibiite, Mg2Sb207 + 5(Mn,Fe),oSb201,. Atopite, ( Ca,Naz,Fe,Mn,Kz)2Sb,07.Monimolite, type I (Nordenskiold), Pb3Sbz08 ; type I (Igelstrom), (Compare Abstr., 1888, 565.) antimonio-arsenates hitherto found in Sweden to be as follows :- + CalSbz07. + CnzSb207. ( Ca,Mg)zSb207. ( Pb,Fe,Ca,Mg)4Sb2O9 ; type I1 (Flink) (Pb,Fe,MnjsS b20R. B. H. B. Thioantimonites from Colorado. By L. G. EAKINS (Amer. J. Sci., 36, 450-453).-The author gives the results of the analyses of two thioantimonites €rom Gunnison Co., Colorado. The first (Analysis I) was found in the Doming0 mine, on the ridge between Dark Cafion and Baxter Basin. It consists of aggregates of small, acicular crystals, forming wool-like masses in the cavities of a highly decomposed siliceous gangue. It is dull, greyish-black in colour, and no crystalline form could be distinguisbed.Its formula is 3(Pb,Fe)S,2Sb2S3. The second specimen was found at a mine on Augusta Mountain. It occurs in a siliceous gangue with iron pyrites and zinc blende, and forms groups of acicular crystals, which are deeply striated, elongated prisms. Its formula is 5PbS,2Sb2Sa. It thus appears to be n freieslebenite in which the silver has been com- pletely replaced by lead. The analytical results were as follows :-MINERALOQICAL CHEMISTRY. 219 Ag. Cu. Pb. Be. Mn. Sb. S. Insoluble. Total. I. Trace trace 39.33 1.77 trace 36.34 21.19 0.52 99.15 11. Trace - 55.52 trace - 25.99 18.98 - 100.49 B. H. I% Hjelmite. By 11. WEIBULL (Zeit. Kryst. Miu., 15, 104-105, from Geol. Fiirela. Forh., 9, 371).-This mineral crystallises in the rhombic system, the axial ratio being a : b : c = 0.465 : 1 : 1-026.The specimens examined were considerably altered, and were seen under the microscope to consist of an amorphous substance containing black metallic grains of unaltered hjelmite. Analysis gave results corresponding with the formula 4R0,3&-O5 + 2H20. B. H. B. Eudidymite. By A. E. NORDENSKIOLD (Zeit. Kryst. Min., 15, 107-108, from Geol. Foren. For?h., 9, 434).-Eudidymite was dis- covered in 1887 in the Island of Upper Aro in the Langesundsfjord. According to Bragger it is monoclinic, with the axial ratio of a : b : c = 1.71069 : 1 : 1.107113; /? = 86’ 14‘ 2i”. Analysis gave the following results :- 5102. BeO. Na20. H2O. Total. 731 1 10.62 7 2.24 3.79 99.76 B. H. B. Analysis of Natrolite. By G. LINDSTROM (Zeit.R y s t . Min., 15, 108? from Ged. B’orew. Forh., 9, 434).-This analysis was made in order to determine whether the so-called byevicite that accompanies the eiididyrnite of Aro (see preceding Abstract) also contained beryllium. This was, however, not the case. The analytical results were as follows :- Si02. A1203. Na20. K20. H20. Total. 47.92 26.80 16-25 0.26 9-51 100.74 B. H. B. Hyalotekite from Langban. By G. LTNDSTROX (Zeit. Kryst. Min., 15, 96-97, from ofmrs. Sv. Vet. Forh., 1887, 589).--The hyalo- tekite described by Nordenskiold has been analysed bp t h e author with the followiiig results :- EiO,. PbO. BaO. CaO. CuO. MnO. BeO. MgO. K20. Na,O. 39-47 23.11 20.08 7-82 0.09 0.29 0.75 0.09 0.89 0.17 Al2O3 Fe203. B203. F. C1. Ignition. Total. 0.18 O*b6 3.73 0.99 0.06 0.59 100.37 The formula deduced from these results is 12(R0,2Si02) + 3R0,2B,Os + RF B.H. B. Gadolinite. By C. RAMMELSBERCI (Jahrb. f. Mi%., 1889, i, Ref., 25-26, from Sitzb. preuss. Akad. Wiss., 1887, 553).-The author has analysed specimens of gadolinite from Hitter0 (I) and from Ytterby (11) w i t h the following results :-280 ABSTRACTS OF CHEMICAL PAPERS. Loss on Si02. Y203. Ce203. Fe20,. FeO. BeO. CaO. ignition. Total. I. 24-36 45-51 7.01 2-85 11.50 8.58 0.36 0.50 100.67 11. 25-35 38.13 13-55 4.07 7-47 10.03 0.57 1.34 100-51 The pdolinite from Hitter0 occurs in large, black crystals ; sp. gr. 4,448 to 4-490; that from Ytterby has a vitreous or amorphous nature, and brilliant lustre; sp. gr. 4.212. The formula of both varieties is R’r5Rff’2Si1019.Gadolinite thus approaches datolite and euclase in composition. B. H. B. Mineralogical Notes. By A. E. NORDENSKIOLD (Zeit. Rryst. Min., 15, 97-98, from Geol. Foren. Forh., 9, 26).-1. Alvite and Ant?erbergite.-Alvite from Alve, near Arendal, gave on analysis the following results :- Metallic” Be0 with some Bi02. acids. PbO. Fe203. MnO. Ce203. Y203. A1203. 26.10 2-78 0-45 3.51 0.27 3-37 1-03 14.73 Zr02. CaO. MgO. LOSS on ignition. Total. 33.48 2.44 1.05 8.84 98.95 This mineral is absent from the felspai- mines of the pegmatite veins. It is, however, replaced by a somewhat similar mineral, which the author regarded as cyrtolite, but which Blomstrand claims to be a new species to which the name of anderbergite should be given. (See following Abstract.) 2. An analysis of monoclinic crystals of hydrargillite from Lange- sund in Norway, gave the following results :- A1203. Si02.H20. Total. 65-90 0.43 33.57 95-90 3. Diaspore from Horrsjoberg in Werrn1and.-An analysis of this mineral, supposed to be identical witli Igelstrom’s new mineral ‘‘ empholite,” gave, when corrected for admixed cyanite and pyro- phyllite, 84.32 per cent. of alumina and 15.68 per cent. of water. B. H. B. The so-called Cyrtolite of Ytterby. By C . W. BLOMSTRAND (Zeit. Kryst. Min., 15, 83, from Sv. Vet. Akad. Handl., 12, 1-lo).- Four analyses of massive somewhat impure material gave the follow- ing mean results :- Si02. Zr02. Y2OP Ce203. FeO. CaO. MgO. CuO. Na,O. H,O. Total. 26-93 41.17 10.53 trace 1.54 5-85 trace 0.17 0.89 12 55 100.03 The results were obtained after 10.51 per cent.of phosphates, $c., regarded as impurities, had been subtracted. The formula js R3Y2Zr,(SiO~)lz + 18H,O. The analysis agrees so well with that of crystals by Nordenskiold, that the author cannot regard the mineral merely as an altered zircon, but considers it a distinct mineral species, * Metallsaiire.MIr\%RALOGICAL CHEMISTRY. 221 and, as its composition differs considerablv from that of the American cyrtolite, proposes for it the name of Anderbergite. U. H. B. Swedish Minerals. By G. FLINK (Zeit. Kryst. dlilz., 15, 88-92, from Su. Vet. Akad. Handl., 13, 1-94).-1. The author gives the following new analysis of manganese-epidote :- SiO,. Al,O,. Fe20,. CaO. MnO. H20. Total. 36.44 24-65 12.44 19.52 4.52 3.19 100.76 The crystals of this mineral occur with titanite, barytes, and man- ganophyll in fissures filled with calcite, in a matrix consisting of berzeliite, calcite, and manganese-epidote.On the crystals. the author has determined the following new forms : OP, dh, -&m, Pm, - $2m, mP, m92, P, sm. With regard to its composition and most of its optical properties, manganese-epidote forms a link between ordinary epidote and piemontite. 2. hlang;tnopliyll occurs at Lhgban in small copper-coloured scales intimately mixed with magnetite and iron-glance, as well as i n crys- tals with tephroite and magnetite in fissures filled with calcite. The analysis gave the following results :- SiO,. F. MgO. MnO. Fe203. A1?03. K20. NazO. H20. Total. 41-36 0.49 13-67 5.41 4.66 16.02 11.43 2-09 4-62 99.35 Manganophyll is thus shown to differ considerably from all the micas hitherto deficribed.3. The author gives the following analyses of (I) hornblende and (11) grammatite from Nordmarken :- Si02. A1203. Fe,03. FeO. MnO. MgO. CaO. Total. I. 49.81 7-83 8.90 13-89 0.95 4.75 12.89 99.82 11. 55-77 - - 2.95 - 24-73 15-92 99.37 The hornblende seems to contain of 50 per cent. Ca(Fe,Mg,Mn),Si,OI2, 37.5 per cent. Ca(Al,Fe),Si,O,,, and 12.5 per cent. Ca( A1,Fe),SiOs. Of these compounds, the first is the ordinary actinolite-silicate, whilst the two others have not hitherto been identified in the hornblende series. The formula of the grammatite is Ca(Mg,Fe)3Si,01a. B. H. B. Auerlite, a new Thorium Mineral. By W. E. HIDDEN and J. B. MACKIKTOSH (Amer. J. Sci., 36, 461--463).-This mineral has hitherto been found at only two places in Henderson Co., North Carolina, namely, at the Freeman mine, and on the Price land, three miles to the south-west.At both places it occurs in disintegrated psnitic or gneissic rock, intimately associated with zircon crystals, on which i t is often seen implanted. The crystals are tetragonal, lemon- yellow to brown-red in colour, and sub-translucent to opaque. The mineral is very brittle ; its hardness is 2.5 to 3, and its sp. gr. 4.422 to 4.766, the darker crystals having the greatest density. Analysis gave the following results :-222 ABSTRACTS OF CHEMICAL PAPERS. H20. COP SiO:. P20,. Tho2. Fe203. CaO. MgO. Al,O,. Total. 10.21 1.00 7.64 7.46 '70.13 1.38 0.49 0.29 1.10 99.70 The formula is Th0,,Si0,,+P,05,2H20, or that of a thorite in which part of the silica is replaced by phosphoric acid.As this mineral was found while mining the zircons necessar,y to supply the denland caused by the invention of the system of incandescent gas-lighting of Carl Auer v. Welsbach, the authors propose to name it Auerlite in his honour. B. H. B. Phosphatic Deposits at Montay and Forest. By J. LADRI&RE (Compt. rend., 107, 960--961).-At Montay and Forest there is a chalky conglomerate covered by a sandstone containing glauconite. The sandstone is from 0.3 to 1.8 metre thick, and coiitains 15 to 17 per cent. of phosphoric anhydride. The conglomerate is less rich in phosphates. C. H. B. Composition of Piperno of the Collina del Vomero. By G. FREDA (Chenz. C'entr., 1888, 1340, from Rend.R. Inst. Lombard0 [2], 2, 177--180).--The grey porous part (I) of the rock has the same composition as the compact part (11). The composition is almost the same as that of the piperno from Pianura, but very different from the tuff of Campi Flegrei. The analytical results of the piperno of Vomero are as follows :- S102. Al,03. Fe203. CaO. MgO. K20. Na20. C1. I. 62.51 18.44 3.88 0.83 0.47 4.98 7.17 0.62 11. 61.65 19-06 4-14 1.28 0 62 3-31 6.72 - J. W. L. Metamorphic and Plutonic Rocks at Omeo. By A. W. HOWITT (Jahrb. f. Min., 1889, i, Ref., 122-125, from Trans. R. S. Victoria) .-About a wile from the northern end of the Hinnomugie Marsh there is a small tributary of Livingstone Creek in which the contact of muscovite granite and a greyish, fine-grained mica-schist is visible.The latter is seen under the microscope to consist of musco- vite, brown mica, and tourmaline, or, in other places, of these mineids and quartz. 'l'he granite contained yellow microperthite (Analysis I), tmd silver-white mica (Analysis 11). Several miles to the soutli-east of this locality, at Wilson's Creek, a series of rocks consisting of mica-schists and gneisses have been collected. They are traversed by eruptive rocks, and at the contact have been subject to various changes. An analysis (111) is given of it finely granular mica-schist, which under the microscope is seen to consist of colourless mica, yellowish magnesia-mica, a little quartz in grains, and graphite. In the author's opinion, this and similar rocks are metamorphosed Lower Silurian sedimentary rocks.An analysis (IV) is also given of a graphic granite, consisting of microcline, quartz, secondary muscovite, and albite.MIXERALOGICAL CHEMISTRY. 223 Fe. SiOz. A1,03. Fe,O,. FeO. CaO. MgO. Na,O. Ego. I. - 62.13 24.35 trace - - - 6-66 8.31 11. 0.15 44.67 37.44 0.48 0.91 0.26 0.42 1.24 10.90 ITI. - 64.00 19.82 3-50 - 0.32 2.14 1.10 4.41 IV. - 70.91 15.32 trace - 0.58 0.07 2.31 10.07 Hygroscopic HpO. C. PzO,. Total. water. Sp. gr. I. 0.50 - I 101.95 - - 11. 3.76 - - 100.23 2.18 2.768 111. 2.23 3.32 0.10 100.94 0.85 2.651 IV. 0.51 - - 99.77 0.15 2.564 B. H. B. Composition of some Rocks from the Shore at Nice. By C. MONTEMARTINI (Gazxetta, 18, 170-179). -These rocks, which were collected soon after the earthquake of February 23rd, 1887, are 31 in number, and maty be divided into seven groups, of which a minule detailed description is given.1. Azcgite-andesite.-‘l’he 10 specimens of this rock, mostly collected at Capo d’Aglio, near Monaco, are of irregular granular structure, in the brown or grey ground-mass of which it is easy to distinguish crystals of augite and of triclinic felspar ; magnetite is also present. The sp. gr. of the specimens varied from 2-64 to 2.83. The silica varied f o r 54.38 to 55.89 per cent. 8. Andesites which contained both Augite and Horntlende.-Of the 11 specimens examined, 5 came from Capo d’Aglio, and 6 from the neighbourhood of Antibo. Some of these were homogeneous and compact, of greyish-black colour, and sp. gr. 2.65 to 2.70 ; magnetite was present. The results of analysis gave- Loss on Si02.Fe203. A1203. CaO. MgO. Alkalis. ignition. 55.50 7.78 19-57 7.67 2.76 4-30 2.42 The alkali was estimated by difference. The other samples were altered and not homogeneous, and con- tained besides augite and felspar, crystals of hornblende, magnetite, atid apatite. 3. Andesites of Trachytic Appearance.-These were yellowish-white, of granular structure, atid contained basaltic hornblende and a large quaxtity of vitreous, crjstalline grain8 of tricliiiic felspar. The sp. gr. of one specimen was 2.49, and i t contained 2-96 per cent.of water and 55.9 8 of dica. 4. Andesite-conglomerate.-The two specimens of this rock have the appearance of a conglomerate formed from fragments of andesite, the rock is much weathered, but neither by analysis nor by microscopical examination could any cementing material be discovered.5 . BnsLcltic-augite.-This has the same composition as the augite- andesite, but differs from it in not being granular in structure, but ti. Andesite coated with Gypsum.-This has a sp. gr. of 2-32, and corrlpact. contains 5-13 per cent. of water atid 60.04 of silica.22 4 ABSTRACTS OF CHEMICAL PAPERS. 7. Compact-semiopal.-This rock is compact, of light greenis h- brown, with resinoid lustre and concho'iclal tracture, and is nearly as hard as quartz. Its sp. gr. is 2.22, and it contains 2.26 per cent. of water and 91.18 of silica. C. E. 0. Examination of the Rocks of the Vulsinian Volcanoes. By L RICCIARDI (Cazzetta, 18, 268--288).--The author has analysed a large number of rocks from the extinct Vulsinian volcanoes, and gives full details of their composition and of the results of their examination both maci~oscopically and microscopically.From the results obtained now and in former researches, and a comparison of these Vulsinian rocks with those of other volcanic districts, the author considers that most, if not all, of the volcanoes of the Italian peninsula, in very early periods, emitted trachytic and other acid rocks which were succeeded by those of basic character. It would Peem, moreover, that the volcanic rocks of the Alpi-Sila group differ in some respects in chemical composition from those of the insular volcanoes o€ the Pilla group. The different basic lavas of the Alpi- Silla group are almost identical in composition, so that it would seem probable that they have a common origin.The acid rocks of trachytic type of Amiata, Bolsena, and Cimini are almost identical in composi- tion with the trachytes and tufas of Campi Flegrei. C. E. G. Meteorite from Novo-Urei'. By M. EROFEEFF and P. LATSCHI- NOFF (J. Russ. Chem. Xoc., 1888, 20, 185-213).-This meteorite fell on September 10, 18813, near Novo-Urei, Penza, together with two other aerolites, the larger of which fell into water, and the smaller was powdered and devoured by the superstitious moujiks. The fragtnent investigated weighed 1900 grams, and its sp. gr. was found to be 3.463 at 16". On being powdered for analysis, it was found to contain extremely hard particles which scratched the agate mortar and pestle. It does riot yield anything to neutral solvents, such a8 water, alcohol, and ether, but partly dissolves i n hydrochloric acid with liberation of hydrogen and hydrogen sulphide, owing t o the presence of iron and probably of magnetic pyrites.Aqua regia dissolves only 70-75 per cent. ; and even when the insoluble residue is treated with hydrofluoric and sulphuric acids from 2-2.5 per cent. of a blackish-grey powder remains undissolved. It contains graphite and another substance, which is very hard, and mvas found to be capable of being burned i n oxygen. An elementary analysis made in this way gave its cornposition : carbon 89.56 per cent., ash 10.44 per cent. Another portion remaining after fusion with potassium pyro- sulphate gave: carbon 95.40, ash 3.23. In order to test it for diflerent allotropic modifications of carbon, the residue was treated with strong nitric acid and potassium chlorate, but Brodie's graphitic acid was not formed, although 40 per cent.of the residue dissolved after three treatments. The residue was now whiter, and its sp. gr. was found on an average to be 3.1, which, considering the small quantity used, agrees well with that of diamond (sp. gr. 3.5). The powder was found to be harder than corundum, as the last (polished and unpolished faces) is scratched by it very perceptibly.X1INERALOGICAL CHEMISTRY. 225 The meteorite contains the) efore diamond (cnrhonado) together with Some soft carbon. The total quantity of diamond in the meteorite is no less than 1 per cent. = 85.4 carats. Analysis of the meteorite gave- Ni.Fe. FeO. MnO. Alz03. Cr,03. MgO. CaO. S. P. 0.20 5.25 1336 0.43 0.60 0.95 35.80 1.40 0.15 0 02 Si02. C. Soft. (carbonsdo). Total. 39.51 2.26 =(1*26 1-00> 99-92 Hard Assuming that ihe sulphur is present R S magnetic pyrites and adding phosphorus to nickel-iron, the composition is- Ni,Fe. Cr20,. FeiS,. C. Silicates. Total. 5.47 0.95 0.43 2.26 90.76 99-87 It was shown further, that 67.48 per cent. of the meteorite consist Mg,SiO,. Fe2Si04. CazSiO,. MnzSi04. of olivine, of the following percentage composition :- 72.93 24.48 1 89 0.70 Another constituent is augite, to the extent of 23.82 per cent. of the mass of the meteorite. Chromium is present partly in the metallic state, 0.2 per cent. being dissolved in cold hydrochloric acid; partly as chrome-iron ore, 0.65 per cent.A table shows the way in which the different constituents are distributed in the meteorite. The paper contains moreover an account of the microscopic examina- tion of the meteorite, which shows khat the mass contains among other ingredients, small, transparent octahedra, in some of which very small black grains were found. They may consist of diamond, but urrfor- tunately the carbon residue obtained in the analysis of the meteorite, after treatment with Brodie’s solution (see above), consists of almost black particles of an irregular form. With high magnifying power, they appear to be partly transparent and without action on polarised light, but no trace of crystalline form could be detected. In conclu- sion the authors discuss different cases of occurrence of carbon in meteorites.Pantsch and Haidinger (1846) found cubes of graphite in the Arva iron (Hungary), and regard them as pseudomorphs after iron pyrites, but G. Rose has shown, that this mineral is not found in meteorites, and the forms are besides quite different. Rose thought the graphite cubes may be pseudomorphs after diamond, especially as an analogous allotropic change takes place when diamond is strongly heated in absence of air. G. Rose’s prediction is thus confirmed by the results of the present investigation, diamond, however, being found in meteoric stones, whereas it was sought in meteoric irons. Fletcher (see Abstr., 1887,30) has described graphite in cubic forms as a new mineral, cliftonite, found in the Youndegin meteorite, but this is totally different in properties from the modifica- tion of carbon occurring in the Novo-Urei: meteorits.The authors find, after comparison with known classes of aerolites, that the meteorite described above differs from all of them in many points, and propose to name this form wrezlithe. B. B.226 ABSTRACTS OF CHEMICAL PAPERS. Black Rivers in Equatorial Regions. By A. MUNTZ And V. MARCANO (Compt. rend,, 10?,908--90Y).--ln the equatorial regions of South America, there are several rivers the water of which is black. Some of the tributaries of the Orinoco and Amazon show this pecu- liarity. The rocks forming the banks of these rivers remain white, whilst the banks of several ordinary rivers become dark colonred. The black rivers do not impart their colour t o the waters with which they mix.They flow through a granitic district covered with a, luxuriant, tropical vegetation. The water has a fresh agreeable taste, and remains perfectly limpid even after two months. It contains 0.028 gram per litre of black organic matter similar to that formed in peat bogs, and has an acid reaction which increases when the water is concen- trated. It contains no calcium and no nitrates, and the inorganic matter, which consists of silica and oxides of iron, manganese, alumi- nium, and potassium, with traces of ammonia, does not exceed 0.016 gram per litre. The waters retain their colour for a long time, because in the absenca of calcium salts there is no nitrification, and the acid reaction and high degree of aeration prevent putrefaction.C. H. B.MINERALOGCICAL CHEMISTRY. 215Mine r a l o g i c a 1 C h em i s t ry.A Remarkable Bed of Sulphur. By PREUSSNER (Chem. Centr.,1888, 1339-1340, from Zeit. deut. geol. Gess., 40, 184--187).-1n1869, when oil was being bored for, an unusually large bed of sulphurwas found in Louisiana, onz mile from t h e South Pacific Coast, eightmiles from Calcasieu River. Siuce 1886 four borings have beenmade, all close together, arid with very similar results. The followingstructure was met with during the first of these : -Thickness of bed. Depth.feet. feet.Yellow and blue clay.. .............. 160 160Grey and yellow sand ............... 173 233Blue sandy limestone.. .............. 48 383Pure sulphur ...................... 108 551Sulphur accompanying gypsum....... 99 650Pure sulphur ...................... 6 656Sulphur accompanying gypsum ...... 24 680Gypsum rich i n sulphur. ............ 440 11 30Sulphur accompanying gypsum ...... 100 1230Rock ............................. 2 235White soft limestone. ............... 60 443J. W. L.Arsenopyrite from Servia. By J. LOCZKA (Zeit. Kryst. Min., 15,40-41).-The crystals analysed by the author had the followingpercentage composition :-s. Sb. AS. Fe. Zn. Insoluble. Total.21.72 0.14 42-33 34.58 0.46 0.22 99 499 216 ABSTRACTS OF CHEMICAL PAPERS.The insoluble residue consists of silica with a trace of calcium. Thesp. gr. of the mineral is 6.0394.Constitution of Arsenopyrite. By J. LOCZKA (Zeit. Rryst. Min,.,15, 41--42).--When heated without access of air, arsenopyrite losesmuch of its arsenic, the loss amounting to 4055 per cent.Theauthor has made a series of experiments to ascertain the chemicalchanges that take place when arsenopyrite is heated, and concludesthat in this mineral an iron sulphide must be present, which loses whenheated a portion of its sulphur. The latter then renders the arsenicfree by combining as iron sulphide with the iron that was present incombination with arsenic. As analysis shows the composition ofarsenopyrite to correspond with the ratio 1Pe : 2S,lFe : AS, it mustbe supposed that this iron sulphide is FeS2, and consequently thatarsenopyrite consists of FeAs2 and FeS2. The decomposition broughtabout by the action of heat may be illustrated by the followingequations:-(l.) FeAs, + FeS2 = FeS + S + FeAs2.(2.) FeAsz +. S = FeS + 2As.B. H. B.(3.) FeAs, + FeS, = 2FeS + 2As.B. H. B.Periclase from Nordmarken. By A. SJOGREN (Zeit. K ~ y s t . M i n .,15, 106, from Geol. Form. Forh., 9, 527).-Periclase occurs withhaiismannite in large and small grains in a bed of limestone in amanganese mine in Nordmarken. The mineral is colourless andtransparent, but is usually coloured green by admixed minerals.Analysis gave the following results :-MgO. MnO. ZnO. FeO. Total.87-38 9.00 2.52 0.19 99-09B. H. B.Psilomelane. By G. LANGHAUS (Jnhrb. f. Niin., i, Ref., 16-17).-The author has analysed three varieties of psilomelane with the fol-lowing results :-BaO. CaO. MgO. K20. Na20.H20. A1203. Fe,O,.I. 0.61 1.18 0.52 2.59 0.18 3-06 1.16 0.37111. 6-43 1.33 0.21 1-89 0.69 3.10 1-10 0.50XnO. 0. SiO,. Insoluble.74.!,7 15-06 O.:% 0.2169.76 13.93 2.72 02467.29 12.19 3-12 2.4711. Ci.')O 0.52 0.66 2.17 0.76 3.90 0.87 ci.49Traces of COO, NiO, CuO. PbO were also observed in each ease,and of Li20 in 11 and 111. The varieties analysed were obtained (I)from the Volle Rose mine, Mittelberg, in the Duchy of Gotha, (11)from the Heinrichsgliiuk mine, Rumpelsberg, Gotha, and (111) fromEisenbach, near Neustadt, in the Black Forest. Qualitative analysesof psilomelane from other mines in the Duchy of Gotlia led t o similarresults. The author calculates the formula of psilomelane to beHJVIXlO6. B. H. BMIXERALOQICAL CHEMISTRY. 21 7Analyses of Monazite an.d Xenotime.By C. W. BLOMYTRAND( Z e d . Kryst. Min., 15, 99-103, from Geol. Foren. B’orh., 9, 160).-The author gives the results of the analyses of nine specimens ofmonazite from Norway. The localities from which the specimenswere derived were MOSS, Dillingso, Liinneby, Arendal, Naresto, andHvalo. The analyses show that monazites are normal salts of tribasicphosphoric acid. There is, however, an excess of bases, which appearto be in combination with silica. The general formula of theseminerals is therefore rn(3R0,P205) + 2R0,SiOz + pH,O, in whichrn is between 5 and 80, and p usually less than 1. The author’sconclusion is that monazites are normal cerium and thoriumphosphates, in which a portion of the phosphoric acid is replaced bysilica.This view is not in accord with that of Penfield, who regardsmonazites as cerium phosphates with mechanically admixed thorite.In an appendix, the author gives two auxlyses of xenotime fromHvalo and Naresto, and concludes that the composition of thismineral is similar to that of monazite. B. El. B.Sulphohalite, a New Sodium Sulphato-chloride. By W. E.HIDDEN and J. B. MACKINTOSH ( A m e r . J . Sci., 36, 463--464).--Thismirieral belongs to the regular system, and occurs in rhombic dodeca-hedra. Its sp. gr. is2.489, and its hardness 3.5. Analysis yielded the followiiigresults :-13-12 42.48 1-77It is transparent, with a faint yellow colour.c1. so,. Ntt2C03.The formula is 3Na$3O4,2NaCl. Excepting the very rare Cornishmineral connellite, no other species is known of analogous com-position.The mineral was found with hanksite at Borax Lake,San Bernardino Go., California. Only three examples are known,arid two of these are in the collection of C. S. Bement, of Philw-delphia. The authors propose for this new mineral the name ofsulphohalite as indicating its remarkable composition.B. El. B.Allactite from Lhgban. By A. SJOGREN (Zeit. Kryst. Min., 15,106-1 07, from fifvers. Vet. Akad. Forh., 1887, 107).-This mineraloccurs, with a manganiferons barytes, calcite, and a mineral resemblingaphrodite, at the Collegii mine at LHngban. It resembles theallactite found at Nordmarken. On analysis, it gave the followingresults :-A S , ~ ~ . MnO. CaO. MgO. H20.Total.29.00 58.87 1.77 1.35 9.00 99.99B. H. B.Pyrrhoarsenite and Berzeliite. By A. G. H~GBOM (Zeit. RrY5t.Jfin., 15, 105-106, from Geol. Foren. Forh., 9,397) .-Two specimensof pyrrhonrsenite were analysed ; one being the usual orange variety(l), and the other a purer yellow, transparent variety (11) having asp. gr. of 4 01. The Both contained admixed barjtes and calcite218 ABSTRAUTS OF CEEMICAL PAPERS.berzeliite (111) examined was a honey-yellow isotropic variety fromLlngban.C 0 2 . BaSO,. FeO. MnO. CaO. MgO. As205. Sb20,. Total.I. 1-27 3.96 trace 19.18 18.35 3.50 50.92 2.60 99.7811. 1.58 1.36 - 14.12 18.54 7.53 53.39 2.90 99.42111. - 0.49 - 5-68 19.97 16.12 57-59 - 99-85B. H. B.Pyrrhoarsenite and other Swedish Antimoniates. By L.J.IGELsTRobf (Jahrb. f. k f i t b . , 1888, i, Mem., 48-53).-The bright straw-yellow anhydrous arsenate from the Sjo mine, in the parish ofGrtbyttnn, Orebro, Sweden, is undoubtedly pyrrhosrsenite, but withdouble the amount of antimonic acid contained in the jellow variety(Analysis 11) discovered by Hogbom in 1885. The analysis gave thefollowing results (I) :-AS~~,. Sb206. CaO. MnO. MgO. Total.I. 53-83 6.54 20.21 10.82 9.20 100.0011. 56-40 3-07 17-50 15.03 8-00 100.00The author considers the formuls of the antimoniates andPyrrhoarsenite (type I, analysed by Hogbom), ZO( Ca,Mg,Mn)3As,08Pyrrhoarsenite (type 11, analysed by the author), lO(Ca,Mg,Mn),As,O,Polyarsenite (Abstr., 1887, 347), 40H,Mn4Asz010 + (Cs,Mg),Sb,07.Xamthoarsenite (Abstr., 1886, 25), 1G(Mn,Mg,Fe,Ca,H2)l&sLO16 +Manganostibiite, 2(Mn,Fe,Ca,Mg),AsZO8 + 5 ( Mn,Fe,Mg)loSb,Olo.Hmmatostibiite, Mg2Sb207 + 5(Mn,Fe),oSb201,.Atopite, ( Ca,Naz,Fe,Mn,Kz)2Sb,07.Monimolite, type I (Nordenskiold), Pb3Sbz08 ; type I (Igelstrom),(Compare Abstr., 1888, 565.)antimonio-arsenates hitherto found in Sweden to be as follows :-+ CalSbz07.+ CnzSb207.( Ca,Mg)zSb207.( Pb,Fe,Ca,Mg)4Sb2O9 ; type I1 (Flink) (Pb,Fe,MnjsS b20R.B.H. B.Thioantimonites from Colorado. By L. G. EAKINS (Amer. J.Sci., 36, 450-453).-The author gives the results of the analysesof two thioantimonites €rom Gunnison Co., Colorado. The first(Analysis I) was found in the Doming0 mine, on the ridge betweenDark Cafion and Baxter Basin. It consists of aggregates of small,acicular crystals, forming wool-like masses in the cavities of a highlydecomposed siliceous gangue.It is dull, greyish-black in colour, andno crystalline form could be distinguisbed. Its formula is3(Pb,Fe)S,2Sb2S3. The second specimen was found at a mine onAugusta Mountain. It occurs in a siliceous gangue with iron pyritesand zinc blende, and forms groups of acicular crystals, which aredeeply striated, elongated prisms. Its formula is 5PbS,2Sb2Sa. Itthus appears to be n freieslebenite in which the silver has been com-pletely replaced by lead. The analytical results were as follows :MINERALOQICAL CHEMISTRY. 219Ag. Cu. Pb. Be. Mn. Sb. S. Insoluble. Total.I. Trace trace 39.33 1.77 trace 36.34 21.19 0.52 99.1511. Trace - 55.52 trace - 25.99 18.98 - 100.49B.H. I%Hjelmite. By 11. WEIBULL (Zeit. Kryst. Miu., 15, 104-105,from Geol. Fiirela. Forh., 9, 371).-This mineral crystallises in therhombic system, the axial ratio being a : b : c = 0.465 : 1 : 1-026.The specimens examined were considerably altered, and were seenunder the microscope to consist of an amorphous substance containingblack metallic grains of unaltered hjelmite. Analysis gave resultscorresponding with the formula 4R0,3&-O5 + 2H20.B. H. B.Eudidymite. By A. E. NORDENSKIOLD (Zeit. Kryst. Min., 15,107-108, from Geol. Foren. For?h., 9, 434).-Eudidymite was dis-covered in 1887 in the Island of Upper Aro in the Langesundsfjord.According to Bragger it is monoclinic, with the axial ratio of a : b : c= 1.71069 : 1 : 1.107113; /? = 86’ 14‘ 2i”.Analysis gave thefollowing results :-5102. BeO. Na20. H2O. Total.731 1 10.62 7 2.24 3.79 99.76B. H. B.Analysis of Natrolite. By G. LINDSTROM (Zeit. R y s t . Min., 15,108? from Ged. B’orew. Forh., 9, 434).-This analysis was made inorder to determine whether the so-called byevicite that accompaniesthe eiididyrnite of Aro (see preceding Abstract) also containedberyllium. This was, however, not the case. The analytical resultswere as follows :-Si02. A1203. Na20. K20. H20. Total.47.92 26.80 16-25 0.26 9-51 100.74B. H. B.Hyalotekite from Langban. By G. LTNDSTROX (Zeit. Kryst.Min., 15, 96-97, from ofmrs. Sv. Vet. Forh., 1887, 589).--The hyalo-tekite described by Nordenskiold has been analysed bp t h e authorwith the followiiig results :-EiO,.PbO. BaO. CaO. CuO. MnO. BeO. MgO. K20. Na,O.39-47 23.11 20.08 7-82 0.09 0.29 0.75 0.09 0.89 0.17Al2O3 Fe203. B203. F. C1. Ignition. Total.0.18 O*b6 3.73 0.99 0.06 0.59 100.37The formula deduced from these results is 12(R0,2Si02) +3R0,2B,Os + RF B. H. B.Gadolinite. By C. RAMMELSBERCI (Jahrb. f. Mi%., 1889, i, Ref.,25-26, from Sitzb. preuss. Akad. Wiss., 1887, 553).-The author hasanalysed specimens of gadolinite from Hitter0 (I) and from Ytterby(11) w i t h the following results :280 ABSTRACTS OF CHEMICAL PAPERS.Loss onSi02. Y203. Ce203. Fe20,. FeO. BeO. CaO. ignition. Total.I. 24-36 45-51 7.01 2-85 11.50 8.58 0.36 0.50 100.6711. 25-35 38.13 13-55 4.07 7-47 10.03 0.57 1.34 100-51The pdolinite from Hitter0 occurs in large, black crystals ; sp.gr.4,448 to 4-490; that from Ytterby has a vitreous or amorphousnature, and brilliant lustre; sp. gr. 4.212. The formula of bothvarieties is R’r5Rff’2Si1019. Gadolinite thus approaches datolite andeuclase in composition. B. H. B.Mineralogical Notes. By A. E. NORDENSKIOLD (Zeit. Rryst.Min., 15, 97-98, from Geol. Foren. Forh., 9, 26).-1. Alvite andAnt?erbergite.-Alvite from Alve, near Arendal, gave on analysis thefollowing results :-Metallic” Be0 with someBi02. acids. PbO. Fe203. MnO. Ce203. Y203. A1203.26.10 2-78 0-45 3.51 0.27 3-37 1-03 14.73Zr02. CaO. MgO. LOSS on ignition. Total.33.48 2.44 1.05 8.84 98.95This mineral is absent from the felspai- mines of the pegmatiteveins.It is, however, replaced by a somewhat similar mineral, whichthe author regarded as cyrtolite, but which Blomstrand claims to bea new species to which the name of anderbergite should be given.(See following Abstract.)2. An analysis of monoclinic crystals of hydrargillite from Lange-sund in Norway, gave the following results :-A1203. Si02. H20. Total.65-90 0.43 33.57 95-903. Diaspore from Horrsjoberg in Werrn1and.-An analysis of thismineral, supposed to be identical witli Igelstrom’s new mineral‘‘ empholite,” gave, when corrected for admixed cyanite and pyro-phyllite, 84.32 per cent. of alumina and 15.68 per cent. of water.B. H. B.The so-called Cyrtolite of Ytterby. By C . W. BLOMSTRAND(Zeit. Kryst. Min., 15, 83, from Sv. Vet. Akad. Handl., 12, 1-lo).-Four analyses of massive somewhat impure material gave the follow-ing mean results :-Si02.Zr02. Y2OP Ce203. FeO. CaO. MgO. CuO. Na,O. H,O. Total.26-93 41.17 10.53 trace 1.54 5-85 trace 0.17 0.89 12 55 100.03The results were obtained after 10.51 per cent. of phosphates, $c.,regarded as impurities, had been subtracted. The formula jsR3Y2Zr,(SiO~)lz + 18H,O. The analysis agrees so well with that ofcrystals by Nordenskiold, that the author cannot regard the mineralmerely as an altered zircon, but considers it a distinct mineral species,* MetallsaiireMIr\%RALOGICAL CHEMISTRY. 221and, as its composition differs considerablv from that of the Americancyrtolite, proposes for it the name of Anderbergite. U. H. B.Swedish Minerals.By G. FLINK (Zeit. Kryst. dlilz., 15, 88-92,from Su. Vet. Akad. Handl., 13, 1-94).-1. The author gives thefollowing new analysis of manganese-epidote :-SiO,. Al,O,. Fe20,. CaO. MnO. H20. Total.36.44 24-65 12.44 19.52 4.52 3.19 100.76The crystals of this mineral occur with titanite, barytes, and man-ganophyll in fissures filled with calcite, in a matrix consisting ofberzeliite, calcite, and manganese-epidote. On the crystals. theauthor has determined the following new forms : OP, dh, -&m,Pm, - $2m, mP, m92, P, sm. With regard to its composition andmost of its optical properties, manganese-epidote forms a link betweenordinary epidote and piemontite.2. hlang;tnopliyll occurs at Lhgban in small copper-coloured scalesintimately mixed with magnetite and iron-glance, as well as i n crys-tals with tephroite and magnetite in fissures filled with calcite.Theanalysis gave the following results :-SiO,. F. MgO. MnO. Fe203. A1?03. K20. NazO. H20. Total.41-36 0.49 13-67 5.41 4.66 16.02 11.43 2-09 4-62 99.35Manganophyll is thus shown to differ considerably from all the micashitherto deficribed.3. The author gives the following analyses of (I) hornblende and(11) grammatite from Nordmarken :-Si02. A1203. Fe,03. FeO. MnO. MgO. CaO. Total.I. 49.81 7-83 8.90 13-89 0.95 4.75 12.89 99.8211. 55-77 - - 2.95 - 24-73 15-92 99.37The hornblende seems to contain of 50 per cent. Ca(Fe,Mg,Mn),Si,OI2,37.5 per cent. Ca(Al,Fe),Si,O,,, and 12.5 per cent. Ca( A1,Fe),SiOs. Ofthese compounds, the first is the ordinary actinolite-silicate, whilstthe two others have not hitherto been identified in the hornblendeseries.The formula of the grammatite is Ca(Mg,Fe)3Si,01a.B. H. B.Auerlite, a new Thorium Mineral. By W. E. HIDDEN and J.B. MACKIKTOSH (Amer. J. Sci., 36, 461--463).-This mineral hashitherto been found at only two places in Henderson Co., NorthCarolina, namely, at the Freeman mine, and on the Price land, threemiles to the south-west. At both places it occurs in disintegratedpsnitic or gneissic rock, intimately associated with zircon crystals, onwhich i t is often seen implanted. The crystals are tetragonal, lemon-yellow to brown-red in colour, and sub-translucent to opaque. Themineral is very brittle ; its hardness is 2.5 to 3, and its sp.gr. 4.422to 4.766, the darker crystals having the greatest density. Analysisgave the following results :222 ABSTRACTS OF CHEMICAL PAPERS.H20. COP SiO:. P20,. Tho2. Fe203. CaO. MgO. Al,O,. Total.10.21 1.00 7.64 7.46 '70.13 1.38 0.49 0.29 1.10 99.70The formula is Th0,,Si0,,+P,05,2H20, or that of a thorite in whichpart of the silica is replaced by phosphoric acid. As this mineralwas found while mining the zircons necessar,y to supply the denlandcaused by the invention of the system of incandescent gas-lighting ofCarl Auer v. Welsbach, the authors propose to name it Auerlite in hishonour. B. H. B.Phosphatic Deposits at Montay and Forest. By J. LADRI&RE(Compt. rend., 107, 960--961).-At Montay and Forest there is achalky conglomerate covered by a sandstone containing glauconite.The sandstone is from 0.3 to 1.8 metre thick, and coiitains 15 to 17per cent.of phosphoric anhydride. The conglomerate is less rich inphosphates. C. H. B.Composition of Piperno of the Collina del Vomero. By G.FREDA (Chenz. C'entr., 1888, 1340, from Rend. R. Inst. Lombard0 [2],2, 177--180).--The grey porous part (I) of the rock has the samecomposition as the compact part (11). The composition is almostthe same as that of the piperno from Pianura, but very different fromthe tuff of Campi Flegrei. The analytical results of the piperno ofVomero are as follows :-S102. Al,03. Fe203. CaO. MgO. K20. Na20. C1.I. 62.51 18.44 3.88 0.83 0.47 4.98 7.17 0.6211. 61.65 19-06 4-14 1.28 0 62 3-31 6.72 -J.W. L.Metamorphic and Plutonic Rocks at Omeo. By A. W.HOWITT (Jahrb. f. Min., 1889, i, Ref., 122-125, from Trans. R. S.Victoria) .-About a wile from the northern end of the HinnomugieMarsh there is a small tributary of Livingstone Creek in which thecontact of muscovite granite and a greyish, fine-grained mica-schist isvisible. The latter is seen under the microscope to consist of musco-vite, brown mica, and tourmaline, or, in other places, of these mineidsand quartz. 'l'he granite contained yellow microperthite (Analysis I),tmd silver-white mica (Analysis 11).Several miles to the soutli-east of this locality, at Wilson's Creek,a series of rocks consisting of mica-schists and gneisses have beencollected. They are traversed by eruptive rocks, and at the contacthave been subject to various changes.An analysis (111) is given of itfinely granular mica-schist, which under the microscope is seen toconsist of colourless mica, yellowish magnesia-mica, a little quartz ingrains, and graphite. In the author's opinion, this and similar rocksare metamorphosed Lower Silurian sedimentary rocks. An analysis(IV) is also given of a graphic granite, consisting of microcline,quartz, secondary muscovite, and albiteMIXERALOGICAL CHEMISTRY. 223Fe. SiOz. A1,03. Fe,O,. FeO. CaO. MgO. Na,O. Ego.I. - 62.13 24.35 trace - - - 6-66 8.3111. 0.15 44.67 37.44 0.48 0.91 0.26 0.42 1.24 10.90ITI. - 64.00 19.82 3-50 - 0.32 2.14 1.10 4.41IV. - 70.91 15.32 trace - 0.58 0.07 2.31 10.07HygroscopicHpO. C.PzO,. Total. water. Sp. gr.I. 0.50 - I 101.95 - -11. 3.76 - - 100.23 2.18 2.768111. 2.23 3.32 0.10 100.94 0.85 2.651IV. 0.51 - - 99.77 0.15 2.564B. H. B.Composition of some Rocks from the Shore at Nice. By C.MONTEMARTINI (Gazxetta, 18, 170-179). -These rocks, which werecollected soon after the earthquake of February 23rd, 1887, are 31in number, and maty be divided into seven groups, of which a minuledetailed description is given.1. Azcgite-andesite.-‘l’he 10 specimens of this rock, mostly collectedat Capo d’Aglio, near Monaco, are of irregular granular structure, inthe brown or grey ground-mass of which it is easy to distinguishcrystals of augite and of triclinic felspar ; magnetite is also present.The sp. gr. of the specimens varied from 2-64 to 2.83.The silicavaried f o r 54.38 to 55.89 per cent.8. Andesites which contained both Augite and Horntlende.-Of the11 specimens examined, 5 came from Capo d’Aglio, and 6 from theneighbourhood of Antibo. Some of these were homogeneous andcompact, of greyish-black colour, and sp. gr. 2.65 to 2.70 ; magnetitewas present. The results of analysis gave-Loss onSi02. Fe203. A1203. CaO. MgO. Alkalis. ignition.55.50 7.78 19-57 7.67 2.76 4-30 2.42The alkali was estimated by difference.The other samples were altered and not homogeneous, and con-tained besides augite and felspar, crystals of hornblende, magnetite,atid apatite.3. Andesites of Trachytic Appearance.-These were yellowish-white,of granular structure, atid contained basaltic hornblende and a largequaxtity of vitreous, crjstalline grain8 of tricliiiic felspar.The sp. gr.of one specimen was 2.49, and i t contained 2-96 per cent.of water and55.9 8 of dica.4. Andesite-conglomerate.-The two specimens of this rock have theappearance of a conglomerate formed from fragments of andesite, therock is much weathered, but neither by analysis nor by microscopicalexamination could any cementing material be discovered.5 . BnsLcltic-augite.-This has the same composition as the augite-andesite, but differs from it in not being granular in structure, butti. Andesite coated with Gypsum.-This has a sp. gr. of 2-32, andcorrlpact.contains 5-13 per cent. of water atid 60.04 of silica22 4 ABSTRACTS OF CHEMICAL PAPERS.7. Compact-semiopal.-This rock is compact, of light greenis h-brown, with resinoid lustre and concho'iclal tracture, and is nearly ashard as quartz.Its sp. gr. is 2.22, and it contains 2.26 per cent. ofwater and 91.18 of silica. C. E. 0.Examination of the Rocks of the Vulsinian Volcanoes. ByL RICCIARDI (Cazzetta, 18, 268--288).--The author has analysed alarge number of rocks from the extinct Vulsinian volcanoes, andgives full details of their composition and of the results of theirexamination both maci~oscopically and microscopically. From theresults obtained now and in former researches, and a comparison ofthese Vulsinian rocks with those of other volcanic districts, theauthor considers that most, if not all, of the volcanoes of the Italianpeninsula, in very early periods, emitted trachytic and other acidrocks which were succeeded by those of basic character.It wouldPeem, moreover, that the volcanic rocks of the Alpi-Sila group differin some respects in chemical composition from those of the insularvolcanoes o€ the Pilla group. The different basic lavas of the Alpi-Silla group are almost identical in composition, so that it would seemprobable that they have a common origin. The acid rocks of trachytictype of Amiata, Bolsena, and Cimini are almost identical in composi-tion with the trachytes and tufas of Campi Flegrei. C. E. G.Meteorite from Novo-Urei'. By M. EROFEEFF and P. LATSCHI-NOFF (J. Russ. Chem. Xoc., 1888, 20, 185-213).-This meteorite fellon September 10, 18813, near Novo-Urei, Penza, together with twoother aerolites, the larger of which fell into water, and the smallerwas powdered and devoured by the superstitious moujiks.Thefragtnent investigated weighed 1900 grams, and its sp. gr. was foundto be 3.463 at 16". On being powdered for analysis, it was found tocontain extremely hard particles which scratched the agate mortarand pestle. It does riot yield anything to neutral solvents, such a8water, alcohol, and ether, but partly dissolves i n hydrochloric acidwith liberation of hydrogen and hydrogen sulphide, owing t o thepresence of iron and probably of magnetic pyrites. Aqua regiadissolves only 70-75 per cent. ; and even when the insoluble residueis treated with hydrofluoric and sulphuric acids from 2-2.5 per cent.of a blackish-grey powder remains undissolved.It contains graphiteand another substance, which is very hard, and mvas found to becapable of being burned i n oxygen. An elementary analysis made inthis way gave its cornposition : carbon 89.56 per cent., ash 10.44 percent. Another portion remaining after fusion with potassium pyro-sulphate gave: carbon 95.40, ash 3.23. In order to test it fordiflerent allotropic modifications of carbon, the residue was treatedwith strong nitric acid and potassium chlorate, but Brodie's graphiticacid was not formed, although 40 per cent. of the residue dissolvedafter three treatments. The residue was now whiter, and its sp. gr.was found on an average to be 3.1, which, considering the smallquantity used, agrees well with that of diamond (sp.gr. 3.5). Thepowder was found to be harder than corundum, as the last(polished and unpolished faces) is scratched by it very perceptiblyX1INERALOGICAL CHEMISTRY. 225The meteorite contains the) efore diamond (cnrhonado) together withSome soft carbon. The total quantity of diamond in the meteorite isno less than 1 per cent. = 85.4 carats. Analysis of the meteorite gave-Ni. Fe. FeO. MnO. Alz03. Cr,03. MgO. CaO. S. P.0.20 5.25 1336 0.43 0.60 0.95 35.80 1.40 0.15 0 02Si02. C. Soft. (carbonsdo). Total.39.51 2.26 =(1*26 1-00> 99-92HardAssuming that ihe sulphur is present R S magnetic pyrites andadding phosphorus to nickel-iron, the composition is-Ni,Fe. Cr20,. FeiS,. C. Silicates. Total.5.47 0.95 0.43 2.26 90.76 99-87It was shown further, that 67.48 per cent.of the meteorite consistMg,SiO,. Fe2Si04. CazSiO,. MnzSi04.of olivine, of the following percentage composition :-72.93 24.48 1 89 0.70Another constituent is augite, to the extent of 23.82 per cent. ofthe mass of the meteorite. Chromium is present partly in themetallic state, 0.2 per cent. being dissolved in cold hydrochloricacid; partly as chrome-iron ore, 0.65 per cent. A table shows theway in which the different constituents are distributed in the meteorite.The paper contains moreover an account of the microscopic examina-tion of the meteorite, which shows khat the mass contains among otheringredients, small, transparent octahedra, in some of which very smallblack grains were found. They may consist of diamond, but urrfor-tunately the carbon residue obtained in the analysis of the meteorite,after treatment with Brodie’s solution (see above), consists of almostblack particles of an irregular form. With high magnifying power,they appear to be partly transparent and without action on polarisedlight, but no trace of crystalline form could be detected. In conclu-sion the authors discuss different cases of occurrence of carbon inmeteorites. Pantsch and Haidinger (1846) found cubes of graphitein the Arva iron (Hungary), and regard them as pseudomorphsafter iron pyrites, but G. Rose has shown, that this mineral is notfound in meteorites, and the forms are besides quite different. Rosethought the graphite cubes may be pseudomorphs after diamond,especially as an analogous allotropic change takes place whendiamond is strongly heated in absence of air. G. Rose’s prediction isthus confirmed by the results of the present investigation, diamond,however, being found in meteoric stones, whereas it was sought inmeteoric irons. Fletcher (see Abstr., 1887,30) has described graphitein cubic forms as a new mineral, cliftonite, found in the Youndeginmeteorite, but this is totally different in properties from the modifica-tion of carbon occurring in the Novo-Urei: meteorits. The authorsfind, after comparison with known classes of aerolites, that themeteorite described above differs from all of them in many points, andpropose to name this form wrezlithe. B. B226 ABSTRACTS OF CHEMICAL PAPERS.Black Rivers in Equatorial Regions. By A. MUNTZ AndV. MARCANO (Compt. rend,, 10?,908--90Y).--ln the equatorial regionsof South America, there are several rivers the water of which is black.Some of the tributaries of the Orinoco and Amazon show this pecu-liarity. The rocks forming the banks of these rivers remain white,whilst the banks of several ordinary rivers become dark colonred.The black rivers do not impart their colour t o the waters with whichthey mix. They flow through a granitic district covered with a,luxuriant, tropical vegetation. The water has a fresh agreeable taste, andremains perfectly limpid even after two months. It contains 0.028 gramper litre of black organic matter similar to that formed in peat bogs,and has an acid reaction which increases when the water is concen-trated. It contains no calcium and no nitrates, and the inorganicmatter, which consists of silica and oxides of iron, manganese, alumi-nium, and potassium, with traces of ammonia, does not exceed0.016 gram per litre. The waters retain their colour for a long time,because in the absenca of calcium salts there is no nitrification, and theacid reaction and high degree of aeration prevent putrefaction.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8895600215

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

226 ABSTRACTS OF CHEMICAL PAPERS. 0 r g a n i c Chemistry. Mineral Matter in Natural Petroleums. By J. A. LE BEL (Bull. SOC. Chiin. 50 359-361).-Bitumen was extracted from a bituminous limestone from Lobsann in Alsace by means of light petroleum ; the greater part of the light petroleum was then distilled off and the rest treated with amyl alcohol which precipitated a black resin. This was again dissolved in light petroleum precipitated with amyl alcohol and the solid precipitate washed with ether which removed a reddish resin. The asphaltene so obtained contains 5.4 per cent. of ash. The latter contains 13 per cent. of silica 17 per cent. of ferric oxide with traces of manganese and the rest consists chiefly of lime and calcium sulphate. Asphaltene from the natural oil of Colom6a in Galicia contains only traces of mineral matter.N. H. M. Oxidation of the Hydrocarbons C,H2,-,. By G. WAGNER (Bw. 21 3343-3346 ; comp. Abstr. 1888 665).-When diallyl is oxidised with potassium permanganate in dilute aqueous solution i t yields in addition to a trace of an aldehyde a mixture of two hexyl- erythrols C6Hlo( OH)4 which can be separated by fractional crystalli- sation on adding SuccesEive quantities of ether to their solution in absolute alcohol. The less soluble hexylerythrol crystallises in aggregates of colourless lustrous right-angled tables melts at 55.5" and is spwingly soluble in cold alcohol almost insoluble in ether and readily soluble in water ; its taste is slight but sweet and cooling. The more soluble hexylerythrol is very hygroscopic andORUANTC CHEMIS'l'RY.227 more soluble in alcol?ol and ether-aicohol than the preceding com- pounds ; its taste is slight but sweet and cooling. The production of two isomeric. hexylerythrols in this way renders it very probable that diallyl is not a homogeneous compound but consists of two isomerides CH,:CH*CH,-CH,*CH:CH and CHMe:CH*CH:CHMe and additional evidence in favour of this view is to be found in the results obtained by Sabaneeff (Abstr. 1885 495) in brominating and by Sorokin (Abstr. 1878 962 ; 1880 370) in oxidising the hydrocarbon. Neither diallyl dioxide nor its first hydrate could be detected among the oxidation prodncts of diallyl and inasmuch as PEibytek has shown that diallyl dioxide is not completely converted into the correspou ding erytirrol by heating with water a t 100" for 40 hours (Irzairg.Diss. St. Petemburg 1887 33) the author concludes that the he~yler~ythrols are obtained directly by the Oxidation of diallyl without the forma- tion of the corresponding oxides as intermediate products. Hydration of Methylarnylacetylene E thy1 Amy1 Ketone. By A. BI~HAL (BulZ. SOC. Chiin. 50 359).-EthyZ ainyl ketone C,H,,O is obtained when the product of the hydration of methglamyl- acetylene is treated with sodium hydrcgen sulphite and kept for 10 days. The product is then pressed in a calico filter the liquid which runs off consisting of an aqueous and an oily layer separated and the oil washed dried and distilled. It boils a t 164-166" has a penetrat- i n g odour is insoluble in water and does not combine wit,h hydrogen sodium sulphite.Sp. gr. = 0.8502at 0". N. H. M. Preparation of Ethylene Cyanide. By A. FAUCONNIER (Bull. Xoc. Chim. 50 214).-Ethylene bromide (300 grams) and alcohol (500 grams) are boiled in a reflux apparatus and a saturated aqueous solution of potassium cyanide (200 grams) is gradually added. Thereaction is completed in less than two hours when the product is allowed to cool and the liquid decanted and evaporated in a vacuum. The residue is then dissolved in absolute alcohol and the solution dis- tilled first from a water-bath then in a vacuum over a flame. It boils at 147" under 10 mm. pressure and solidifies to a colourless mass some- times crptalliiie and somet'imes amorphous. The yield is 75 to 80 per cent. of the theoretical.Perthiocyanic and Dithiocyanic Acids. By P. KTASON (J. pr. Chern. [ a ] 38 366-337. Compare Abstr. 1887 1025).-The iso- perthiocynnic acid prepared by mixing a solution of ammonium thio- cyanate (1 kilo. in 6.50 c.c.) with hydrochloric acid (1 litre of 35-40 per cent.) contains 10-15 per cent. of dithiocyanic acid even after fractional crystallisation from 60 per cent. acetic acid. The pure acid is best obt,ained by decomposing the barium salt with hjdrochloric acid and recrystallising from a solution in 60 per cent. acetic acid. Isoperthiocyanic acid is very sparingly soluble in water alcohol and ether bat crgstallises from acetic acid in beaut'ful yellow dichroic prisms which are the better formed the freer they are from dithio- cyanic acid ; its constitutional formula according to Glutz is w.P. w. N. H. M.228 ABSTRACTS OF CHEMICAL PAPERS. CS*NH <NH.CS> S. When treated with alkalis it is partially decomposed into dithiocyanic acid and sulphur ; but a recombination takes place between some of the dithiocyanic a,cicl which is converted into the normal acid by the action of tho alkali and the sulphur giving rise tso a salt of normal perthiocyanic acid ; thus the final result of the action of an alkali on isoperthiocyanic acid is a mixture of the alkaline salts of dit hiocyanic acid and normal perthiocyanic acid. Normal perthiocyanic acid is best prepared as follows :-lo0 grams of barium hydroxide 50 grams of crude isoperthiocyanic acid and 300 grams of water are gently warmed together until the sulphur at first separated has mostly redissolved. The mixture is then concen- trated and cooled when the barium perthiocyanate crystallises out and is decolorised and recrystallised.If a fairlv strong solution of this salt is mixed with hydrochloric acid the iso-acid crystallises out ; but if the solution is weak and is cooled to 0" nothing crystallises ; if the cooled solution is shaken with ether the normal acid is ex- tracted and is obtained together with some of the iso-acid when the ethereal solution is evaporated at a low temperature. It is colourless and easily soluble in water and in ether ; it easily passes into the iso- acid and its constitution is probably expressed by the formula <N:c(sH)>S its properties indicating the presence of two SH- groups. When a solution of iodine is added to a solution of a perthiocyanate the colour of the former disappears and a white precipitate is after- wards formed but it is too nnstable for analysis.Potassium permm- gantte is also bleached by a perthiocyanate 1 mol. of the acid absorbing 8 atoms of oxygen ; this would account for the oxidation of two of the sulphur-atoms to siilphuric acid and the formation of an acid of the formula <N:C(OH)>S ; but this has not been ob- tained in a state fit for analysis. A solution of potassium perthiocyanate gives a green precipihte with copper sulphate a yellow one with lead and bismuth salts and a white one with silver nitrate-all insoluble in excess of the perthio- cyanate ; the precipitntes formed with cadmium zinc mercury cobalt nickel and ferrous salts are all soluble in excess of the perthiocyanate.Ferric chloride gives a black precipitate which gradually becomes white. Barium perthiocyanate crystallises in slender needles contain- ing 4 mols. H,O three of which are lost a t 110" and the fourth at 150" ; it is easily soluble forming an alkaline solution which is converted into barium thiocyanate and sulphur when heated for 12 hours on the water-bath. The neutral aud acid potassium salts the calcium lead and silver salts are also described. The ethyl salt Et,C2N,S3 is a strongly refract,ive colourless oil of the consistency of olive oil ; its sp. gr'. is 1.2544 a t 18"; i t has a faint sweet smell and boils in a vacuum at about 190". When heated with strong hydrochloric acid i n which it is soluble in a waled tube it is decomposed with forma- tion o f ammonia carbonic anhydride hydrogen sulphide.ethyl hydro- sulphide and ethyl polysulphide. Alcoholic potassium hydrosulphide C(SH):N C(0H):NORGANIC GHlC X I ISTRY. 229 converts it into ethyl 11 ydrosulphide and potassium perthiocyanate. The ethyl and siilpliur thus appear to be directly united. Perthiocyairoglycollic m i d C,N,S( S-CH,*COO H)2 is obtained when isoperthiocyanic acid (1 mol.) is first shaken with a solution of potas- sium hydroxide (2 mols.) for some time and a solution of sodium chloracetate (2 mols.) then added. This mixture is heated on the wa ter-bath and hydrochloric acid added when the free acid crystallises out on cooling in long slender obliquely cut colourless tables.It melts with decomposition a t 177" and is nearly insoIuble in cold but eady soluble in h u t water. I t s solution gives white precipitates with lead acetate and silver nitrate and a yellow one with ferric chloride. When heated with hydrochloric acid in a sealed tube thioglycollic acid is formed among other products. Tbe potassium blnriuliz (with 3 mols. H,O) calcium (with 3.5 mols. H,O) zinc cadixiurn and copper salts are described. The ethyl salt cannot be distilled; the atnide forms slender prisms which melt at 125". The dithiocyanic acids were first described by Fleischer ; the iso- acid is always obtained along with isoperthiocyanic acid when a thiocyanate is decomposed by an acid; but the author has never obtained i t in the puye state. The normal dithiocyanates are colourless not yellow as Fleischer has stated; the author has not obtained them free from perthio- cyanates from which they differ in that with ferric chloride they give a dark-red coloration which rapidly changes to yellow and finally to a greyish-white precipitate.When it is attempted to prepare the ethyl salt ethyl thiocyanate is obtained; nor can the hydrogen in the acid be displaced by any organic radicle without decomposing the molecule with formation of a thiocyanic derivative. A. G. B. Platinum Compounds of Methyl Sulphide. By C. ENEBUSKE ( J . pr. Chem. [Z] 38 358-365).-Three isomeric chlorides of the general formula PtC12,2Me,S are obtained by the action of potassium platinosochloride on methyl sulphide. The a-plufosonzethylaulphine chloride Pt(S.Me,),CI crystallises from chloroform i n citron-yellow transparent monosymmetrical crystals melting a t 159" ; after melting i t dissolves in chloroform with formation of both the a- and p-chlo- rides.The P-chloride forms quadratic tables which contain 1 mol. of chloroform ; i t melts a t 159" and gives both chlorides after melting. A red pulveralent chloride is tirst formed when potassium platinoso- chloride acts on methyl sulphidc and this becomes yellow and floccu- lent at a temperature of 50"; both forms are insoluble in chloroform and are stable towards reagents ; the author regards this a s a double chloride of the formula Pt ( S MeL C1.C 1. P t*SMt,. SMe,C 1)2. Platoso m et hy E- sutphine bromide P ~ ( S M ~ B Y ) ~ forms bright yellow monoclinic crys- tals ; the iodide forms ruby-red crystals which decoinpose at 172" ; the sulphrtte Pt:( SMe,0)y:S02 + 2H20 forms yellowish crystals easily solnbIe in water ant1 melting a t 91" ; the nityate nitrite chromate and hydroxide are also described. The author has obtained saits of the radicle yllrtosomethyldisu~~hine Pt ( S M e2) 4.'l'he platiriic derivatives are obtained from the platinous derivatives VOL. LVI. T230 ABSTRACTS OF CHEMICAL PAPERS. by treahing their chloroform solutions with the halogens. Plativo- nrethylsulphine chloride PtCI,( SMe,Cl) is a yellow crystalline powder decomposing a t 21 8" without melting. The bromocldoride bromide iodochloride iodobromide and iodide are also described. A. G. B. Action of Hot Manganese Dioxide on Alcohol Vapour.By E. DONATH (Chem. Zeit. 12 1191-1192).-Carbonic anhydride acetone and small quantities of some higher boiling products are obtained when alcohol vapour is exposed to the action of manganese dioxide heated to temperatures varying from 150" to 360" the latter being reduced to manganese sesquioxide Mn,O?. Barium is frequently present a8 an impurity and in combination with the manganese and such compounds give rise mainly to barium and manganese acetates but also to salts of these metals with the higher homologous acids in small quantities. Mixing with lime did not increase the yield of acetic acid; but soaking the dioxide with sodium hydroxide and drying well was more successful in this respect. D. A. L. Platinum Compounds of Ethyl Sulphide. By C. W. BLOM- STRAND ( J.pr. Chern. [2] 38. 352-358).-a-Platosethylsulpl~ine chloride PtC1*SEt2*SEt,C1 is directly obtained by the action of potns- sium platinosochloride on ethyl sulphide. It melts a t 81". The crystals are bright yellow and inonoclinic [a b c = 1.3876 1 1.2610; = 86" 4'1. The /?-chloride Pt(SEt,Cl) is formed from the a-chloride and ethyl sulphide. It crystallises in greenish monoclinic tables melting a t 106" [ a b c = 1.5567 1 1.2961 ; /? = 82" 44'1. The browbide Pt (SEbBr) forms yellowish-red monoclinic crystals melting at 118" [ a b c = 1.5072 1 0.98239; 6 = 87" 2.5'1. The iodide P t ( SEtJ) forms large dark red monoclinic crystals which melt at 136" [a b c = 1.4714 1 0 9885; p = 89" 43'1. Platosethy lsulphine ylatinosochloride P t ( SEtzCI),,PtCl is obtained by heating platinous chloride for some time with ethyl sulphide (1 mol.) ; i t is a yellow powder insoluble in alcohol.Platoseth y lmethylsulphzne chloride SEt,Cl-Pt*SMe,Cl is formed when platinous chloride acts on a mixture of ethyl and methyl sul- phides; it is a heavy oil with a Low freezing point. PlittosethyZ- propylswlphine chloride SEt2C1*Pt*SPr,C1 is a syrup which solidifies slowly ; the iodide is precipitated by alcohol from a chloroform solu- tion in small lustrous y~llowish-red crystals. Platosethylsulphine nztrite Pt(SEt,*O.NO) is obtained by the action of fuming nitric acid on the sulphate (see below) ; it crystnl- lises from chloroform in large rhombic pure white crystals which are sparingly soluble in cold water. The sulphute is formed from the chloride and silver sulphate it is very soluble and crystallises in large short and thick crystals which have the formula Pt(SEt20),SOz + 7&0.The plaosFhate nitrate chrornate and oxalate have been obtained and also b j treating the sulphate with barium hydroxide a strongly alkaline solution of the hydroxide. The platinic derivatives are obtained by dissolving the platinous derivatives (preferably in chloroform) and acting on the solution with the halogen. Platinethy lsulphine chloride PtCl,( SEt,Cl) crystallisesORGANIC CHEMISTRY. 231 in small bright-yellow tables and prisms which are triclinic and melt with decomposition at 175"; the bromide forms red monoclinic prisms p = 88" 30' ; the browtochloride forms yellowish-red crystals and the iodide crystallises from chloroform in pretty dichroic prisms melting at 1O4" dark-red by transmitted and dark-blue by reflected light.A. G. B. Oxidation of Unsaturated Compounds. By G . WAGNER (Ber. 21. 3347- 3:155 ; compare Abstr. 1888,665).-When ethyl vinyl car- binol (b. p. = 114-114.5") is oxidised with a dilute aqueous solution of potassium permanganate it is converted into a series of compounds which can be partially separated by steam distillation. The neutral products volatile with steam in addition to unaltered ethyl vinyl carbinol consist of propsldehyde and a small quantity of a pungent substance distilling below 1 lo" which yields a reddish-brown oil containing nitrogen with phenylhydrazine and is most probably ethyl vinyl ketone. The neutral product not volatile with stearn (yield 63 per cent.of that theoretically possible) is p e n t e n y Zglycerol OH.CHEt-GH(OH).CH,*OH a sweet thick and very hygroscoprc syrup which boils a t 192" under 63 3 mm. pressure has a sp. gr. = 1.0851 a t 34" (water at 0" = l ) and is soluble in all proportions in we er and alcohol and also soluble to some extent in ether. Its t r i a c e f u t e i\ a syrup with a Faint alliacenus odour boils a t 177' under 52 mm. pressure and at 261-26.5" under the ordinary pressure has a sp. gr. = 2.122 a t 0" and = 1.103 at 18" (water a t 0" = l ) and is soluble in the ordinary solvents. The acids volatile with steam consist of a mixture of formic and propionic acids and the non-volatile acids comprise oxalic avid and a compound which from the analysis of its zinc salt and behavionr with phenglhgdrazine is almost certainly propionylformic acid.To only a limited extent therefore under these conditions is ethyl vinyl carbinol oxidised as a secoiidary alcohol to the corresponding ketone ; on the contrary it undergoes oxidation as though it were an olefine (Abstr. 1888 665 j yielding pentenylglycerol which by further oxi- dation yields on the one hand probably propionic and oxalic acids on the other formic and propionylformic acids the last by its decomposi- tion forming carbonic anhydride and propaldehyde. Methyl allyl carbinol when oxidised in like manner yields as chief product (82 per cent. of that theoretically possible) pentenylglycerd OH-CMeH*CH,.CH(OHj*CH,*OH which boils a t 180" under 27 mni.pressure has a sp. gr. = 1.135 at O" and = 1.120 a t 22" (water a t 0" = l) is somewhat more mobile than its isomeride and has a sweet but burning taste. Its triacetate has a cucumber-like odour and a sp. gr. = 1.120 at 0" and = 1.101 a t 20" (water a t 0" = 1). The neutral product volatile with steam is acetaldehyde and the acids volatile with steam are formic and acetic acids traces only of non-volatile acids being present. Inasmuch as no trace of a ketone could be found methyl allyl carbinol under these conditions seems to be oxidised exclusively as an olefine. Ally1 alcohol under like conditions yields glycerol acraldehyde and formic acid and therefore forms oxidation products characteristic both of an olefine and of a primary alcohol. r !232 ABSTRACTS OF GEERIICAI PAPERS.Unsaturated aldehydes are known to yield the corresponding acids on oxidatiori and herice behave like the saturated compounds. Un- s;1 turated ketones however probably yield the corresponding hydr- oxyketones ; thus the production of hydi oxpisohutyric and acetic acids by the oxidation of mesityl oxide (Pinner Abstr. 1882 941) is most probably prereded by the formation of the dihydroxyketone. I n the author's view hydroxy-compounds are the primary oxidation- products of unsaturated hydrocarbony alcohols and ketone9 when the oxidation is effected not only by dilute aqueous potassium perman- ganate b u t also by any substance which exerts a purely oxidising action these primary products subsequentlg undergoing various further changes under the different ronditions obtaining in each oxidation.The view hitherto gene~ally accepted that unsaturated compoucds on oxidation break up a t the point of the '' double bonds," is no longer tenable even in those cases wliere decomposition is effected by fusion with potassium hydroxide sirice this reaction finds its most probable explanation in the view that for example an acid CHR:CR'*COOH (where R = C1zH2n+l and R' = H or CnHPn+l) is first oxidised t o the compound CHR( OH).CR'(OH)COOH which then undergoes reduction to the /I-ketonic acid R.CO*CHR'.COOH which in the presence of the alkali hydrolyseu in the usual way into the acids R-COOH and CH,R'-COOH. w. P. w. The Part played by Water in the Oxidation of Unsaturated Compounds. By G. WAGNER (Ber. 21,3856-3360) .-The author's experiments (Abstr.1888 665 ; preceding Abstract) show that un- saturated compounds when oxidised i n the presence of water cannot combine directly either with oxygen or water but invariably yield compounds formed by direct union with hydroxyl. Water therefore plays a very important part in the oxidation and the reaction is probably represented in the case of ethylene by the equation C,H + 0 + H,O = C,H,(OH)?. Therniochemical data show that the formation of glycol by the oxidation of ethylene according to this equation involves the liberation of 58.4 cal. whereas the produc tivn of acetaldehyde by the action of oxygen on the hydrocarbon would Preparation of Epichlorhydrin. By A FAUCONNIER (BdZ. SOC. Chim. 50 218-214).-Dichlorhydrin is best obtained by the action of hydrogeu chloride on glycerol a t 120-130" (Abstr.1888 244). Water and acid with traces of the symmetrical dichlorhydrin (h. p. 176") distil over. The fraction boiling at 50-120" contains the two dichlorhydrins and the fraction boiling at 120-150" the two monochlorliydrins. The monochlor- hydrins with the addition of more glycerol are again treated with hydrogen chloride. With 3 or 4 kilos. of glycerol the operation takes 30 to 40 hours. Ep ichlorhydrin is prepared by treating the crude dichlorhydrin with very strong potash or soda following Reboul's method. The product is decanted and distilled in a I acunm ; the epic*hlorhydrin distils over below 75" ; the fraction boiling a t 75-120° is nil- require an absorption of 33 cal. w. P. w. The product is distilled in a vacuum.0 ROANlC CHEIIISTRY.233 changed dichlorhydrin. The crude epichlorhydrin is washed with water and distilled without previously drying i t ; the fraction boiling a t llti-118° is redistilled in a vacuum. The yield is very good and with little trouble 1500 to 2000 grams can be prepared in a week. N. H. M. Benzoic Acetals of Mannitol By J. MEUNIER (Compt. rend 107 910-911 ; compare Abstr. 1888 950).-The benzoic acetal of mannitol is very readily obtained by dissolviiig mannitol in sulphurio or hydrochloric acid adding the requisite quantity of benzaidehyde and agitating wfieii the mixture becomes completely solid. Pure mannitol is uot necessary. The acetal is insoluble in water acids alkalis and cold alcohol &c. and hence is easily purified by washing. It is readily reconverted into mannitol and benzaldehyde and hence may be utilised to separate mannitol from mixtures such as plant juices in which it occur9 along with albuminoids glucose &c.When the benzoic acctal is perfectly free from benzaldehyde it resists the action of acids as well as alkalis and is not decomposed even by prolonged boiling with acidified water. If however a small quantity of the aldehyde is present t,he acetal i8 readily decomposed the rate of decomposition increasing with the quantity of aldehyde. I n fact decomposition will take place when it is treated with sulphuric acid of only 1 per cent. C. H. B. Sugar obtained from Plantago Psyllium. By R. W. BADE& (Annulev 248 140-144).-l'he carbohydrate obtained from the epidermis of PqZlium gallicum by boiling the aqueous extract with dilute sulphuric acid is xylose.It was identified by its melting point rotatory power and by its compound with phenylhydrazine. w. c. w. Amylene Nitrosate and its Derivatives. By 0. WALLACE (Annulen 248,161-1'75).-Am,~lene nitrosat,e N0,*O*CMe2*CMe:NOH is prepared by the action of nitric acid (sp. gr. 1.385) on a mixture of nmyl nitrite amylene and glacial acetic acid. The best yield is obtained with an amylene boiling at 36-38". The crude product decomposes in closed vessels but is tolerably stable when exposed tcS the air. It is purified by recrystadlisation from warm benzene and afterwards from ethyl acetate ; if the solvent is rapidly evaporated the nitrosate is deposited in needles but on slow evaporation fine monoclinic crystals resembling cubes in appesra nce are deposited ; axial ratios a b c = 0.977 1 1.4485 ; /? = 8:3" 32'.By the action of potassinm cyanide on amplene nitrosate (Abstr. 1888 38) the pitrile CN.CMe,*CMe:NO H is formed. This substance melts at 99-100" and boils at 230" with partial decomposition. It is freely soluble in water aicohol ether and benzene. On saponification i 4 yields an amide CONH,-CMe*CMe:NOH and the hydroxylamitie- derivative of dimethylacetic acid or ketoximedimeth~jlacrtic avid OH.N:CMe.CMe,*COOH. The acid is freely soluble in alcohol benzene and water. The silver salt is deposited from aqiieous or alcoholic solutions in needles. The acid nielts at 96-97> with de-234 ABSTRACTS OF CHEMICAL PAPERS.oomposition yielding carbonic anhydride and the ketoximo of methyl isopropyl ketone CHMe,-CMe:NOH. The synthesis of ketoximedi- mei hylacetic acid from amylene nitrosate shows that this compound is derived from trimethylethylene. ,inzyZens~itl.o~i;f,e,.idide C5NH,,*CMe2*CMe:iSOH is best prepared by the action of amylene nitrosate on an alcoholic solution of piperi- dine. It is deposited from alcohol in glistening prisms. Hy the action of boiling dilute sulphuric acid it is converted into the keto-base C,NH,,*CMe2*C014e a colourless liquid boiling at 219-220" sp. gr. 0.934. The hydrochloride is very hygroscopic but the platino- Aldehyde and Acetone Sulphites of Organic Bases. By H. SCHIFP (AnmaZen 248 14&146).-Not only primary monamines but also secondary and tertiary amines and diamines have the power of uniting with aldehydosulphites t o form crystalline compounds.Sulphines. By G. PATEIN (Hull. SOC. Chim. 50 201-206 ; com- pare Abstr. 1888 664).-When the compound SEt2Br2 prepared by Cahours by the action of bromine on methyl sulphide is dissolved in water (8 mols.) i t is decomposed with liberation of hydrogen bromide. When the alcoholic solution is treated with zinc the solution evapo- rated and the viscous product dissolved in water and treated with mercuric chloride the compound SMe,,HgCl + SMez,ZnBr2 is obtained as a white precipitate. The iodide SMeJ prepared by the action of iodine on the sulphide is crystalline and resembles iodine in appearance; it dissolves in alcohol ether and benzene but not in water and has an unpleasant odour.It is conrerted by anhjdrous alcoholic ammonia into iodo- form and a compound of iodoform with methyl suphide. When treated with silver cyanide silver iodide cyanogen iodide and methyl sulphide are formed. chloride ( CI,HI9N O),,H,PtCl forms fine crystals. w. c. w. w. c. w. N. H. M. Symmetrical Dibromacetone. By E. HJELT andV. 0. SIVEN (Her. 21 3288-3289) .-Dibromacetone (symmetrical) can be pre- pared by oxidising dibromhydrin (50 grams) with a mixture of potassium dichromate (25 grams) sulphuric acid (40 grams) and water (40 grams) and purifying the product by means of the sodium hydrogen sulphite compound (compare Aschan this vol. p. 31). The yield is 20-25 per cent. of the dibromhydrin employed. It is tt colourless liquid with a pungent odour (compare Volker Abstr.1878 781). The hydrogen sodium sulphite compound C,H,0Br,,NaHSS03 + 1hH20,. crystallises in nacreous plates and emoresces on exposure to the air. Dibromacetone yields a very unstable compound C3H40Br,,N H3 with ammonia and it also reacts with phenylhydr- azine. The oxime crystallises in slender needles. When the acetone is heated with Fehling's solution the latter is reduced and when it is dlssolved in baryta-water or potassium carbonate solutions are obtained which probably contain dehydroxgncet,one as they reduce Fehling's solution when warmed with it and jield a sjrupy liquid when evapo- rated and extracted with alcohol. B. S. K.ORGANIC CHEMISTRY. 235 Preparation of Ketones. By J. HANONET (Bull. SOC. Chim. 50 355-358) .-Propione COEt is prepared by digesting propionic chloride (1 mol.) with ferric chloride (1 mol.) using a reflux apparatus.The mixture is at first cooled and afterwards heated at about 60". The product is poured into a little well-cooled wat'er and the oil washed with water and distilled. The yield is about 34 per cent. of the theoretical. Butyrorze COPr2 is obtained by heating butyric chloride (4 mols.) and ferric chloride (1 mol.) at 45" or 50"; the black oil is washed with alkaline water before being distilled. It is lighter than water and boils at 142-1U". It boils at 101-102". Qhanthylone was prepared from heptylic chloride. Diethoxyacetone. N. H. M. By E. GRIMALJX and IJ. LEFAVRE jCompt. rend. 107 914-916).-Ethyl ethoxyaceto-ethoxyacetate is allowed to remain 48 to 72 hours at the ordinary temperature with a sufficient quantity of a 2.5 per cent.solution of potassium hydroxide to convert it into the potassium salt. The liquid is then acidified with sulphuric acid which liberates the free acid and the latter at once decomposes with evolution of carbonic anhydride. The liquid is extracted with ether and the ethereal solution dried and distilled. The greater part of the residue boils at 193-196" and the yield is 20-25 per cent. of the original ethereal salt. Dietkoqacetone CO (CH,*OEt) boils at 195" and is a colonrless liquid with an aromatic odour and a sweet burning taste ; sp. gr. at 17.8" = 0.980 ; vapour-density 4.95. It dissolves in alcohol and ether and is slightly soluble in water; it volatilises in steam.Diethoxy- acetone combines with sodium hydrogen sulphi te with great develop- ment of heat forming a very soluble compound. Its reducing power is very much greater than that of an equal weight of glucose. It readily reduces Pehling's solntion and yields a mirror with am- rnoniacal silver nitrate even at the ordinary temperature. When treated with sodium ethoxide an energetic reaction takes place with formation of brown resinous products insoluble in water but soluble in alkalis. Diethoxyacetone is remarkable in having the properties of both ketones and ethereal derivatives of glycols. Action of Copper Acetylacetone on Carbonyl Chloride. By THOMAS and LEF~VRE (Bull. Xoc. Chim. 50 293-194).-When the powdered copper-derivative is heated at 60-70" with carbonyl chloride dissolved in benzene the product filtered and evaporated crystals are obtained which are recrystallised from ether.The new compound melts at 120-121". When heated a sublimate of large yellow needles is obtained which seems to be a different substance. It dissolves in alcohol ether and benzene very readily in chloroform ; warm water seems to decompose it. When heated with ammonia it dissolves at once and yields a compound melting at 250". The com- positiou of the compounds has not yet been determined. It cannot be converted into symmetrical dichloracetone. C. H. B. IS. H. M.236 ABSTRACTS OF CHEMICAL PAPERS. Arrangement of Atoms in Space. Geometrical Constitu- tion of the Crotonic Acids and their Halogen Substitution Products. By J. WISLICENUS and in part E.TEISLER and H. LANGBEIN (Annulen 248 281-35s) .-a-/3-Dichlorobutjric acid and its derivatives have already been described by the author (Abstr. 1887 6Fj5). a-p-Isodichlorobutyric acid is prepared by saturating a mixture of isocrotonic acid and carbon bisulphide with chlorine. After removing the solvent by passing a current of dry air through the product a small quantity of a-p-dichlorobutyric acid is deposited in crystals but the a-p-isodichlorobutyric acid remains as a non- crystallisable oil. a-P-Isodichlorobutyric acid yields d-chlorocrotonic acid when it is treated with &n excess of an aqueous solution of sodium hydroxide and an aqiieous solution of i t s sodium salt decom- poses at 80° yielding carbonic anhydride and a-chloropropylene (b. D. 36").\ A I CH,*C*H H.b.Cl is easily attacked by alkalis at 100" a-Isoc hloropropylene H-C.CHs and converted into allylene. a-Chloropropplene H,b,CI is less readily attacked. In the preparahion of a-P-dichlorobutgric acid by the action of chlorine on a solution of solid crotonic acid in carbon bisulphide aq oily bye-product is obtained It consists of a mixture of a-p-isodichloro- butyric acid with the normal isomeride. ?'he amount of this bye- product is increased by raisixig the temperature a t which the reaction takes place. the action of bromine on isacrotonic acid mixed with carbon bisulphide is a-P-isadi bromobutyric acid. A small quantity of solid rt-p-bromocrotonic acid is also formed. a-G-Isodi- bromobutyric acid is decomposed by an excess of alkali yielding a t the ordinary temperature a-bromocrotonic acid b u t a t 100" a mixture of a-isobromopropylene (b.p. 39-60d) and a new a-bromopropylene (b. p. 63-64'). The lqttep is more conveniently prepared by con- verting a-isobromopropylene (from a-@-dibrornobutgric acid) into t,ribromopropane by the action of bromine. The asp-tribromo- rJroDane is mixed with alcohol and treated with zinc-dnst. The chief product A L H*C'CHB ig not easily attacked by alkalis but H & ~ B ~ a- Brow oprop 9 1 ene CB,*C)*H H*E,ur ' is converted into allylene. a-is0 brom opropy lene One part of potassium bromocrotonate dissolves in 493.4 parts of 99.5 per cent. alcohol a t 21". Under similar conditions potassium isobromocrotonatt! only requires 10.8 parts of alcohol. a/3-Dichlorobutyric acid is partly converted into ap-isodichloro- butyric acid by expodure to a temperature of 100-285" and chloro- arid bromo-cratonic acids are always farmed in small quantities when &-isochloro- 01' bt-omo-crotonic adds are distilled in a current of steam.Exposure to a mall quantity of hydrogen chloride a t 100" partially converts isocratonic into crotonic acid.ORGANIC CHEJlISTRT. %37 a-Isobromocrotonic acid is completely converted into crotonic acid by the action of sodium amalgam in alkaline solution but in an acid soliition isocrotonic acid is formed as well as crotonic acid. The nnthor concludes by replying to the criticisms of Michael (Abstr. 1888 1147 and 1176). w. c. vcr. Action of Phosphorus Sulphides on Dibromosuccinic Acids. By I. OSSTPOFF ( J .RIW. C'hen2. Soc. 1880 20 245-2,>4).-if as is generally admitted dibromosuccinic acid is a derivative of fumai ic acid and isodibromosuccinic acid of maleic acid the first ought to be convertible into thiophen or its derivatives. The author finds however that dibromosnccinic acid when heated with phosphorus trisulphide o r pentnsulphide under the ordinary pressure a t 140° does not give R thiophen cornpound. In sealed tubes with phosphorus tri- snlphide nothing but thionialic acid was formed. No better result v as obtained whea the sodium salt of dibronlosuccinid acid was eniployed or with isodibromosuccinic acid or its anhydride. These results are not in accordance with the equations Kues and Paal give (Ber. 19 555) as representitig the format ion of thiophen.The E€hereal Salts of Fumaric and Maleic Acids. By I. OSSIPUFF ( J . %ss. Cheni. Xoc. l888,20,254-267).-Silver fnrnarate was treated with isobutyl iodide i n the presence of ethyl ether hut hardly any reaction took place. Silver maleate with isobuhyl OF isdamyl bropide gave no better results; the same is the case w i t h the iodides of higher alcohol radicles. Ethyl and isopr(opyl maleates *ere found to have a normal vaponr- density. The same is the case with isopropyl fumarate but the isobutyl salt is found to decompose under these circumqtances ; even isnpropyl fumarate which shows the normal vapour-density a t the boiling point of arhyl benzoate decomposes at the boiling point of ,&naphthol (28.5-290"). The mono-silver salt of male'ic acid (acid silver maleate) gave with ethyl iodide hydrbgen ethyl maleate and from this the sodium salt C,H,O,EtNa was obtained.This after decomposition with sul- phuric acid gives free ethylmaleic acid which is not identical with ethylfumaric acid. With acetic chloride the above sodium salt gives a compound which would seem to be the acetyl-derivative of ethylmale'ic acid as when it is treated with ethyl alcohol at the ordinary temperature it yields ethyl acetate and ethyl maleate. When male'ic anhydride is heated in a sealed tube with benzyl dt!ohdl 8 mixture of substances is obtained consisting chiefly of sodium benz+ylmaleate. Phehol gives no reaction with male'ic anhydride. Comp6unds of Dibromopyruvic Acid With Hydrazines. By 0. NASTVOGEL (Annaleir 948 85-92). -Phefiylosazonglyoxalcarb- ozylic acid N,HPh:CH:C( N,HPh)*COOH i d deposited in orange- coloured crystals on mixing aqueous solutions of phenylhydrazine and dibromopyriivic acid.It melts at 201-203" with decomposition and is soluble ih acetone acetic acid and in boilihg alcahoi or ben- B. B. B. B.238 ABSTRACTS OF CHEMICAL PAPERS. zene. The sodium potassium and ammoniuni salts are crystalline and are sparingly soluble in water. Paratol2/ZosazoneglyoxaEcarboxyl ic acid C,,EI,,N402 melts at 186-188O with deconiposi tion and dissolves freely in warm alcohol acetone benzene and acetic acid. The sodium potassium and ammonium salts are much more soluble in hot than in cold water. a-Naphthylosazoneg1yoxaIcarboa:ylic acid forms cherry-red crystals and melts at 196". (3-Naphthylhydrazine and di bromopyruvic acid unite together forming a hydrazide probably C,H,*N,H CH*C 0.C (0 H) :N,H.C loH7.This substance i s insoluble in alkalis and is decomposed by boiling with an alcoholic solution of potassium hydroxide. Dibmnwmth y lh ydroaytoluquinoxalin~ C7H6<N:C(oH) -> is formed when a mixture of orthotoluylenediamine and dibromopyruvic acid in molecular proportions is boiled. It melts with decomposition at 235" and is reprecipitated on adding an acid to its solution in a1 kal is. w. c. w. N:C ( CHBr,) Tricarballylic Acid. By P. DAUMICHEN (Chem. Centr. 1888 1347-1348).-1n the preparation of ethyl malonate from monochlor- acetic acid and potassium cyanide an oil of high boiling point (286-287") was obtained as a bye-product. Its behavionr with barium hydroxide and hydrochloric acid its elementary analysis and the analysis of its silver and copper salts shored it to consist of t rieth yl tricarball ylat e.No well-characterised substance is obtained from tricarballylic acid by subjecting it to distillation. Bmzy I tricarballylate prepared from the sodium salt and benzpl chloride consists of lustrous pearly leaves soluble in alcohol sparingly in ether insoluble in water. It may be prepared more readily by neutralising the alcoholic solution of tricarballylic acid with potash distilling off the greater portion of the alcohol and boiling with benzyl chloride in a reflux appayatus. Acetyl tricarballylic anhy- dride ClaHloOll prepared by boiling carballylic acid with excess of acetic chloride melts a t 128-129"; when exposed to moist air it becomes hydrated with formation of acetyl tricarbaliylic acid.Tri- carballylanilic acid Cl2HI1NO4 prepared by heating '1 gram of tricarb- allylic acid with 3.18 grams of aniline forms lustrous pearly scales and melts at 137". Tricarballylrparatoluic acid crystallises with 1 mol. H,O and melts at 174". These two acids take up water when dissolved in it and pass into the bibasic derivatives; their silver salts are amorphous as also the copper salts of the toluyl-derivative. The tricnrballylparaditolzLic acid was also obtained ; it melts a t 174" is monobasic and with the heavy metals forms salts which are amor- phous TricarbnllylparatoZuidide was also found as a product of the action of toluidine on tricarballylic acid ; it melts at 253'.Tricarb- ullylparaditoluyl is formed by dissolving paratoluidine and tricarb- allylic acid in alcohol ; it melts a t 178" anti when boiled with alkalis passes into $he paraditoluic acid.ORGANIC CHENISTRT. 239 Tricarbd Zy Zamid e is prepared by treating ammonium tricarbally 1 ate in ammoniacal solution in a sealed tube or bv protracted agitation of the triethyl salt with ammonia ; it melts a t 218" with decomposition ammonia being evolved and trica? ballylamideimide remains ; this melts at 172-173". J. W. L. By J. KRGTWIG ( Z e d . physikal. Chem. 2 787-795).-The author doubts the generality of the conclusions arrived a t by Dreyfus (Abstr. 1888,24) and gives the details of an investigation on the oxidation of tartaric acid by means of potassium permanganate under different conditions.He shows that the rate of oxidation increases with the amount of tartaric acid present and that it also proceeds more rapidlj without than with the addition of sulphuric acid. The reaction takes place much more readily in sunlight than in the dark and tlhe addition of excess of sulpburic acid up to a certain point has an accelerating influence as has also the presence of manganese sulphate in the solution. Alloxan Sulphites of Organic Bases. By G. PELLIZARRI (Annalen 248 146-152).-The following compounds were pre- pared by adding an aqueous solution of alloxnn to solutions of organic sulphites saturated with sulphurous anhydride :-Alloxon ethylamine sulphite C2H7N,S03Hz,C~H2N204 + H,O forms colourless monoclinic crystals ; a b c = 0.8341 1 1.2462 ; p = 1OU" 40' 20".Alloaan aniline sulphite CsH7N,S03Hz,C4HzK20~ + 2Hz0 crystallises in large quadratic plates. The methylaniline compound C7H9N,8O3Hz,C4H2NzOa + 2H,O forms small yellowish prisms. AZloxan dimethylaniline suZphite CBHIIN,SO3HP,C4H2NZO4 + 4H& forms monoclinic plates ; a b c = 1.33'19 1 0.3394 ; 13 = 99" 22' 40". The benzidine compound forms triclinic prisms containing 3 mol. HzO. Tolidine and amidobenzoic and aspartic aclds yield similar compounds. Alloxan pyricline sulphite is triclinic. The crystals are anhydrous. Anhydrous crystalline compounds are also obtained with quinoline picoline morphine and cinchonine. The strychnine com- pound crystallises with 1 rnol. H20 and the brucine compound with I& niol.H20. Alloxan ammonium sulphite forms triclinic crystals ; a b c = 0.6648 1 0.7121 ; a = 71" 11' 20" /3 = 99" 47' 20" and y = 80" 40'. The aqueous solution decomposes on boiling forming a small quantity of murexide ; in presence of ammonia or ammonium Rate of Oxidation of Tartaric Acid. H. C. carbonate ammonium thionurate is produced. w. c. w-. Glycocine-derivative of a-Thiophenic Acid. By M. J A F F ~ and H. LEVY (Ber. 21 3458-3461).-a-Thiophenic acid is not poisonous and can be given to rabbits in the form of sodium salt i n daily quantities of 2 grams by subcutaneous injection. It is excreted in the urine as a-thiophenuric acid the glycocine-derivative of a-thio- phenic acid. a- Thiophenuric acid C7H,NS03 crystallises from water in colourless transparent strongly refractive thin prisms closely resembling those of hippuric acid nielts a t 171-1 72" and is very sparingly soluble in ether but readily soluble in alcohol and hot water.When boiled with bary ta-water it hydrolyses almost quantitatively into a- thiophenic acid240 ABS I'RXCl'S OF CHEMICAL PAPERS. and qlycocine but when hydroljsed with hydrochloric sc'd if yields only small quantities of a-thiophenic acid although the yleld of glycocine is quautitative. The siZcer salt C7HsNS0.3Ag crgstallises in colour- less microscopic needles dissolves sparinglv in water and is un- affected by exposure to light ; the bariurn salt (2 mols. H?O) crystal- lises in colourles4 slender needles and is readily soluble in water but insoluble i n alcohol ; the calciurrz salt (? 5 mols.H,O) crystallises in thick prismatic needles and is extremely soluble in water. Influence of Light on the Action of Halogens on Aromatic Compounds. By J. SCHRAMM (Monafsh. 9 842-853).-Tbe pre- sent) work a contiriuntion of the author's investigations (Abstr. 1885 4,51) was conducted with the object of ascertainidg the behaviour to wards the halogens of aromatic compounds containing side-chains which are not iiormal. Isoprop!lZbenzene.-In the dark or in pr'esence of iodine bromine enters the benzene nucleus a small quantity in the first case also dis- placing; hydrogen in the side-chain. The product boils a t 217-219" under a pressure of 739 mm and on oxidation yields a mixture of para- arid ortho-brombenzoic acids chiefly the former. In direct snnlight bromine (1 mol.) acts rapidly the product being a clear liquid which solidifies a t -20".On distillation this gives off large quantities of hydrogen bromide and about one-half of the original isopropylbenzene is recovered. I t appears in this latter case that substitutiou i n the side-chain takes place a di bromisopropylbenzene being formed which decomposes on distillation. IsnbutyZbelzzene.-In the dark or in presence of iodine bromine enters the benzene nucleus a bromisobutyZbesLzene being formed wliich boilr a t 232-5-2333" under a pressure of 739 mm. and solidifies at -18". On oxidation i t yields parabrombenaoic acid. In direct sunlight bromine rencts to form a compound which on distillatioti loses hydrogen bromidr and yields a hydrocarbon boiling a t 180-185".This lather combines with bromine to form an oily bromide but in other respects does iiot resemble Perkin's isobutenylbenzene. Secondary butylbenzene when tpeated with bromine in the dark or i n presence of iodine gives a brornobutylbenzene boiling at 235.5-237". It is not readily oxidised but yields parabrotnbenzoic acid wheh heated for seven days with a concentrated solution of alkaline permanganate. The action of bromine in sunlight is rapid but the product was not examined. By the action of bromine in the dark or in presence of iodine ter- tiary butylbenzene (trimethylphenylmethane) is converted iiito zb br-ornobutylbensene boiling a t 230-230.5" under a pressure of 736 mm. and of sp. gr. 1'2572. This compound cannot be oxidised unless with dichromate and excess of sulphuric acid when it is destroyed.It is % remarkable thing that tertiary butylbenzeiie is dot attacked by bromine in sunlight even when the solution is heated to the boiling point. As substitution of bramine i n the side-chain alwajs takes place with elimination of the hydrogen-atom attached to the capbun nearestl the beuzene nucleus the absence of such a hydrogen-atom in tertiary butylbenzene may perhaps explaifi this behaviour. w. P. w.ORQAKlC CHEBIISTHY. 2-1-1 I n the dark or in presence of iodine isoamylhenzene yields with bromine a bl.oinisoamylbenzerte boiling a t 253-255" under a pressure of 736 mm. and of sp. gr. 1.2144. On oxidation it gives parabrombenzoic acid. Isoamylbenzene is readily acted on by Fromine in direct sunlight the product being a liquid Eromisoamylbenzene which decom- poses on distillation into hydrogen bromide and phenylisoamylene.Tre;rted with another molecclar proportion of bromine in the dark it yields a dibromisoamylbeiizene melting at 128-129". It appears from the author's researches that the action of halogens on aromatic hydrocarbons in the dark and in direct sunlight may be com- pared in its results to action a t low and a t high temperatures. By the first substitution in the benzene nucleus takes place with formation of an ortho- or para-bromo-derivative whereas by the second substitu- tion in the side-chaiii is effected. H. C. Aromatic Cyanates and their Polymerides. By W. FRENTZEL (Chem. Cwtr 1888 1361-1 362).-Ethyl pseudocum!jlr.arbamate pre- pared from pseudocumidine and ethyl ch'orc carbonate dissolves readily in alcohol and melts a t 91.5".Phosphoric anhydride eliminates 1 mol. H,O from it with formation of pseudocurnylc~aiiate boiling a t 221". Triethylphosphine and more readily potassium acetate change the cyanate into its polymeride the cyanicrafe melting at 234". Dlcuni y l c a d a m i d e prepared from the cyanate me1 ts a t From unsymmetrical metaxylidine [Me NH =1 3 41 the curb- amatr melting at 57" and from this the c.!/anci,te boiling at 205". were prepared and b7 means of potassium acetate the cyanurate melting a t 162" was obtained. From the symmetrical metaxylidine [Me NIT = 1 3 51 the carbamate melting at 77.5" the cyanate boiling a t 208.5" and by means of carhonyl chloride dizylylca barnitie melting at 275" were prepared. ~ ~ ~ n o z y l y l c a r b a n i i d e melting a t 162" was prepared from the last-mentioned compound by eveporating the aqueous solntion of the hydrochloride with potassium cyanate.New General Method for the Synthesis of Aromatic Corn- pouads. By C. FRIEDEL and J. M. CRAFTd ( A n n . Cltim. Phys. [ci] 14 43;3-472).-When dry air or oxygen is passed into cold benzene in presence of aluminium chloride a very small quantity of phenol is formed but when the mixture is heated almost t o its boiling point this compound is produced in much larger quantities. After passing the gas for some time the mixture is poured iiito water the super- natiint oil separated and the phenol obtained in a perfectly pure state by extracting the acidified aqueous solution with ether and evaporat- ing.The oily product contains unaltered benzelle and red compounds; the latter are soluble in ether benzene and carbon bisulphide but insoluble in alcohol acetic acid and watrtr and cannot be distilled. Metacresol can be obtained from toluene in like manner. In this reaction also oily bye-products are formed ; these compounds are brown soluble i n toluene and cannot be distilled. When benzene and powdered sulphur are heated together at 75-80' 2tj0-270". J. W. L.2 t2 ABSTRACTS OF CHEMICAL PAPERS. i n presence of aluminium chloride until the evolution of hydrogen chloride and hydrogen sulphide ceases the mixture poured into water and the supernatant oil fractionated the following compounds together with unaltered benzene are obtained (I) Phenyl mersaptan boiling at 170-173" ; (2) plien-jd sulphide boiling at about 288"; and ( 3 ) diphenylene disulphide boiling at 364--366" (compare Stenhouse AnnaZen 149 252 and Graebe this Journal 1874 469).A com- pound C12H8Sz02 is obtained when diphenylene disulphide (1 mol.) is oxidised with chromic acid (18 mol.) in glacial acetic acid solution (compare Graebe Zoc. cit.). It cryst~llises from benzene in small prisms melts at 241" is readily soluble in glacial acetic acid sparingly in cold benzene and dissolves in concentrated sulphuric acid with a violet-red coloration. Benzoic acid is produced with evolution of hydrogen chloride when a stream of dry carbonic anhydride is passed for some days through a mixture of benzene and aluminium chloride heated almost to its boiling point. Phenylsulphinic acid is obtained by passing sulphurous anhydride into a warm mixture of benzene and aluminium chloride until the weicht of the hydrogen chloride evolved i s about half that of ?he aluminium chloride employed and then gradually pouring the whole into cold water.If the reaction is continued too long or if the mixture is allowed to cool a crystalline aluminium salt separates. The filtered aqueous solution is acidified with hydrochloric acid and the product extracted with ether. When aluminium chloride is gradually added to a warm mixture of benzene and pb thalic anhydride hydrogen chloride is evolved and orthobenzoylbenzoic acid is formed. ParatoZtLolrZlorthobenzoic acid C6H4Me*C0.CcH4*COOH is obtained when aluminium chloride (14 parts) is added in small portions at a time t o a mixture of phthalic anhydride (+part) and toluene (1 part).The whole is then poured into a large quantity of water and after keeping for some time the crystalline product is separated. Further quantities can be obtained by e-raporating the toluene. It crystallises from boiling toluene in white prisms melts at 146" is very readily soluble in benzene and alcohol more sparingly i i r ether and very sparingly in boiling water. Dilute aqueous solutions of the acid and solutions of many of its salts have a sweet taste. The ammoiiiitm salt crystallises from boiling water in which it is very readily soluble i n silky needles. The sodizm salt crystallises in small needles and is rery readily soluble in water but more sparingly in alcohol.When heated with soda at about 340" it is decomposed almost quantita- tively into sodium benzoate and sodium paratoluate. The barium salt (+ 4 mols H20) crystallises from water in prisms or needles and loses its water at 110". Most of the salts of the heavy metals are sparilzglg soluble in water. Orthoduroylbenzoic acid CGHMe4*CO*C,H4*COOH obtained in like manner crystallises from glacial acetic acid in plates melts above 260" and is readily soluble in alcohol ether acetone benzene and toluene but insoluble in water. The potassium salt crystallises in microscopic needles and is readilj soluble in cold water. The sodiumORGANIC CHEMISTRY. 243 salt is sparingly soluble in alcohol and separates from the solution again only partially i n the form of small plates.The ammonium salt crystallises in needles. The barium salt (+ 1 mol. H,O) crys- tallises in slender needles and is moderately soluble in alcohol but sparingly in water. The culciihm salt (+ 1 mol. H,O) crystallises from water in needles. The lead silver and copper salts are insolu- ble in water. Acetophenone is formed when benzene is treated with acetic anhy- dride in presence of aluminium chloride. When pure dry ethylene is passed into a mixture of benzene arid aluminium chloride heated at about 70-90" ethyl- diethyl- and triethyl- benzene are produced together with other higher boiling compounds. Aluminium phenyl is formed when mercury phenyl is heated with aluminium foil at 123-130". This compound will be fully described in a subsequent paper.It melts a t about 2:30" and absorbs moisture with great avidity but only absorbs oxygen very slowly when ex- posed to dry air. It yields diphenylmethane when treated with benzyl chloride but it does not react with chlorobenzene a t 100" in benzene solution. Yheuol is formed when oxygen is passed through a benzene solution of aluminium phenyl and when a xylene solution is heated with sulphur dipheriylene disulphide phenyl sulphide and probably also phenyl mercaptan are produced. These results show that aluminium phenyl behaves like a mixture of benzene and aluminium chloride and the authors consider that this fact is evidence in favour of the view t h a t an organo-metallic compound probably C6H6*Al2Cl5 is temporarily formed in all reactions similar to those described above and those already described (Ann.Chirn. Phys. [6] 1 449) in which aluminium chloride is employed. Gustavson (Abstr. 1885 363) considers that the brown liquid which is formed when aromatic hydrocarbons are placed in contact with aluminium chloride or bromide has a definite composition which i n the case of benzene is A1C1,(C6H6) or A1Br,(C6H6) and that it is this compound which reacts with the chloride bromide or iodide of the alcohol radicle. The authors find that when pure aluminium chloride or bromide is mixed with dry benzene or toluene this liquid is not formed or only produced in very small quantities and that in the case of aluminium chloride a considerable quantity remains un- dissolved in presence of excess of the hydrocarbon. When hydrogen chloride or bromide is passed into the mixture as recommended by Gustavson it was observed that the liquid was formed in some cases but not in others; when however a small quantity of water was admitted the liquid was always produced Analyses of the liquid obtained in various experiments showed that it was a complex mixture perhaps consisting of a compound of the hydrocarbon with alumiiiium chloride or more probably with a chlorhydroxide of aluminium the organo-metallic compound C6H5*Al2CI5 excess of the hydrocarbon and hydrochloric acid.F. S . IC. Influence of the Presence of Halogens and Alkyl-groups on the Replacement of Oxygen in Quinone-derivatives by the Isonitroso-group. By F. KEHRMANN (Bey. 21 3315-3321).-244 ABSTRACTS OF CHEMICAL PAPERS. Chloroquinone melting at 54" and bromoquinone melting at 55-56" react with hydroxylamine hydrochloride in alcoholic solution a t the ordinary temperature. The monoximes obtained have the constil u- tion [SOH X 0 = 1 3 41 and are unstable decomposing when heated for a long time a t 80-90".They are not easily obtained in the pure state crystdlise in small bright-yellow needles and are very readily soluble in alcohol and ether but only moderately so in bot water arid very sparingly in boiling benzene light petroleum acetone and carbon bisulphide. When reduced with tin and hydro- cliloric acid they yield halogen amidophenols [NH2 X OH = 1 3 41 and when treated with cold concentrated nitric acid they are converted into orthochloroparoximidoquinone decomposing at 140" and orthobromoparoximidoquinone decomposing a t 24'2" respect- ively.They are with difficulty converted into halogen dioximes [(NOH) X = 1 4 31 when boiled f n r a long time with excess of hy d roxy Inmine hydrochloride in aqueous solution. The dioximes crystalhe in small greyish-yellow needles are sparingly soluble in boiling water aloohol and ether moderately so in benzene and are converted into halogen dinitroso-derivatives when oxid ised with alkaline potassium ferricyapide solution or warm dilute nitric acid. The halogen dinitroso-derivatives are yellow crystalline com- pounds with a smell resembling both that of qninone and iodoform. They are readily volatile with steam and dissolve in fuming nitric acid from which they are precipitated unchanged on adding water but are only very sparingly soluble in ordinary solvents.They yield diamines which are readily oxidised to quinones when treated with cllrornic acid or ferric chloride. Me tadichloroquinone nielting a t 120-121° metadibi-omoquinone melt,ing a t 130-131" and metadi-iodoquinone melting at 1713" [O X = 1 4 2 61 do not form dioximes. The monoximes are yellow crystalline conipounds a lid me readily soluble in alkalis alcohol and ether but sparingly in boiling water benzene and carbon bisulphide. The ch loro-derivative decomposes a t 140" the bromo-derivative at 145". These oximes are readily converted into metadihalopenpara- nitrophenols when treated with cold moderately concentrated nitric acbid (compare Fischer and Hepp Abstr. 1888 456).Their consti- tution is therefore [ 0 NOH X2 = 1 4 2 61. P~radichloroquinone (m. p. ltil-162") parachlorobromoquinone (m. p. 171-172") and prtradibromoquinone (m. p. 188-189") [O X = 1 4 2 51 react with hpdroxylamine hydrochloride under the conditions described above forming both monoximes and dioxirnes which can be separ<ited by means of alcohol or benzene. Ptrrctd~chloro~ai~oximidr,quinone crjstallises in bright yellow needles decomposes without melting when heated a t 138" and is readily soluble in alcohol and ether but only sparingly in hot water benzene and carbon bisu'phide. It is slightly volatile with steam but resini- fies when boiled f o r a long time with water. [OH C1 NO = 1 2 5 41 ob- tained by dissolving the oximidoqninone i n well-cool( d concentrated nitric acid crystaliises from hot water or dilute a-lcohol in colourless Pa,.adichloropnranl'trophi nol,ORQANIC CHEMISTRY.245 needles and from absolute alcohol in short thick quadratic prisms melting at 115-116". It does not taste bitter and is somewhat volatile with steam. I t yields an amine which is converted into paradichloroquinune melting at 161-162" when oxidised with ferric chloride. Paradichl~roquinonediozime separates from benzene in greyish- yellow granular crystals and is readily soluble in boiling benzene b u t sparingly in alcohol and ether and insoluble in boiling water. Puradichloroparadsnitrosohenzene prepared by dissolving the di- oxime in fuming nitric acid crystallises in citron-yellow needles explodes when heated at 120-130" and is insoluble in the ordinary fiolvents.It is not oxidised when boiled with nitric acid. Ths amine obtained by reducing the dioxime or the dinitroso-cornpound is converted into paradictiloroquinone when treated with ferric chloride. Trichloroquinone and tribromoquinone yield dark brown resinous products when treated with hydroxylamine hydrochloride in alcoholic sol ut4ion and no crystalline compound except tetrachloroquinol was obtained. Chloranil and bromanil are gradually reduced to the correspondinq quinols when boiled with hydroxylamine hydrochloride in alcoholic solution. Trichlorotoluquinone tribromotoluquinone metadiclilorometaxylo- quinone [O Me C1 = 1 4 2 6 3 51 dichlorothymoquinone @p-dichloro- and dihromo-a-naphthaquinone do not combine with hydroxylamine under the conditions described above.It seenis therefore that the quinone-derivative cannot yield an oxime when the hydrogen adjacent to the CO-group is displaced by halogens or alkyls. Parachlorotoluquinone yields both a monoxime and a dioxime but bromotoluquinone LO Me B r = 1 4 2 61 and dibromotolu- quinone LO2 Me Br = 1 4 2 3 51 only yield monoximes. F. S. K. Dihydroxythiobenzenes. By G. TASSINART (Chem. Centr. 1888 1354 from Rend. Acad. dei Lincei [4] 4 ii 47-51).-The author considers that the componnds he has obtained as well as theii- homo- lopes have a symmetrical constitution. Several isomeric corn- pounds were never obtdined a t the same time. The reaction is much inore violent when the compounds are prepared from phenols in which the para-position to the hydroxyl-group is free and the derivatives so prepared have a higher melting point than their isomerides.I n the action of parabromophenol on sulphur dichloride con- siderable quantities oE each of the reacting substances remain u1i- changed. The acetyl-deriv:i tive of the dihydroxythiobenzene (Abstr. 1888 805) melts at 86 -87". From this the acrtylhydroxysul~hoiru was prepared by oxidation; it forms colourless crystals which are sparingly soluble in cold alcohol and insoluble in water ; it softens a t 160' and melts at 186-18i'. B y dissolving it in a little alcoholic potash and re-acidifying a hydroxysulphone hydroays7ili)honebenzid C,,H,,O,S was obtained which must be either a di-meta- o r a di- VOL. LVI. 6246 ABSTRACTS OF CHEMICAL PAPERS.ortho-derivative. It is white crystalline melts at 186-187" and is soluble in alcohol little soluble in water and in acetic acid. The acetylhydroxysulphone becomes readily soluble in potassic hydrate after heating to 187" ; it is therefore probable that the acetyl-group becomes separated by heating. I n order to determine the constitution of the dihydroxythiobenzene melting a t 150" Annaheim's hydroxysulphonebenzide was nitrated in order to obtain the di- and tetra-nitro-derivatives. Picric acid was formed as is also the case when the nitro-derivatives of hydroxy- sulplionebenzid are boiled with nitric acid. The acety 1 -derivative of orth odirnethy l d i h y drox y thiobenzene crys- tallises from alcohol and melts a t 44". When oxidised with potassium permanganate the corresponding benzide C11H1104S is formed which melts a t 132-133" is insoluble in water but soluble in hot alcohol.By saponifying with alcoholic potash dimethylhydroxysulphonebenzide melting at 263" is formed; i t dissolves in alkali hydroxides and carbonates and is reprecipitated from these solutions by carbonic acid. Diacety 7parad irnethy Zdihydroxy fl~iobenzene melts a t 83-84' and when oxidised yields the corresponding benzid melting a t 206-208" ; the latter is little soluble in hot alcohol. Saponification with alco- holic potash gives pwradimethylhydroxysulphonebenzide which is rather soluble in alcohol and acetic acid and melts a t 209" ; it dissolves in a1 kali hydroxides and carbonatds and is reprecipitated from such solutions by carbonic anhydride.The acetyl-derivative of dihydroxythionaphthnlene melts a t 200° is little soluble in and decomposed by hot acetic acid. Fluorescein. J. W. L. By R. MEYER and 0. OPPELT ( B e r . 21 33i6-33i8). -When fluorescein is heated for eight hours with aqueous ammonia a t 180-200" a basic compound C2,H,,N30 is formed which on cool- i n g cry stallises in the tube in large thick reddish-yellow rnonoclinic prisms and tables. The hydro- chloride crystallises in tufts of reddish-yellow prisrnq and from its rery dilute and boiling solution ammonia precipitates the base in scales of bronze-like lustre ; under the microscope these are seen to consist of extremely characteristic X-like interpenetrating twins. The authors point out thatl the constitution assigned to fluorescein by Knecht (Annale?z 215 83) is very improbable and propose instead the formula It is a direct yellow dye for wool.< ~ ~ b > C < C 6 H 4 ( o H ) > 0 C,H*( OH) [C OH 0 = 1 4 61 that of the derived base being <cfio.~>C<c6H4(NH,) C H C6Hk(NH2)>NH. The base must contain a t least one NHz-group inasmuch as its hydro- chloride yields a diazo-compound when treated with nitrous acid. On treatment with cold aqueous soda the lactone-ring is readily broken up and the base yields a sodium salt crystallising in slender needles ; the solution when acidified and then precipita ted by ammonia is at once reconverted into the original base. Eeduction with zinc-dust in theORGANIC CHEMISTRT. 247 alkaline solution converts the sodium salt into a colourless compound which is not precipitated on treatment first with hydrochloric acid and then with ammonia.Orcinphthalein when heated in like manner with aqueous ammonia yields a base similar to that just described ; the chief product how- ever is a colourless crystalline neutral compound containing Desmotropy in Phenols. By J. HERZIG and S. ZEISEL (Monatsh. 9 882-899).-An examination of the indifferent oil obtained in the preparation of pentethylphloroglucinol (Abstr. 1888 822) has been undertaken. It was subjected t o the action of hydrogen iodide the product dissolved in ether and then extracted with potash. The greater part is taken up by the potash but a portion is not attacked and remains dissolved in the ether. If the potash solution is acidified and the product again dissolved in ether and crystallised a crystalline mass is obtained one portion of which is sparingly soluble in alcohol and melts a t 209-212" whilst the other is more readily soluble in alcohol melts at 91-93" and is in every way identical with the pentethylpliloroglucinol already de- scribed.The sparingly soluble portion has the coniposition of a fetl.eth~lphZorogZieeinoZ. One atom of the hydrogen is replaceable by a metal and it is converted by the action of ethyl iodide into a mon- e t h \ l salt and by the action of acetic anhydride into a rnonacetate melting about 60-62". It readily exchaiiges one atom of hydrogen for bromine the product being probably a mixture of several isomerides. A similar reaction with bromine is found to occm in the case of pent- ethyl phloroglucinol.The portion of the original product which is insoluble in potash consists chiefly of a secoiidary hexethylphloroglucinol which as it is unattacked by hydrogen iodide must be regarded as hexethyltriketo- hexamethylme isomeric with the ethyl salt of the bi-secondary pent- nitrogen. w. P. w. ethylphloroglucinol already described. H. c. Derivatives of Parabromobenzyl and Parachlorobenzyl Al- cohols. By G. EBRERA (Gazzettu 18 236-243) .-Parabromobenzyl chloride cannot be obtained by the bromination of benzyl chloride or by the action of chlorine on parabroinotoluene but the author has succeeded in preparing it from parabromobenzyl alcohol. The latter was prepared by Jackson and Lowery's method (Abstr.18i8 64) of boiling parabromobenxyl bromide with water for several hours using a reflux condenser operating on small quantities at a time (4 to 5 grains) and using abundance of water (500 c.c.). The mixture bumps very much but a metal vessel cannot be used as it acts on the bromide in fact when the latter is boiled with zinc-dust nothing but pal-adibromobenzyl (m. p. 114') is formed; the chloride is acted on in like manner. The authors find that besides parabromobenzyl alcohol C6H4Br*CH2*OH the corresponding ether is also formed; tbe two however can be s s248 ABSTRACTS OH' CHEMICAL PAPERS. easily separated by crystallisation from water in which the latter is insoluble. The alcohol crystallises from water in long flattened needles melting a t 75" ; Jilckson and Lowery give 77" the higher melting point being probably due to the presence of some of the ether.Purabromobenzyl chroride C6HJ3r*CHC1 is obtained when the alcohol is treated wit)h phosphorus pentachloride but as other products are formed at the same time it is far better to heat the alcohol with fuming hydrochloric acid a t 150' in closed tubes for three to four hours. The reaction is complete and tbe chloride is obtained in a pure state by once recrystallising the product from alcohol. It forms lustrous colourless needles which melt at 38-39'. It is very soluble in hot alcohol and its vapour attacks the eyes but much less than that of the bromide. It is isomorphous with para- chlorobenzyl chloride and with parachlorobenzyl and parabromobenzyl bromides. Yarabroinobenxyl ether (C6H,Br.CH,),0.-As stated above this ether is formed at the same time as the alcohol when parabronio- benxyl bromide is boiled with water and is left as an insoluble residue when the product is treated witli hoiling water.It may be purified by repeated crystallisation from boiling alcohol. It can also be pre- pared by the action of dehydrating agents such as sulphuric acid boric anhydride or zinc chloride on the a,lcohol; the two first- mentioned do not yield satisfactory results but with zinc chloride the yield is almost theoretical. The ether crystallises from alcohol in long flattened needles which melt a t 85-86". It is insoluble in water and only sparingly soluble in alcohol even when boiling. If the ether is boiled for some time it is decomposed splitting up into parabrornotoluene and parabromobenzaldehyde ( CaH,Br*CH,)20 = CsH4Br*COH + C6H,Br°CH ; these can be easily separated by distil- lation.The ether is attacked by nitric acid with formation of para- bromobenzaldehyde and other products but the amount of material at the author's disposal was too small to allow of a complete investi- gation of the r( action. Purachlorober 8yZ Ether ( C6H4C1*CH2),O.-When parachlorobenzyl bromide is boiled with water or dilute soda solution it does not behave like the bromine-derivative as no trace of the ether is produced. The latter can be easily obtained however by boiling the alcohol with zinc chloride. It crystallises from alcohol in needles or plates which are much less soluble than parachlorobenzyl alcohol.It melts at 54-55" and when boiled splits up into parachlorotoluene Nitrobenzyl Ethyl Ethers. By G. ERRERA (Guzzetta 18 232-235).-This is a continuation of former work (Abstr. 1887 1 103). Paranitrob enz y 1 Et h y I Ether 0 E t C H C H4*N0,. -T he gen era1 method for the preparation of the substituted benzyl ethyl ethers that is the action of alcoholic potash on the corresponding derivatives of benzyl chloride is not applicable in the cilse of paranitrobenzyl ethyl c ther as paranitrobenzjl chloride under these circumstances is con- and parachlorobenzalde hyde. c. E. G.ORGAXIC CHEMISTRY. 249 verted into paradinitrostilbene. I n order to prepare it the cl-iloride is heated for a long time with ordinary alcohol in a clo,e vessel in a boiling brine bath as a higher temperature cannot be employed.The product even after long heating still contains much unaltered paranitrobenzyl chloride and in order to remove it a few drops of alcoholic potash are added to the liquid whilst i t is still hot; this at once converts the unattacked chloride into dinitrostilbeue which being almost insoluble i n alcohol is precipitated arid can be removed by filtration. The potash is then neutralised with hydrovhloric acid and the product distilled with steam when the ether passes over with the aqueous vapour and solidifies on cooling. Paranitrobenzyl ethyl ether is pale yellow and very soluble in alcohol and in ether sparingly in light petroleum from which i t crystallises in needles and insoluble in water. It melts at 24-24*S0 and a t a higher temperature distils but is a t the same time partly decomposed. Treatment with fuming nitric acid converts it in to paranitrobenz aldehyde. 21Zefanitrobeizzy 2 Ethyl Ether.-This is prepared by heating meta- nitrobenzyl chloride with a slight excess of alcoholic potash on the water-bath and when the reaction is complete neutralising the liquid with hydrochloiic acid and distilling the product with a current of steam.This ether is a yellow oil which solidifies to a crystalline mass in a mixture of snow and hydrochloric acid (melting point not given). It resembles the para-derivative in its behaviour to solvents and yields metanitrobenzaldehyde when treated with nitric acid. Orthonitrobenzyl Ethyl Ether.-The orthonitrobenzyl chloride em- ployed for the preparation of this ether was obtained by the nitration of benzyl chloride.The liquid product when cooled by a freezing mixture deposits para- and ortho-nitrobenzyl chlorides which can be easily separated by fractional cry stallisation. This may be much accelerated bF introducing a crystal of one or other chloride into the super- saturated alcoholic solution when crystals of the same species separate at once while the other chloride remains in solution and is deposited later. It can then be obtained in a pure state by one re- crystallisation. The ort honitrobenzyl ethyl ether prepared like the para-derivative is a yellow liquid which gradually becomes brown on exposure to the light. It does not solidify when cooled in a mixture of snow and hydrochloric acid and is converted into orthonitro- benzaldehyde by the action of nitric acid.Derivative of Tetrole and Synthesis of Tribenzamidophloro- glucinol. By L. RUGHEIMER (BPY. 21 3325-3331).-When ethyl hippurnte (5 parts) is gradually heated with dry sodium etlioxide so that in the course of about three hours the temperature rises to about 160-170" alcohol distils and on adding water to the residue two sodium salts are formed one of which is only very sparingly soluble in dilute soda. Dibenzavzidod ih y droz y tetrole CleH ,,N,O is obtained by separating the sparingly soluble sodium salt dissolving it i n boiling water and Rdding hydrochloric acid t,o the warm filtered solution. It can also be preparad by heating ethyl hippurate with sodium at 160-170". It crptallises from hot alcohol in needles containing $ mol.H,O loses C. E. G.250 ABSTRACTS OF CHEMICAL PAPERS. its water at 108-llO" the anhydrous crystals melting at 137-138". It is very readily soluble in hot benzene and alkalis but only moderately so in alcohol ; the alcoholic solution gives a violet colora- tion with ferric chloride. The bariurri salt is readily soluble in water. The silver salt is very unstable and rapidly darkens. The ethyl- derivative was obtained in an impure state as an aromatic smelling oil ; the acid seems to yield an acetyl-derivative when treated with acetic anhydride. When boiled for a long time with dilute hydrochloric acid or better with eight times its weight of a mixture of equal parts of concenti-ated sulphuric acid glacial acetic acid and water it is decomposed into benzoic acid and diamidoacetone.Its constitution is probably either COPh*NH*C<C(oH)>C.NH-COPh or C(OH) C 0Ph.N H*C H < > C H*NH*C OP h . Diamidoncetone platiwchlorida C3H8N20,H2Pt GI crystallises in small orange plates and turns bright yellow when warmed on the water-bath. Tribenzarnidophloroglucinol C27HZ1N3O6 is formed when the readily soluble sodium salt obtained in the reaction described above is decom- posed with hydrochloric acid. It crystallises from water in small needle3 containing 1+ mol. H20 and melting a t 153.5-158.5'. It is very readily soluble in alcohol but only very sparingly in hot water and insaluble in ether ; the alcoholic solution gives a blue colorntiori with a small quantity of ferric chloride but on adding more of the reagent the colour changes to green.It is decomposed with libera- tion of benzoic acid when heated at a comparatively low temperature. The lead salt (C27H,8N30,),f?b3 is sparingly soluble in water but the calcium barium and silver salts are readily soluble. The copper salt ( C27H,8N30,)2C~ is bright green. By J. V. JANOVSKY (Monatsh. 9 828-841).- Parazotoluene is best prepared by adding to 100 parts of 20 per cent. aqueous soda heated to loo" 100 parts of paranitrotoluene and then adding slowly and with constant agitation 100-110 parts of zinc- dust. An orange-coloured oil is formed which should at once be separated from the solution and left to crystallise. One recrystxllisa- tion from glacial acetic acid is sufficient to obtain pure parazotoluene melting at 144".It crystallises in rhombic needIe8 soluble in alcohol ether benzene and light petroleum and also in boiling hydroct~loric acid. When oxidised with chromic mixture it gives an orange- coloured crystalline compound melting a t 132". The acetic acid mother-liquor from the parazotoluene contains three other products which melt a t log" 75" and 70" respectively. The last of these is identical with the P-azoxytoluene of Melms and Petrieff whilst the compound melting a t 75" appears to be a peculiar isomeride of the same. Both these compounds yield two bromides when treated with bromine (2 mols.) those from the first melting at 85" and 57" those from the second a t 92" and 57". By actirag with nitric acid on the bromide of parazotoluene melting F.S. I(. Azotoluenes.ORGANIC CHEMISTRY. 251 a t 128" (Abstr. 1888 686) a nitrobromo-derivative melting a t 138" has been obtained. The nitration of pnrazotoluene with nitric acid of sp. gr. 1.5 yields chiefly trinitro-derivatives. Two of these are formed one (a) melting a t 189" and the other ( p ) a t 138". A dinitro-compound melting a t 114" is obtained a t the same time. All these compounds give sulphonic acids with fuming sulphuric acid. By the further treatment of a-trinitrazotoluene with nitric acid a tetr(tnitraaoto1uene melting a t 198-'200" is produced and p-trinitrazotoluene when nitrated gives the same compound. A mononitrazotoluene is formed on treating parazotoluene with nitric acid of sp. gr. 1.45. It melts a t 80" and on further nitration yields the dinitro-compound melting a t 114".H. C. Halogen-derivatives of Phenylhydraaine. By -4. N E UFELD (Annalen 248 93-99) .-The preparation of parachloro- and para- bromo-phenylhydrazine from the corresponding aniline-derivat,ives has already been described by Elsinghorst (Inau7. Diss. Erlangen 1884). These substances readily unite with aldehydes aud ketones. Acetorze- plrrabromopIienylhydrazone crystallises in glistening plates and melts at 93". Acetaldehydeparnbromophenylhydraaone forms yellow needles and melts a t 83". Dibrornophenylhydraaine [N,H Br = 1 2 51 prepared from dibromaniline by reduction with stannous chloride or sodium sulphite melts a t 97" and is freely soluble in alcohol ether and benzene. The hydrochloride is crystalline. Symmetrical tribromo- phenylh?ydraz.cne [N,H Br3 = 1 2 4 61 melts with decompo- sition a t 146".It is soluble in benzene chloroform warm alcohol and hot water. The hydrochloride and sulphate are stable salts. The acetone compound melts a t 54." TetrabromophenzJlhydrazine [N2N3 Br4 = 1 2 3 4 61 crystallises in prisms and melts at 167". It dissolves in chloroform benzene and hot water. The hydrochloride is crystalline. The compounds with acetone and acetaldehyde are solid. PariodophenlilhydrazirLe melt9 a t 103" and is freely soluble in alcohol ether chloroform benzene and acetic acid. The acetone compound crystallises in plates and melts a t 114". Metadi-idophenyl- hydraxine "2H3 T2 = 1 2 41 forms silky crystals which melt at 112" and are freely soluble in alcohol ether and benzene.The hydrochloride melts a t 163" with decomposition. The base unites w. c. w. with acetone and acetaldehyde to form hydrazones. Phenylhydrazones. By 0. RUDOLPH (Amalen 248 99- 105).- ~Metntoluylaldehy&ephenylhydrasone is deposited when a solution of phenylhydrazine in acetic acid is added to toluylaldehyde suspended in water. The compoiind crystallises in prisms melts a t 87-88.5" and dissolves in ether chloroform and alcohol. CicmaZdehydephenyZ- hydrazone melts a t 127-129". It rapidly turns red on exposure to the light. D~hen~l~rcetaldehydephe.nylhydrazone is freely soluble in hot alcohol. Metahydroxy benzaldehyde~hen~lh~d~axone prepared from252 ABSTRACTS OF CHEMICAL PAPERS. metamidobenzaldehyde forms colourless prisms. It melts at 1 30-131*5" and dissolves freely in warm alcohol chloroform benzene or acetic acid.Parahy~rozyhenzaldehydephenylh~drazone melts a t 17'7-178" and is freely soluble in ether.. Anisaldehyde- y h m y l l y d ~ - a z o n e forms white needles or plates and melts a t 120-121". It is freely soluble in ether and in hot alcohol or benzene. Pijieyonnl- yhrnylhydrazone melts a t 102-103". P-Resorc~ilaldehydephen,yIhydr- alone melts with decomposition between 156" and 160". It dissolves freely in the usual solvents. Resorcindial dehy dep hen y 111 y dyazon e melts about 230" with decomposition. It dissolves in warm solutions of the alkalis. w. c. w. Phenyltrimethylenimine. By L. RALBIANO ( C h e w . Cpntr. 1885 1356 from R e n d . Acnd. d e i Litrcei [4] 4 ii 44-46).-1f dry phenyl trimethj lenediamine hydrochloride is heated over a bare flame until the whole of the salt has volatilised and the vapours are condensed in dilute hydrochloric acid phenyltrimethylenirnlne and ammonium chloride are found in the solution.From the solution of the distillate after concentrating to a syrup alcohol precipitates the latter whilst the base is separated from the solution by acidifying with hydrochloric acid precipitating with potassiiim bismuth iodide and washing the red precipitate. After treating with potash and distilling with steam it may be precipitated as the platinochloride C,H,:NPh,H,PtCI an orange crystalline compound soluble in hot water. The hydrochloride could not be obtained in crystals from the aqueous solution J. W. L. Hippuroflavin.By L. R~GHEIMER (Ber. 21 3321-3325)- HippuroJavin C9H5N02 is prepared by gradually heating a mixture of ethyl hippurate (1 mol.) and phosphorus pentachloride (1 mol.) until the latter is dissolved and then adding a little more phosphorus pentachloride and heating a t 160" for about eight hours. The whole is poured into alcohol and the crystalline product collected and washed with alcohol. T t separates from hot nitrobenzene o r hot glacial acetic acid in small yellow crystals partially decomposes but without melting when heated a t 3W0 and sublimes with partial tlwomposition in citron-yellow crystals. It is very sparingly soluble in glacial acetic acid and nitrobenzene and almost insoluble in water alcohol and ether. When warmed with alcoholic soda it is decom- posed with evolution of ammonia and when heated at 100" for 8 to !) hours with concentrated ammonia the red solution obtained deposits a colourless crystalline compound. It yields benzoic acid when warmed with alkaline potassium permanganate or when heated a t 130" with nitric acaid of sp.gr. 1.15 ; and w-hen treated with concen- trated hydrochloric acid at 1 1 O" it is completely decomposed into beilzene carboil and dark-coloured products. When boiled with zinc-dust and glacial acetic acid i t yields a yellowish substance which dissolves in soda with a brown coloration but is reprecipitated in greenish flocks on adding hydrochlaric acid. It is gradually con- verted into a colourless compound when warmel with stannousORGANIC C t1E:JlISTRY. 253 chloride and hvdrochloric acid in glacial acetic acid solution.Its /N(COPh)*.C*CO -\* - CO*&(COPh)N/ F. S. K. constitution is probably \ Phthalimidine and Methylphthalimidine. By P. RARBIER (Compt. rend. 107 9 18-921).-Phthdimidine is readily obtained by the gradual addition of small quantities of hydrochloric acid to an acetic acid solution of phthalimide containing the calculated quantity of granulated tin. It forms white needles melting. a t l50" and can be recrystallised from boiling water it is isomeric with oxindole and is both au amine and an amide. It forms an unstable hyclrochloride which can only exist in presence of free acid and loses all its hydro- chloric acid in a vacuum. The hydrochloride is completely decom- posed by water ; the platinochloride ( CsH,N0)2,H2PtC16 and the aurochloride ( CeH7N0,HC1),,2AuC1 are both unstable.A deriva- tive CeH,NOAg is obtained as a white precipitate by adding silver nitrate to a solution of phthalimidine in potassium hydroxide solution. When a solution of phthalimidine in potassium hydroxide is heated in sealed tubes a t 100" for six hours with excess of methyl iodide methylphthalimidine C9HgN0 is obtaitied in slender white needles which melt a t 120". It forms an unstable hydrochloride and an unstable aurochloride ( CgHgNO) HAuC14. The properties of methyl phthalimidine indicate that it has the constitution C6H,<CH,>NMe CO CH2*NH and not c6H4<co.cH >. This view is confirmed by the fact that a concentrated alcoholic solution of methylamine yields methylphthal- imidiire when heated with phthalide a t 220" for 12 hours.C. H. B. Derivatives of Diphenylacetaldehyde. By W. G. M. WEISE (AnnaZen 248 34-56). Hydrobenzoin is most conveniently pre- pared from benzo'in by the method described by Breuer and Zincke (Abstr. 1880 118). It is converted into diphenylacetaldehyde by treatment with dilute sulphuric acid at 200"; this substance is converted into a nitrile by adding powdered potassium cyanide and finally hydrochloric acid to its ethereal solution. When dry hydrogen chloride is passed into a mixture of the nitrile and absolute alcohol (in molecular proportions) crystals of ethyl $-diphrnylimidolat tate hydrochloride CH Ph?*CH( OH) C ( O E t ) :NH,HCl are deposited. The hydrochloride melts a t 135" with decomposition ; it is also decomposed by dissolution in water yielding in this case ammonium chloride and ethyl P-diphenyllactate.The latter is a micro-crystal line powder melts at 66O and yields a monacetyl-derivative CHPh,.CH(OAc)-COOEt melting a t 53". P-DiphenyZZactic acid CHPh,-CH(OH)*COOH crystallises in needles,'and melts at 159". It is freely soluble in alcohol ether and hot water. The salts of this acid do not readily crystallise. At 170" the acid is converted into the anhydride COO H*CH (C HPh,).O*CO*CH( 0 H) *C H P h,. Hydriodic acid d ecom- poses P-diphenyllactic acid a t 150" into carbonic anhydride and254 ABSTRACTS OF OEEMlOAL PAPERS. diplienylethane. Jf the reaction takes place at a higher temperature dtbenzyl is also formed. w. c. w. Passivity of certain Polyketones towards Hydroxylamine and Phenylhydrazine.By J. HERZIG and S. ZEISEL (Ber. 21 3493-3494 ; compare Kehrmaun this vol. p. 243).-Tetrethyl- and pentethyl-phloroglucinol (Abstr. 1888 822) do not react with hydroxylamine or phenylhydrttzine and it would therefore seem that meta-diketones no longer give the characteristic ketonic reaction with these compounds when the hydrogen-atoms in the ortho-positions to the cnrbonyl-groups are almost completely or completely replaced by alkyl-groups. w. P . w. Nitriles. By J. A. MILLER (Chem. Centr. 1888 1359).-Para- methoxybenzaldehyde reacts with hydroxylamine with formation of pammethoxybenzaZdoximp OMe*C6Hd.CH:NOH melting at 64". By the action of sodium nitrite and hydrochloric acid the aldehyde is regenerated. When heated with acetic chloride the nitrile OMe*C6H4*CN is formed which melts a t 61-62'.By heating this riitrtle with hydroxylnmine hydrochloride and soda param,ethoxy- benzen ylumidoxime OMe*C6H,*C(NH,):NOH is formed melting at 122-125'. I t s hydrochloride melts a t 1 68". Paramethoxybenzenyl- ainidoxime ethyl ethei- OMe*C,H4.C(N H,):NOEt melting at 51-52" is prepared by heating the amidoxime with sodium ethoxide and ethyl iodide. Plnra?.lzefhoxylbenzenylacety lamicloxime OMe*C6H4*C(NH2):N0 Ac is formed when a chloroform solution of the amidoxime is treated with acetic chloride. Puramethox y benzenylethen~~lazoxime OM~C6&'C<&~>C&3 melt- ing a t 68" is formed by heating the acetyl compound or by the direct action of acetic anhydride on the amidoxime.With acet- aldehyde paramethoxybenzeu y lethylideneimidoxime melting a t 127.5" is formed. The ethyl carbonate of the amidoxime OMe*C6H4*C(NH,):N.0.c~oEt melting a t 119-120" i q formed by the action of ethyl ohlorocarbonate on the amidoxime in chloroform solution. When treated with solution of soda or potash this car- bonate is changed into pal-amethoxybenzen~li~id~~~mecarboriyl ; this may also be prepared by heatirig the chlorocarbonate with the amidoxime. It melts at 208". Paratnethoxybenzoylbenzenylnmidoxime O~~e.C,H,.C(NH,):N*OBz melting at 148" is prepared by the action of the amidoxime in alka- line solution on benzoic chloride a t the ordiiiary temperature. If heat be employed pararnethoxy b enxeny lazoxim ebenzenyl N.0 OMe*C6H4.C< - N>C Ph is formed which melts at 102".ORGANIC CHEMISTRY.255 melting at 140-141" is formed by melting succinic anhydride with the amidoxime. The salicyl derivatives are formed in a similar manner. Salicylaldoeinze melts a t 57" ; sa7icyzonitrile OH.C6H,*CN melts at 99-100" ; a polynitrile is formed a t the same time as a secondary product ; it is decomposed on heating with concentrated hydrochloric acid a t '200" into phenol carbonic anhydride and ammonia. SalicyZ- arnidozime OH.C6H4*C(NH2) :NOH melts a t 98.5". Si~1icyZamidoa:inze ethyl carbonate OHoc6H4*c(NH,):N.0.COOEt melts at 96". Salicyl- arnidoximepropenyl-w-carbox?llic acid melts at 116-11 7". Ortho- nzethoxybenzonitrile OMe*C6H4*CN boiling point 255-256" is pre- pared from salicylonitrile by the action of methyl iodide; oytho- rnefhoxybmzenylamidoxirne OMe.C,H,.C'(NH,):NOH melting at Us" is formed from the last-named substance by the action of hydroxyl- amine.By melting this amidoxime with benzoic chloride ortho- inethoxybenzenylazoxi~nebenze~i yl OMe*C,H,*C<-,>C N-0 Ph is formed ; it melts at 117". J. W. L. Derivatives of Metamethylphenylacetic Acid. By M. S ~ N - KOWSKI (Monafsh. 9 854-856).-Methyl metamethylphenylacetale is prepared by saturating a solution of the acid in five times the amount of methyl alcohol with hydrochloric acid. It is a liquid of sp. gr. 1.044 a t 17.5" boiling at 228-229". The ethyl salt prepared in similar manner has a sp. gr. of 1.018 a t 17.5" and boils a t 257-238". By dissolving metamethylphenylacetic acid in concentrated nitric acid carefully cooled a product is formed which melts at 70-llO" but cannot be obtained of constaiit melting point.It gives an ethyl salt which is still liquid a t -30". If the nitric acid solution of the acid is heated for some minutes on the water-bath a dz'nitro-derivative ~ 6 ~ ~ e ( N ~ ) * ~ ~ o ~ ~ ~ ~ is obtained melting a t 173-174". The salts of this acid are very unstable decomposing i l l aqueous solution even a t the ordinary temperature into dinitro-xylene and carbonic anhydride. The methyl salt prepared by saturating the solution of the acid in methyl alcohol with hydrogen chloride crystallises in yellow needles melting a t 41". The ethyl salt similarly prepared melts a t 68". H. C. Scopoletin. By D. TAKAHASHI ( Chem. Centr. 1888 136%-1365 €rom Mitt. nzed.F a k . Univ. Tokio) .-Scopoletin C10H804 the fluorescent substance occurring in Scopoliajaponicu is extracted from the roots by treatment with alcohol evaporation of the alcoholic solution treat- ment with strong hydrochloric acid drying with admixture of sand extraction with chloroform and finally recrystallisation several times from absolute alcohol. It consists of colourless needles melting at 198-199" little soluble in cold water readily soluble in alcohol ether and chloroform. AcetyZscopoZdia Cl,,H704Ac melts at I76O,256 ABSTRACTS OF CHEMICAL PAPERS. and is little soluble in water but soluble in alcohol. BenznyZscopoZetin is insoluble in water little soluble in alcohol and melts a t 158". ikIethylsoopoZetin CloH70iMe is prepared by heating a mixture of scopoletin (1 mol.) methyl iodide (2 mols.) and potassium hydroxide (2 mols.) in methyl alcohol on the water-bath.It foyms long colourleQs needles melts a t 144" is insoluble in cold water soluble in hot water alcohol. ether benzene and ciirbon bisulphide insoluble in alkalis in the cold. This characteristic together with the pnrt,ial decrease in the fluorescence in alkaline solution indicate in the same way as the charatoteristic reactions of coumarin that scopoletin is also a coumarin-derivative. Since dimebhylaesculetin and methylscopoletin have been proved to be identical and since also the bromine-derivatives are alike scopoletin must be a derivative of hydroxyquinol. Methylscopoletilic acid CllH1,,05 is prepared by heating monobromomethylscopoletin with potash a reaction which is also similar to those which the dibromo-derivatives of coumarin undergo when heated with potash.If its silver salt is decomposed by carbonic anhydride a colourless pleasant-smelling oil is obtained which when treated with strong aqueous soda and distilled with steam bscomes converted into dimethoxycaumarin C10Hlo03 melting a t 58". Methy7 tl.imetl27JlcescuZetate C,H2(Me0)3*CH:CH*COOMe is prepared by melting methylscopoletin with potash extracting the mass with methyl alcohol and heating wibh methyl iodide in a closed flask for three hours. By recrystallising several times from alcohol the pro- duct remaining after the alcohol has been evaporated off it is obtained as a yellow cr-ystalline substance melting at 102" insoluble in water but readily soluble in alcohol and ether ; it yields the free acid on hydrolysis &c.By reduction with sodium amalgam t w h e t h o x yph eny lpropionic acid C,H,( OMe) 3*C H,*C H,.C 0 OH is formed from which by oxidation with potassium permanganate trimethoxybenzoic acid is obtained. From this t'rimethoxyquinol can be obtained ; the constitution of scopoletin is therefore concluded to be < H:CH> CdL( OMe) *OH. co-0 J. W. I;. Homo-orthophthalic Acid. By M. LE BLANC (Chem. Cpntr. 1888 1352-135:3).- Dipropy Zhom o-orthoph thalimide C9H,Pr,N0 prepared by the action of propyl iodide on homo-orthophthalimide in alcoholic cJolution melts at 141.5". DipropyZhonzo-orthophthalic anhydride C,H4Pr203 pTepared by heating the h i d e at 240" with fuming hydrochloric acid melts at 88".Di~oi3.'/lhomo-orthoiphthnlic acid CgHGPr201 prepared by treating the anhydride with potash melts at 127". Homo-orthophthalopropylirrcide prepared by distilling a solution of homo-orthophthalic acid in propylamine crystallises in leaves which melt at 69-7~". Nitrobenzenehomo-orthophthalopropy limide prepared from the last-named iruide by treating it with nitrobenzaldehFde melts a t 119". Xa.Zicylhomo-mtho~ht?~alopropyli~ide prepared in like manner to the last-named compound melts a t 157". Aldehydes of the fatty series such as isovaleraldehyde react in a manner quite different from t h e aromatic aldehydes.ORffXNIC CHEMISTRY. 257 Dibronzo-orthophthalimide prepared by the action of bromine on Synthesis of Dialkyl Phthalides. phthalimide in acetic acid solution melts a t 168.5'.J. W. L. By R. KOTHE (Annalen 248 56-7l).-Dirrteth~jlphtlzalide C6H4<C0 :>O prepared by acting on a mixture OE methyl iodide and phthalic anhydride with zinc-dust melts a t 67-68" and boils a t 270-271". It is easily obtained in laage crystals exhibiting the phenomenon of double refraction. It dissolves in a solution of potassium hydroxide forming the potaqsium salt of orthohydroxyvisopropylbeneoic acid. Reduction with sodium amalgam converts dimethylphthalide into dimethylhydrophthalide C H 4 < ~ ~ ~ o G > 0 and hydriodic acid reduces it to orthoisopropyl- benzoic acid. Potassium cyanide acts on dimethylphthalide at 250" ; dilute sulphuric acid converts the product into an acid probably orthoprnpenylbenzoic acid.The acid melts a t GO-61" and forms rh crystalline barium and silver salt. Diethylphthnlide is an oily liquid boiling at 210-214" under 210 mm. pressure. It appears to be identical with the compound described by Wischin (Annalen 143 262). Benzyl chloride acts energetically on a mixture of zinc-dust and phthalic anhydride yielding an amorphous product solcble in ether and benzene. It CM This substance melts a t 73" and is non-volatile. does not contaiii oxygen. w. c. w. 7-Ketonic Acids. By A. DITTRICH and C. PAAL (Rer. 21 3451-3457).-Ethyl P-benxo!ll-a-eth!llisosuccirtilte (ethyl phenacyl- ethylmalo?/ate) COPh.CH,*CEt (COOEt) is prepared b.y treating ethylic ethylsodomalonate suspended in absolute ether m ith the cal- culated quantity of bromacctophenone (phenacyl bromide).It is an oil which dissolves in the ordinary organic solvents and decomposes when distilled in L vacuum. The corresponding acid crystallises from most solvents in slender white needles or long scales but can be obtained in cruciform aggregates of fairly la~ge four-sided prisms with oblique terminal faces by the slow evaporation of its solution in a mixture of chloroform and light petroleum ; the prisms however contain chloroform of crystallisation and effloresce on exposure to the air. The acid melts at 150" with evolution of carbonic an- hydride; is insoluble in light petroleum sparingly soluble in hot water and benzene and readily soluble in alcohol ether chloroform and acetic acid. Treatment with phosphorus pentachloride converts it into the dichloride which is readily decomposed by water.The ammonium potassium calcium (1 mol. H20) and silver salts are described. The hydrazone C,,H,,NaQ3 cystallises in concentrically- grouped slender white needles melts a t 132" is readily soluble in the ordinary organic solvents and when heated above its melting point loses carbonic anhydride and is converted into a substance insoluble i n alkalis or alkaline carbonates. ~-nenzo1/l-a-et7Lylpropionic acid (pl2erLacyleth!/lacetic acid) COYh.CH,*CHEtCOOH is formed when ~-benzogl-r-eth~ lisubuo-258 ABSTRACTS OF CHEMICAL PAPERS. cinic acid is heated above its melting point. It crystallises from acetic acid in small aggregates melts at 81-F13O decomposes on distillation and vields a hydrazone insoluble in alkalis. The calcium salt (C,2H,30,)2Ca + H20 crystallises in white scales and is in- soluble in absolute alcohol but readily soluble in water; the ethyl salt is a yellowish oil.2 4-Phen~ZethyZt~iophert CAH2SPhEt is obtained by distilling sodium p-benzoyl-a-ethylpropionate or sodium hydrogen/3-benzoyl- a-ethylisosuccinate with phosphorus pentasulphide. It crystallises in small white scales melts at about 40° and has the characteristic w. P. w. Reissert's Deoxypyranilpyroic Dibromide and Bromodeoxy- pyranilpyroic Acid. By R. ANSCHUTZ and 3'. HENSEL (AnnaZen 248 269-281).-The anthors have previously shown (Abstr. 1888 1092 j that Reissert's diliydropyranilpyroic acid (Abstr. 1888 696) is identical with the pyrotartaric-anilic acid. On repeating Reissert's experiments on the action of bromine-water on dihydropyranilpyroic acid they find that the so-called deoxypyranilpyroic dibromide con- sists of a mixture of tribromaniline and pyrotartaric-parabromanilic acid and the so-called monobromodeoxypjranilpyroic acid is impure pyrotartaric-parabromanilic acid.Pyrotartaric-parabromanilic acid is the chief product ol the reac- tion of bromine-water on sodium pyrotartrate ; no tribromaniline is produced. Parabromaniline unites with pyrotartaric anhydride in benzene solution forming the parabromanilic acid of pyrotartaric acid (m. p. 158-158.5'). It is converted into the corresponding para- bromanil by the action of phosphorus pentachloride. Dibromaniline [l 2 41 yields a pyrotartaric-dibromanilic acid melting a t 139"; but tribromaniline does not combine with pyro- Dyes from Diamidoethoxydiphenylsulphonic Acid.By A. FEER and H. M ~ L L E R (Chem. Cedr. 1888 1358 from BUZZ. Xoc. indust. Mulhouse 1888 488-490).-Diazobenzene and sodium para- phenolsulphonate react together with formation of a dye of the constitution PhN2-CaH3(OH)*S03Na [ = 1 41 of light-yellow colour little soluble i n cold water readily so in alkaline solutions. I f this is heated in a sealed tube with ethyl bromide and soda in mole- cular proportion the corresponding ethyl salt of ethozyazobenzenesul- phonic acid is formed. Reduction with stannous chloride in hydro- chloric acid or with zinc-dust in alkaline alcoholic solution leads to the formation of diamidoethosydi~he,2ylsulphonic acid odonr of the two known phenylethylthiophens.tartaric anhydride in solution in benzene. w. c. w. NH,.CsH4*CsH4(NH2)(OEtl).S03H [OEt S03H = 1 41. Sodium acetate precipitates the free acid in crystals from its con- centrated solution. By treating the hydrochloric acid solution of this sulphonic acid with sodium nitrite (2 mols.) tetrazoethoxydiphenyl- sulphonic acid is obtained which by treatment with phenol (2 mols.) or amines in dilute alkaline solution yields yellow red and violet dyes ;OROASIC CHEXISTRP. 25 9 these dye cotton without the use of a mordant although the dye is not so fast as when one is used. J. W. L. Indole-derivatives. By L. WOLFF (Ber. 21 3360-3366) .- 3 2' ~'-Trin?ethylindoZe CIIHLaN is obtained when p-bromolevulinic acidis heated with three times its weight of paratoluidine.tallises in white scales having a peculiar odour melts a t 121*5" boils at 297" (corr.) is volatile with steam and dissolves sparingly in water but readily in alcohol chloroform and light petroleum. When allowed to rema.in for a few days it becomes yellow and finally brown and its acetic acid solution is coloured at first green and afterwards an intense blue on boiling with a small quantity of ferric chloride. The p i c r a t e crystallises from alcohol in brownish-red needles and melts a t 189" ; the nitroco-derivative CIIH12N*N0 forms lustrous golden-yellow needles melts a t i3" and is sparingly soluble in water readily soluble in alcohol and acetic acid. 1 2' 3'-Trirnethylindole prepared in like manner from ortho- toluidine crystallises in white scales melts a t 79" boils a t 282-283" and closely resembles the 3 2' 3I-derivative in its solubility and behaviour with ferric chloride.The picrate C11Hl~N,C6H2(N02),-OH crystallises in purple-red needles and melts a t 152". Ethyldzmethylindole [Et Me Me = 1' 2' 3'1 obtained in like manner from ethylaniline is a yellow oil which boils a t 280-282" has the persistent indole odour dissolves readily in alcohol ether and benzene and when boiled in acetic acid solution with a small quantity of ferric chloride or potassium dichrornate vields a very characteristic- intense red coloration. The picrate C d 15N,CsH2( N02),.0H crystal- lises in small dark-red needles melts at 105" and is soluble in benzene. 2'' 3"-Dirneth~j~-~-nap~2thi~ndoZe formed under similar conditions from p-naphthylamine crystallisea from alcohol in colourless brittle strongly refractive tablets melts a t 132" boils above 360" and is only slightly volatlile with steam.It is insoluble in water soluble in alcohol and acetic acid and readily soluble in ether and benzene and its solution in acetic acid is coloured green on boiling with ferric chloride. The picrate crystallisw in lustrous dark- brown needles melting at 175". 2" 3"-DimPthyl-a-naphthindole prepared in like manner from a-naphthylamine crystallises from alcohol in small white granules or prisms melts a t 150" and is insoluble in water sparingly soluble in cold alcohol and acetic acid and readily soluble in ether and benzene. When heated in acetic acid solution with a trace of ferric chloride it yields a beautiful cherry-red coloration whilst with potassium dichro- It crys mate it gives an intense blue.w. P. w. Indoles. By B. TRENKLER (AnnuZen 248 106-113).-~a]er- aldehydephenylhydrazone boils a t 280" under a pressure of 150 mm. I t is converted into 3'-isopropylindole by fusion with zinc chloride. 3'-Isopropylindole is a pale-yellow crystalline mass freely soluble in alcohol ether benzene chloroform light petroleum and acetic acid. It boils at 287-2288". The picrate crystallises in needles260 ABSTRACTS OF CHEMICAL PAPERS. and melts at 96-99". H!idroisopropyllinaole prepared by the act>ion of zinc-dust and strong hydrochloric acid on an alcoholic solution of isopropylindole resembles hydroscatole in its properties (Abstr. 1887 957). 3'-Pen,fyZindoZe from oenanthaldehydephenylhydrazone bods a t 345-347" and is freely soluble in alcohol ether and benzene.The picrate is crystalline. 2' .3'-r~~efhyZ~henyZindoZe from methjlbenzyl- lretonephenylhydrazone crystallises in colourless prisms and me1 ts a t 59-60". The picrate and tthe nitroso- compound are crystalline. 2' 3'-BewzyZphenyZindoZe from dibenzyl- ketone forms six-sided prisms and melts a t 100-101". It is freely soluble i n alcohol ether benzene chloroform and acetic acid and It' does not stain pinewood. does not exhibit the pinewood reaction. w. c. w. Decomposition of Benzidine Hydrochlorides by Water. By P P E w r (Cornpi. rend. 107 839-841).-Benzidine monohydro- chloride is stable in solution and when potassium sulphate is added an insoluble sulphate (C12H,2N2)2,H2S0 is precipitated but no free acid is liberated.I n the case of the dihydrochloride dissociation takes place according to two distinct laws. If the concentration of the solution does not exceed 5.4 grams per litre a constant fraction (0-034) of the salt is dissociated into the monohydrochloride and hydrochloric acid. When the concentration exceeds 5.4 grams part of the monohydrochloride formed is precipitated and the quantity of dihydrochloride decomposed is the sum of two quantities namely the fraction corresponding with a concentration of 5.4 grams and a quantity proportional to the excess of dihydrochloride over arid above 5.4 grams per litre. C. H. B. Similar Reactions of Carbazole and Pyrroline. By S. C. HOOKER (Rer. 21 3299-3301).-Carbazole like pyrroline gives the pinewood reaction a fact which is not in accordance with Fisclier's conclusion respecting this reaction (compare Abstr.1886 806). Carbazole gives with isa.tin and concentrated sulphuric acid a deep blue solution from which water precipitates an indigo-blue substance the colour of which rapidly becomes lighter. When a small quantity of sulphuric acid diluted with one or two volumes of acetic acid is added to an acetic acid solution of carbazole and quinorie a carmine- red solution is obtained from which water precipitates a red o r reddish-violet substance soluble in ether chloroform and alcohol. (Compare Meyer and Stadler Ahstr. 1884 1045.) A green solution is produced when oxidising agents such as quinone are added to a solution of carbazole i n sulphuric acid and the colouring matter which is precipitated by water is insoluble in ether.(Compare Grabe and Glaser this Journal 1872 302.) Pyrroline also yields i l green substance when treated with a very small quantity of an oxidising agent in dilute sulphuric acid solution; this green com- pound is rapidly destroyed by strong oxidising agents. (Compare Mever and Stdler Zoc. cif.). Pyrroline yields a crjstalliue compound with picric acid ; i t meltsORGANIC CHEIIITSTRY. 261 at about 71" and is unstable. Phenylpyrroline also combines with picric acid. F. S. I(. Malachite-green and Derivatives of Paramidodiphenyl- methane. By A. MANNS (Chem. Centr. 1888,1363) .-The leuco- base of malachite-green when distilled over zinc-dust is reduced to aniline dimethylaniline and paramidodiphenylm ethane together with hydro- carbons of the fatty arid aromatic sevies.Paramidodiphenylmethane was prepared synthetically from para- nitrobenzyl chloride by means of Friedel-Craf t's aluminium chloride reaction in benzene solution. NitrodipheiLy1,rLethatLe thus obtained melts at 30-31". It is reduced by tin and hydrochloric acid to paramidodipheny lmethane and from this diazoamidodiphenyl methane C2sH27N3 is prepared by treatment with nitrous acid. Meth y7paramidodiphenylmethane CI3HIl*NHMe i R obtained from amidodiphenylmethane by the action of methyl iodide ; it boils above 360" aud is a light yellow oil. The hpdriodide melts a t 150". AcetylparamidodiphenyImethni~e melts at 127.5" ; the benzoyl-derivative melts at 162a. Diphenylmethalze hydrazine C17H11*NH-NH2 is obtained as hydrochloride by reducing diazodiphenglmethane with stannous chloride in hydrochloric acid solution. The free base crystallises in yellow scales melts at 85" and boils above 360" without decomposition.Parabenzy7-a-quinoline C1,H13N7 is prepared from paramidodi- phenylmethane by means of Skraup's reaction ; it melts at 80*5" boils above 360" and is characterised by the large number of well-crystnl- lised simple and double s d ts it forms. Di23aradi~henylmetharzethio- carbamide CS(NH.C,,H,,) prepared by the action of carbon bisulphide on nmidodiphenjlmethane crys tallises in yellow scales and melts a t 147". The sulphur-atom is replaced by oxygen by the action of plumbic oxide. If however an excess of amidodiphenyl- methane is employed triparadiphenyZrnethanegu(x nidine C40N35N3 is formed melting point 100".Parad~henyImet~ianecarbamide NH2*CO-NH*C13Hll melting at 160" is prepared from paramidodi- phenylme thane hydrochloride by the action of potassium cyanate. The disubsfituted carbnmide GO (NH*C13H11)2 is prepared by the action of carbonyl chloride on the base or by fusing the last-named carbamide ; it melts a t 226". &'thy1 dipl~en~lmethanecarbainate C,,H,,.NH*COOEt melts at 65" and is prepared by the action of ethyl chlorocarbonate on the base. J. W. L. Arrangement of Atoms in Space. Part 111. Members of the Stilbene-group. By J. WISLICERUS and A. BLANK (Annalen 248 1-34).-After referring to the researches of Grimaux Zinin Goldenberg Zagoumenny Limpricht and others on the action of reducing agents on benzoin the authors state the results of their own experiments on the action of zinc-dust and acetic acid on an alcoholic solution of benzoin.The yield of deoxybenzoxn dirninishes if the reduction is carried on for more than three hours; the amount of deoxybenzokpinacone increases. Small quantities of stilbene are formed together with a substance crystallising in needles and melting VOL. LVL. t262 ABSTRACTS OF CHEMICAL PAPERS. a t 172" which proves to be p-deoxybmzohpinacone. and p-pinacones decompose on distillation yielding phenyl bemy1 ketone and phenyl benzyl carbinol. The pinacones are optically inac- tive and probably stand in the same relation t o each other as mesotar- taric and racemic acids. for a-tolane dichloride Both the Ph*C*Cl Ph*h*Cl Wislicenus suggests the formula Ph*C C1 Cl*&Ph for p-tolane dichloride which melts a t melting.at 143" and 63". A determination of the molecular weight by Raoult's method and the vapour-density show that the substances are isomeric. When tolane tetrachloride is reduced by zinc the yield of a-tolane dichloride is increased and that of the /3-dichloride diminished by raising the temperature from 20' to 80" or 130". Ditolane hPxnchloride CPhCI,*C'PhCl.CPhCI*CPhCl i s formed hv dissolving tolane tetrachloride and a-dichloride in molecular pro- portion in boiling alcohol ; on cooling the hexachloride is deposited in rhombic plates soluble in benzene; it melts a t 150'. Although Raoult's method giveq 266 as the molecular weight of this com- pound instead of 568.4 the authors regard it as a definite com- Found and not as a mixture of the di- and tetra-chlorides as i t i s formed by the action of chlorine on a mixture of the a- and p- dichlorides.p-Dichlorotolane will not unite directly with the tetrachloride to form the hexachloride. w. c. w. Nitroparadiphenols. By E. KUNZE (Ber. 21 3331-3335).- ~etadinitroparrzd.?lzenol [(NO,) (OH) = 3 3' 4 4'3 is formed when the calculated quantity of nitric acid of sp. gr. 1.45 is added t o paradiphenol in glacial acetic acid solution. It separates from glacial acetic acid in brown needles o r nodular crystals melting a t 272". ~~etadiamidoparadi~?ienol [ (NH,) (OH) = 3 3' 4 4'1 crystal- lises in colourless plates decomposes when heated and dissolves in qlcoholic ammonia with a green coloration.The hydrochtoridr C,,H,(OH),(NH,),,~Hcl crystallises in colourless needles. The acetyZ-derivative Cl2H8N2O2Ac4 crystallises i n colourless needles and melts a t 225". Dietheizyldiamidodihe~oZ C M e ~ ~ > C H . C 6 H < N ~ C M e 0 0 is ob- tained when the acetyl-derivative is heated above its melting point. It crystallises in colourless prisms melting a t 193". TetrazodiphmoZ NGN> C6H,*C6H,<N>N obtained by diazotising t h e diamidodiphenol dissolves in hydrochloric acid with a red colora- tion but is reprecipitated unchanged when ammonia is gradually added to the solution. Dipherboldihydl-azine hydrochloride [(N,H,) (OH) = 3 3' 4 4'1 prepared by reducing the tetrazo-compound with stannous chloride and hydrochloric acid crystallises in slender needles.When ammonia is added t o the aqueous solution the free base is precipitated in 0 0ORC,A'ETIC CHEJIISTRT. 263 mlourless crFstills ; it mcJlts a t 140" with decomposition and reduces Fehlin$s and ammoniacal silrer solutions. DiacetonPdiluhe~ioklih2/nraznne Cl,H,,N402 is obtained when acetone is added to an aqueons solution of the dihydrazine hydrochloride until the mixture commences to become trrbid. It crystallises in colourless rhombic plates melts a t 200" and is readily soluble in soda but only sparingly in ammonia and insoluble in alcohol and ethw. Analogous condensation-products are obtained with ethyl aceto- acetate pyrnvic acid benzaldehyde and salicylaldehyde. The tetranitrodiphenol whirh is formed when paradiphenol or metadinitroparadiphenol is nitrated in glacial acetic solution or when benzidine is treated with nitric acid (compare Caro; Griess arid Schmidt Schultz Abstract 1881 909) has the constitution [(NO,) (OH) = 3 3' 5 5' 4 4'3.It yields tetramidoparad~lzenol when reduced with tin and hydrochloric acid. Tetrnmidoparadiph e H 01 crys tallises in cnlourlew needles and decom - poses but does not melt when heated. It oxidises very readily turns blue on exposure to the air 2nd is converted into a brownish-black crystalline compound C,2Hl,N40?. M hen R stream of air is passed for a long time through an ammoniacal alcoholic solution. I?. S. K. New Method of Formation of Benxhydrol-derivatives By K. ALRRC CHT (Re?.. 21 329'L-3.29~).-Dimefhylnmidobenl.hydrol OH*CHPh-C6H4*NMe can be obtained by heatinz a mixture of benzaldehyde (1 mol.) and dimethylaniline (1 mol.) with 20 times its weight of concentrated hydrochloi-ic acid a t 100" for 50 hours neutralising the solution distilling the unchanged compounds with steam and recrystallising the residue first from alcohol and then from light petroleum.It can also be prepared by reducing dimethylanlido- benzophenons with sodium amalgam in alcoholic solution. I t crys- tallises in slender needles melts a t 69-70' and is very readily soluble in most solvents but only moderately so in ligbt petroleum and insoluble in water. It dissolves in acids yielding colourless solutions which become yellow when warmed. It is converted into leucomalachite-green when heated with dimethylaniline and zinc chloride.NO,-C,H,.CH (0 H).C6H,*NMe is prepared by heating a iriixture of paranitrobenzaldehyde (15 I gramsl dimethylaniline (121 grams) and hydrocliloric acid ( 3 kilos.) for 40 hours neutralising the filtered solution washing the precipi- tate and separating the dimethjlaniline by distilling with steam. The yield is 80 per cent. of the theoretical. It crystallises from dilute alcohol in slender yellow needles melts at 96" and is very readily soluble in most ordinary solvents but insoluble in water and light petroleum. The cold acid solutions are colourless but turn yellow when heated. It yields paranitroleucomalachite-green (m. p. 176-177" j when warmed with dimet,hylaniline and zinc chloride and when treated with alkaline reducing agents i t is converted into the corresponding azoxy- azo- and hydrazo-compounds.When heated with met,hyl iodide in methyl alcoholic solution a colourless crys- ParanitrodimethriZa?nidobenz hqdm I t 2264 ABSTRACTS OF CHEMICAL PAPERS. talline cornpound,. probably the rnethiodide is obtained it meIts a t about 175" with liberation of methyl iodide. The salts are all very readily soluble and difEcult to obtain crystalline. The platinochloride (C,,H,,N,O,),,H,PtCl crystallises in needles and is decomposed by boiling water. Dimethy7diamidobenz~?/~rol NH,*C,H,.CH(OH)*C,H(*~Me~ pre- pared by reducing paranitrodimethylamido benzhydrol with zinc and hydrochloric acid melts a t 165" and loses 1 mol. H,O when heated above its melting point. It dissolves in acetic acid with a blue coloration and cr,ystallises from benzene in shininq needles containing benzene which melt and lose their benzene a t 142".It yields tetra- methylparaleucaniline when condensed with dimethylaniline. The leuco-bases obtained by the condensation of dimethyldiamido- benzhydrol with other aromatic bases yield reddish-violet or blue dyes whereas those obtained from paranitrodimethylamidobenzhydrol yield greenish colouring msttters. Diw ethy Id iamidodiphen!y Zmef harte NH,. C6H1.CHL*C6H4*N Me2 is o b- tained by boiling paranitrodimethylamidobenzhydrol or the corre- sponding diamido-derivative with zinc and hydrochloric acid. It is a colourless crystalline compound melts a t 93" and gives a bluish- violet coloration with chloranil or lead peroxide but not with acids.The condensation of paranitroberizaldehyde and dimethylaniline is best effected by dilute hydrocliloric acid or dilute sulphuric acid ; tlie hydro1 formation only takes place in presence of excess of acid ; if alcohol is also present the ethyl ether is produced. When only a small quantity of acid is employed or if it is very dilute nitroleuco- malachite-green is formed. Hydrols are not formed or only in very small quantities when phosphoric acid acid salts or organic acids are employed and with excess of concentrated sulphuric acid the only product is tetramethylbenzidine which is obtained in small quantities. Dimetbylaniline diethylaniline methylariiline and ethylaniline on the one hand and paranitro- and metanitro-benznldehyde on the other hand condense without difficulty and the hydrols formed resemble paranitrodimethylamidobenz hy drol.The ethyl compounds melt a t it lower temperature than the coiw- sponding methyl-derivatives ; the dialkylhydrols melt a t a lower temperature than the nionalkyl-derivatives and the para-compounds at a higher temperature than the isonieric meta-bases. Aniline also combines with paranitrobenzaldehyde but not so readily as the secondary and tertiary bases. The amidohydrols dissolve in cold mineral acids and in dilute acetic acid yielding colourless or only slightly coloured solutions ; the diamido-derivatives behave in like manner towards excess of concen- trated mineral acids but dissolve in acetic acid formiug deep blue solutions especially on warming. The diamido-derivatives also give blue solutions when an insuficient quantity of mineral acid is added or when dilute only slightly acid solutions are warmed.The author finds that tetramethyldiamidobenzhydi 01 does not dissolve in alcohol with a blue coloration as stated by Mivhler and Dupertius (this Journal 1877 ii 333) but that it dissolves in d l neutral solvents forming colc~ urless solutions. F. S. K.ORGANIC CHEMCSTRP. 2(i5 Formation of Benzamarone. By F. R. JAPP and F. KLINGEMANN (Ber. 21 2934-293;) .-Benzamarone is formed when deoxybenzoyn and benzaldrhyde (each 5 grams) are dissolved in cold alcohol treated with an alcoholic solution of potash (2 grams) and kept over night. The yield is 5 grams. A small quantity of the compouud was also obtained by keeping a mixture of b e n d deoxybenzoin and weak alcoholic potash for some days in a closed vessel; in this case the benzaldehyde necessary for its forniation is produced together with benzoic acid (which was found in the product) by the slow decompo- sition of the bend Benzamarone prepared as described above or by Zinin's method (this Journal 1871 639) melts a t 214-215" (not 225").Its mode of formation points to the formula C,,H,,02 rather than to the double formula (Knoevenagel Ber. 21 2356). N. H. M. Constitution of oertain Dichloronaphthalenes. By H. E RD- MANN (Bpr 21 3444-3448) .-Orthoparadrchloro~rherc ylparaconic acid can be prepsred by the action of succinic acid on orthoparadichloro- benzaldehyde and crysiallises from water in white scales melting a t 1 6 4 - 5 4 65.5".On d is t,illa tion i t yield 8 ort hoparadich lwoy hen y 1 iso- crofonic acid CsH,CI,*CH:CH.CH2*CO~~H [Cl C1 CH = 1 3 41 which crystallises from carbon bisulpliide in white prisms. When this acid is heated for some minutes a t its boiling point it decomposes into dichZoro-a-r~a~hthoZ CloH,C1,*OH [Cl C1 OH = 1 3 4'1 which crystallises from carbon bisulphide in large prisms melting a t 132". The corresponding d ic h Zoro-a-riap hthy Zamine CloH5Cl ,*NH can be prepared by heatiug the dicbloro-a-naphthol with aqueous ammonia ; it melts a t 116-lli" yields a hydrochloride melting at 204-205" and when diazotised and treated either with alcohol or with stannous chloride and cupric chloride is converted into 1 3 dichloronaphtha- lene which crjstallises in white needles melting a t 60-61". The a n t h w has therefore now prepared synthetically the t w o dichloro- naphthalenes melting a t about the same temperature one of which is homo- and the other hetero-nuclesl (compare this vol.p. 150). The remainder of the paper is devoted to a reply to Armstrong and Wynne's criticism of the constitution assigned by Erdmann and Kirch- hoff (7oc. c i t . ) to the heteronucleal diuhloronaplithalenes melting at 48" and at about 61.5" (Proc. 1888 104). w. P. w. Note by Abstractor.-The author puts forward as original the dis- covery of the existence of two isomeric dichloronnphthalenes melting at about 61"; a reply to this and other claims in the paper has been Action of Chlorine on Phenols. Part 111. ,&Naphthol.By T. ZINCKE and 0. KEGEL (Be?.. 21,3378-3390,%540-3559 ; compare Abstr. 1888 708) .-Cleve has described the preparation oE chloro-@- naphthol [Cl OH = 1 21 by the action of chlorine on &naphthol i n acetic acid solution (Abstr. 1888 597). Experiments show tha,t dichloro-/?-ketonapht balene is simultaneously formed and the best method of obtaining the chloro-P-naphthol consists in treating the @-naphthol dissolved in acetic acid with a slight excess of chlorine and published in the Proceedings 1889 p. 5. w. P. w.266 ABSTRACTS OF CHEMICAL PAPERS. reducing the dichloro-p-ketonaphthalene formed by addition of an excess of concentrated stannous chloride. The acetgl compound CloH6C1*OAc crystallises in thick colourless oblique-angled tables melts a t 42-43' aiid is very soluble in alcohol.aP-Diclzloro-p-naphthol Cl0H5C1,.OH [Cl OH C1 = 1 2 31 can be obtained by the reduction of tetrach loro-,&ketohydronaphthalene (see below) but when prepared from this source is always mixed with 9 larger or smaller quantity of the isomeric ao-dichloro-13- naphthol. It is best prepared however by reducing trichloro-$- ketonaphthalene dissolved in acetic acid either with stannons chloride or a sulphite. It crystallises in aggregates of sleuder lustrous needles melts a t 60-81' and is readily soluble in alcohol ether benzene and acetic acid. The ncetyl-deri vative CloH5C1,*OAc ci-ys- tallises in flat rhombic tables showing a peculiar striation on some of the faces melts a t 79-80" and is readily soluble in alcohol and acetic acid.When treated with chlorine in acetic acid solution a/3-dichloro-P-naphthol is converted into 6-trichloro-p-ketonaphtha- leoe which by further addition of chlorine forms p-pentachloro-p- ketohydronaphthalene. Chromic acid converts it into a yellow amorphous substance probably a diquinone-derivative but on careful oxidation with nitric acid (sp. gr. = 1*4) it yields chloro-@naphtha- quinone as chief produck a second quinone-like compound probably an ap-nitrochloro-p- napht h aquinone being simultaneously formed which melts at 172" and is characterised by dissolving in aqueous alkali with an intense bluish-green colour and in alcoholic alkali with a deep blue colonr. aa-Dichlol.o-P-na~htho2 CloH5C12*OH [Cl OH C1 = 1 2 41 is obtained together with the a/?-derivative by the reduction of tetra- chloro-@-ketohydronaphthalene with stannous chloride in the cold and is separated from its ieomeride by repeated crystallisation from light petroleum.It crystallises in long hard white asbestos-like needles melts at 123-124' and is readily soluble in ether alcohol and acetic acid. Its acetyl-derivative C,H,CI,*OAc crystallises in small colour- less needles and melts a t 90-91". On treatment of its acetic acid solution with the calculated quantity of chlorine it is converted into a-trichloro-P-ketona-phthalene which by the further action of chlorine yields a-pentachloro-6- ket ohy dronaphtb alene ( P). When oxidised with chromic acid it is converted into a yellow amorphous substance whilst with nitric acid (sp. gr. = 1*4) it yields as chief product alj-chloro- nit ro-p-naphthaquinone a-ch loro- p-naph thaquinone being formed simultaneously in very small quantities.a~-Chloronitro-~-napl~tha- puinone c6&<ccI.C (No,)> crystallises in red or brownish-red needles melts at 1%" and is readily soluble in hot benzene or acetic acid sparingly soluble in alcohol light petroleum and cold benzene or acetic acid. It dissolves in concentrated alkali with a n intense greenish- blue and in dilute alkali with a reddish-brown colour. When treated with aniline it yields anilidonitronaphthapuinone anilide co*co - CO-C(NHPh) C6H4<C (NPh) -C( NO2)>'ORGANIC CHERIISTRP. 267 which crystallises in dark violet scales showing a metallic lustre melts a t 249-650" and is insoluble in alkalis sparingly soluble in acetic acaid and benzene but more soluble in toluene.The salts of this base w e decomposed by alcohol or acetic acid unless acid is present when thev dissolve with a violet colour. J a- Chloro-P-nnphthaqz~inone C6H,< ::;%%> crystallises in red- dish-brown strongly dichroic needles melts a t 136' and yields CO-CCOH)> P-h y drox yn aph t haquinone anilide C6H4 < C(Nph).CH 9 On treatment with aniline. TriclLloro-a-nnphtiioz C,,H,CI,*OH [Cl OH C1 C1 = 1 2 3 41 is obtained by the reduction of /?- pe II tachloro-/?-ketohydroiiap hthalene with stannous chloride or sodium sulphite. It crystnllises in colourless needles melts at 162' and is less soluble than the diclilorinated deriva- tives. Its acetyl-compound C H4Clj-OAc crystallises from acetic acid in white lustrous needles and melts a t 133.5-134".On treatment in acetic acid solution with chlorine it is converted into tetrachloro-& ketomphthalene. Chromic acid oxidises it to a yellow amorphous substance containing probably a diquinone whilst nitric acid (sp. g!. = 1.4) converts it in to orp-dichloro-f3-naphthaquinone. a - ~ z c h l o r o - l j - k e t o n ~ p hthalene (p-naphtlLayuinone chloride) CC'l,.CO C6H4< CJ-JCH / 9 is obtained by treating chloro-/?-naphthol or /%naphthol dissolved in acetic acid or chloroform with the calculated quantity of chlorine It is a liquid and rapidly decomposes on distillation in a vacuum. When treated with aniline i t is converted into P-hydroxynaphthaquinone anilide if dissolved in alcohol but into anilidonap hthaquinone anilide C6H4< if dissolved in acetic acid.Phenylhydrazine reacts with the compound in a peculiar manner inasmuch as it does not convert it into the so-called benzeneazo-/?-naphthol but into a chlorinated azo-compound /?-benzenenzo-a-chloronay/Lthalene CloH6C1*N:NPh [Cl N2Ph = 1 21 which crystallises in slender reddish or pale-orange needles melts a t 115" is readily soluble in alcohol benzene and acetic acid and on reduction in acetic acid solution with stannous chloride yields not chloro-/%naphthylamine but a basic compound free from chlorine. A mixture of brown substances is formed by the action of hydroxyl- amine on dichloro-/3-ketonaphthalene. 6- Trichloro-p-ketona~htl,alene (I-3-cliloro-/3-naphtfia~u~none chloride) CsHI<CH:cc1> CCl,*CO is formed by withdrawing the elements of hydro- gen chloride from tetrachloro-P-ketohydronaphthalene. It is not however necessary t o first prepare this compound in the pure state since the product obtained by treating a well-cooled 10 t o 12 per cent.sotution of &naphthol in acetic acid with an excess of chlorine readily evolves hydrogen chloride when poured into an equal volume of alcohol,268 ABSTRACTS OF CHEMICAL PAPERS. and yields the trichloroketone. It crystallises from alcohol or acetic acid in thick yellow needles which darken in colour on exposure to light and melt at 95-96'; whilst from ether it separates in larw monoclinic prisms which show however a marked rhonibic habit if the solution is impure. When finely powdered it dissolves slowly in dilute alkali and yields in addition to brown resinous substances PP-chlorh ydroxpapht haquinone tion is accounted for by supposing that the P-chloro-a-hydroxy-p-naph- thaquinone which would most probably be formed in the first instance undergoes isomeric change.When heated either with dilute alcohol or withdilute acetic acid it forms resinous compounds together with some chlorhydroxynaphthaquinone and a compound which crystallises in needles and seems to be a dichloro-p-naphthol. Stannous chloride and sulphites reduce it to ap-dichloro-@-naphthol; phenylhydrazine in alcoholic solution reduceq it hydroxylamine converts it into resinous products and orthotoluylenediamine reacts with it forniing crystalline compounds. When the hot alcoholic or acetic acid solution of the trichloroketone is treated with aniline Plj-chlorhydroxyna~lzthapzcinons anilide C ~ H I < ~ ~ ~ ~ ~ ~ ~ ~ > is obtained melting at 253" ; if how- ever a cold alcohblic shhtion is used this comDound is formed onlv in relatively small quantities the chief produ'ct being a&dkhlo&-+ hydrox~-a-naph'thy123hsnylamine C,H,<c(~Hph):ccl>.This crys- CCl-C(OH) - tallises from chloroform in colourless transparent hard thick crystals from acetic acid in slender lustrous needles aud from a mixture of ether and light petroleum in large prisms melts a t lt;2" and dissolves without decomposition in a1 kalis. Its acetyl-derirati\ e CIGHIONCI~*OAC crystallises from alcohol or acetic acid in small lustrous prisms and melts at 164". In one preparation of this compound a third substance was once obtained which crystal- lised in small white scales melted at 223" and gave results on apalysis indicating i t to be a chlorhydroxydiphenylnaphthylene- diamine.a-Trichloro-P-ketonaZIhthaZe.ne (a-chloro-P-naphthaqui?~one chloride) c,&<<ccl:cH> is prepared by treating an acetic acid solution of az-dichloro-P-naphthol with the calculated quantity of chlorine. It crystallises from light petroleum in thick white needles and from a mixture of ether ahd benzene in well-formed transparent rhombic prisms melts at 86-87' and is readily soluble in hot alcohol benzene ether and acetic acid. On treatment with alkali it yields B-hy- droxynaphthaquinone ; aniline converts it in alcoholic solution into p-hydroxynaphthaquinone anilide and in acetic acid solution into anilidonaphthaquinone anilide ; stannous chloride redures it to aa-dichloro-,~-naphthol and hydroxylamine reacts with it forming an oxime.CCI,*CO Tetraphloro-P-keton aphthalene (dichloro-&nap hth aquinone chloride) CsH4<CC1:CC1> is obtained by suspending trichloro-P-naphthol iu cc12*coORGANIC CHERlISTRT. 269 acetic acid and passing chlorine until the whole has gone into solution and the liquid has a distinct odour of the gas. It c.rystallises from alcohol or acetic acid in yellowish scales and melts a t 96-97". When treated with concentrated alkali it yields dichlorhydroxyindenecwr- boxylic acid which can be recognised by transforming it into dichloro- ketoindene C6H4<C/C1>CC1 ; alcoholic potash on the other hand con- verts it into the supposed ethyl-derivative of chlorhydroxy-S-naph t hn- quinone &'3-clilorhydroxynaphthaquinone anilide.CO C6H4<C(oH):CCr>. co-co Aniline reacts with it forming Tetracldoro-p-ketoh ydronaphthal ene C6~4<C~C].CHC1>' is the CC1,-CO most easily prepared of all the keto-derivatives of &naphthol and is obtained by treating a carefully cooled solution of &naphthol in wetic acid with an excess of chlorine and a t once precipitating the product with water. It is necessary that the chlorination should be completed in one operation since a partially chlorinated solution after rernclin- i n g 1% hours gave on further chlorination a crystalline separation consisting of thick yellowish needles which had the composition (CloH6Cl,0) melted a t 193" and were sparingly soluble in most solvents.Obtained in this way the tetrachlorhydroketone crystal- lises with 1 mol. HzO in white lustrous scales melts at 90-91" and is converted into the anhydrous form by repeated crystallisation from light petroleum ; it then crystailises in white lustrous scales melting at 102-103" white needles melting at 101-102" or occasionally in colourless monoclinic prisms. It dissolves in cold alcohol but on standing or more rapidly on warming it undergoes conversion into P-trichloro-@-ketonaphthalene. Stannous chloride and sulphites reduce i t to a/-l-dichlor0-8-naphthol on warming and to a mixture of tliis with the aa-derivative in the cold ; solution of sodium carhonate converts it into /3-chloro-@-naphthaquinone aqueous soda dissolves it with the format ion of @P-c hlorh y drox ynaph thaquinone and aniline reacts with it as with p-trichloro-@-ketonaphthalene.When a-trichloro-/j-ketonaphtbalene is further chlorinated it yields a compound crystallising in small forms which resemble rhombic sul- pliur crystals both in colour and shape. Although this compound always shows the same melting point it is very probable that it is a mixture of tetmcliloro-/3-ketorlaph t halene and hexacti loro-@- ketonap'n- thalene in molecular proportions which cannot be separated by crystal- lisation and not a-pen tachloro-@-ketohydronaphthalene inasmuch as a portion of the finely powdered subLtauce dissolved rapidly in alkali yielding a solution in which dichlorhydroxyindenecarboxylic acid could be detected whilst the residue was white and resembled hexa- chloro-6-ketohydronaphthalene in its properties.P-Pentachloro-P-keto h ydronapht h alene CsH4< cc12-c0> HC1.C c is ob- ' 2 tained by saturating a solution of /?-trichloro-p-ketonaphthalene in acetic acid with chlorine. It crystallises in well-formed colourless friclinic prisms which melt at 116-117" ; if crystallised from ether howeb er ir forms very large and appareutly rhombohedra1 crystals,2 TO ABSTLtACTS OF CHEJIICAL PAPERS. and when crystallised from benzene yields both transparent forms and crystals which effloresce on exposure to the air. On reduction with stannous chloride sodium sulphite or less readily witb phenylhydr- azine it is converted into trichloro-/I-naphthol and only reacts with aniline at the boiling point when it yields /3/hhlorohydroxynaphtha- quinone anilide.When treated in alcohdic solution with 25 per cent. aqueous potash the ring is split and o?.thoclich2orovinylJz'chlol.ubenzyI- cnrboxylic acid C2HCl2*CtiH4*CCI2-COOH is obtained which crystal- lises from chloroform in transpareut lustrous forms and from light petroleum in thick white needles melts at 130-131" with decomposi- tion and evolution of hydrogen chloride but not of carbonic anhydride aiid is readily soluble in the ordinary solvents. It dissolves i n aqueous sodium carbonate without decomposition but is slowly converted into the corresponding benzoylcarboxylic acid by caustic alkalis. On oxidation itt yields dichlorovinylhenzoic acid.The methyl salt C9H5C14-COOMe crystallises in slender white needles melts a t 99 - loo" and is readily soluble in alcohol and ether. O~-thodichlorirvinyZZ,enzoyZcarbozyZic acid C2HC12*C6H,-C0.C00H is prepared by dissolving the finely-powdered pentachloroketone in 25 per cent. aqneous potash and acidifying. It crystallises from dilute alcohol in long slender yellowish needles melts without decomposition at 106-107" and is readily soluble in alcohol and acetic acid but only sparingly i n light petroleum. The methyl salt has not been solidified and no solid compound could be obtained by the action of hodrosvlamine. J J Eexachloro-/3-ketonaphthalene C6H4<<ccl~.&-,l,,> CCl co is prepared by heating the tetrachloroketone with 1 part of rna&mese dioxide and 5 parts of fuming hydrochloric acid (sp.gr. = 1.19) at 140-150" for 6 t o 8 hours. It cryst'allises in long colourless prismatic needles or in compact seemingly monoclinic and occasionally tabular crystals melts at 129" and dissolves in ether benzene hot alcohol and hot acetic acid. On reductmion i t is converted into trichloro-/3-naph thol. When treated in warm alcoholic solution with concentrated aqueous potash the ring is split and orthotl.ichlorovinyldichlorobenzylcarbo.cy lic ucid C2C1,*CsH,*CC1,*COOH can be obtained from the solution by saturating it with hydrochloric acid. I t crystallises in colourless needles or long thick tables melts at 150" with decomposition and is readily soluble in alcohol and ether. On oxidation it yields oi-thotri- chlorovinylbenzoic acid.The methyl salt C9H4C1,-COOMe crystallises in colourless slender needles and melts a t 83-84". When the acid is dissolved in concentrated aqueous soda and afterwards acidified an oil is obtained which coiild not he crystallised and probably consists of the corresponding ketonic acid. w. P. w. Reduction Products of the Azo-dyes of the Naphthalene Series. By 0. N. WITT (Bey. 21 3468-348S).-The azo-dyes obtained by t h e action of diazotised bases on the isomeric mono- and di-snlphonic acids of a- and /+naphthol and naphthylamine are converted by reduction into two aiiiines one being the base from which the diazo-compound was obtained and the second beingORG14XIC CHEMISTRY. 271 the amido-compound of the naphthalene-derivative employed.The actual o r supposed instability of these reduction products has hitherto led to the neglect of this method of determining the constituents of the naphthalene azo-dyes but this instability is to be ascribed to the secondary action of the reducing agent employed the use of alkaline reducing agents such i l ~ j zinc-dust with ammonia or soda or the addition of alkali to the reduction product leading in all cases to decomposition. The method however is the only one capable of giving t’rustworthy r&ults and experiment shows that with a suit- able reducing agent a solution of “ tin salt. ” in hydrochloric acid the reduction products of the naphthalene azo-dyes can be isolated for subsequent identification. For analytical purposes 1 gram of the azo-dye freed from dextrin sodium sulphate arid like impurities is dissolved in 10 c.c.or in the case of the less soluble dyes 20 C.C. of boiling water the source of heat is then removed and 6 c c. of a s o h - tion of 40 grams of “ tin salt” i n 100 C.C. of pure hydrocllloric acid (sp. gr. = 1-19> corresponding to 2 grams of. tin salt is added. The amidonapht hol- or nap h t haleuediamine-sulphonic acid formed may separate from the warm or cold solution or not at all according to the nature of the substance and in the last case precipitation with sodium acetate halt or hydrochloric acid as determined by experi- ment must be resorted to. This process is termed by the author a normal reduction. In order to isolate and characterise the reduction products the aniline-azo-dyes derived from p-naphtfho1 Ij-iiaphthylamine and their mono- and di-sulphonic acids were alone employed but the iuet’hod presents no difficulties wlieu applied to those azo-dyes found i l l commerce which are derivatires of these naphthalene-compounds.Dericatives of P-NuplLthuL-The azo-dyes derived from p-naphthol are known to give amido-/3-naphthol on reduction (Liebermanti Ber. 14 1310). f3-Nttphtiiol-orange (mandarin) o u normal reduction yields a clear and coluurless solution from which white needles and stellar aggregates of amido-p-naphthol hydrochloride separate on cooling. ‘l’his salt dissolves readily in hot water but cannot be pre- cipitated either by alkalis or soda the solution becoming dark brown iii colour.. Sodium acetate however precipitates amido-&naphthol from the solution in lustrous scales which dissolve readily in ether and crystallise in smail? quadratic tables on spontaneous evaporation of the solvent.The addition of ferric chloride to the hydrochloride in aqueous solution converts it into /%naphthaquinone. Uerivu tives of the fl-il-ap h t 11 olsulphonic Acids .- ( 1. ) Arnido-,d - niiphtliol-a-sulpholLic acid NH,*C,,H,( OH)*SO,H.-The orange from diazobenzene chloride and Bayer’s $-naphthol-a-sulphonic acid on normal reduction yields arnidonaphtliolsulphonic acid which c r j stab lises from the hot solution in small well-formed rectangularly Litriated .pale rose-coloured scales and can be purified by recrj stal- lisation from a dilute solution of sodium acetate. It is very sparingly soluble in hot water and in sodium acetate solution ; alkalis and alkaline earths however dissolve it readily and the solutions very rapidly become deep orange-brown 011 exposure to air.Oxidising agents colour bot,h che neutral aud a l k a h e solutions of the acid deep J ellow272 ABSTRACTS OF CHEMICAL PAPERS. or brown and silver salts are a t once reduced b.y it and each of the following acids in both acid arid ammoniacal solution. It does not vield a diazo-compound on treatment in acid solution with sodium nitrite and diazo-compounds do not react with it but decompose with the evolution of nitrogen and formation of ft brown colour. When treated with nitrosodimet~hylaniline hydrochloride in a 50 per cent. acetic acid solution it forms a characteristic violet colouring matter which in aqueous solution is coloured red on addition of aqueous soda.(2.) Amicto-P-nn~hthol-P-sul~honic Acid (Meldola Trans. 1881 47 ; Crriess Abstr. 1882 50).-The orange from diazobenzene chloride and Suhaff er’s p-nap11 thol-P-snlphonic acid on normal reduc- tion yields this amido-acid which separates from the hot solution as a crystalline magma. It is insoluble i n alcohol and oannot be purified by solution in water Rince decomposition ensues with the formation of brown solutions which on the addition of hydrochloric acid become violet. It is soluble in hot 20 per cent. aqueous sodium acetate in the presence of acetic acid and is precipitated from the solution on addition of hydrochloric or dilute sulphuric acid. With oxidising agents and sodium nitrite i t behaves like the precedigg compound b u t differs from it in not yielding a colouring matter with nitroso- dimethylaniline hydrochloride.I t is cbarncterised by readily yielding 011 treatment with diazo-compounds beautiful colouring matters which however do not dye wool ; thus with diazobenzenesulplionic acid a magenta colouriiig matter is obtained whose shade is rendered bluish on addition of hydrochloric acid whilst with tetrazos t i I benedi- sulphonic acid a reddishdviolet colouring matter is formed which on addition of hydrochloric acid is p~ecipitated in beautiful blue flocks so1iil)le in water to a blue solution. (3. ) Amido-/?-?zaplz th ol- 6-sulph o nic A cid .-T he an iline-azo- deri vative of Casella’s naphtholsulphonic acid F on uornial reduction yields this aniido-acid which crjstalliaes from the warm solrition in shimmering rose-red needles.I t closely resembles :tmido-/3-naphthol-~3-sulphonic acid in its properties and reactions but is less sensitive and is characterised b.y reacting only with some diazo-compounds and then but slowly. Thus addition of the diazo-compound from Bronner’s /3-naphthylaniine-~-sulphonic acid results in decomposition and the evolution of nitrogen whereas amido-13- napht hol-6-sulp honic acid forms with it a reddish-violet colouring matter. Diazobenzene- sulphonic acid produces with it a transitory red coloration followed by decomposition and evolution of nitrogen ; tetrazostilbenedisnlphonic acid however reacts with it forming a dull brownish-violef colouring matter which is precipitated without change of colour by hydro- chloric acid.(4) A mido-P- nap7i t h ol-ry- suzphonic Acid.-T he aniline-azo-derivative of /j-naphthol-y-sulphonic acid on normal reduction yields this amido- acid which separates in a crystalline form from the warm solution and can be purified by repeated solutioii in hot aqueous sodium acetate and precipitation with hydrochloric acid. I t i s the most sparingly soluble as well as the most! stable of the isomerides and forms small rose-red aggregates which are scarcely soluble i n hut water. WithORG-INIC CHEMISTRY. 273 alkalis oxidising agents and silver salts i t behaves like its isomerides and is characteiised by reacting neither with diazo-compounds nor \jrith nitrosodimethylaniline hydrochloride i n acetic acid solution. Derivatives of p-Naphtholdisuli,honic Acids.(1 .) Amido-p-naphthol- a-disulphonic acid.-" Ponceau 2 G," the aniliiie-am-derivative of p-nap hthol-a-disulphonic acid (R-acid) on normal reduction yields a clear solution which after cooling and standing some time de- posihs slender snow- white silky needlerJ ; an immediate separation in the form of satiny needles is however produced by the addition of an equal volume of saturated salt solution directly the reduc- t.ion is complete. The sodium hydrogen salt of the amido-acid NH,*C,,H,(OH) (SO3H)@SOaNa thus obtained is collected washed with alcohol and ether and dried but is still impure owing to the presence of amido-p-naphthol-/3-sulplionic acid obtained from the Schaffer's acid which is always present in the R-acid employed techni- cally ; it can be purified by rapidly dissolving ii; in 10 times its weight of acidified water adding an equal volume of ice-cold alcohol and a t once immersing the solution in a freezing mixture in order to bring about rapid crystallisation.In the dry state the compound is stable hut in aqueous solution it is extraordinarily unstable decomposing at once into what is almost certainly sodium ammonium dihydroxy- napht halenedisu l p honate S03Na*C10H4( 0 H )?-S03NH4 wb ich separates from the solution on addition of salt in grey scales. This compound is readily soluble in water less so in alcohol decomposes rapidly on addition of alkalis with the formation of brown solutions and is a salt of the supposed amido-6-naphthol-a-disulphonic acid described by Griess (Abstr.loc. cit.). The amido-acid is rapidly oxidised by alkalis does not react with diazo-compounds and nitrosodimethyl- aniline and immediately reduces silver salts to metallic silver. (2.) Amido-a-na~hthol-(y-dipul~horLic Acid.-" Orange G" the ani li ne-azo-deriva tive of /%nap h t h 01-y- d iso Iphon ic acid (pure G-acid) on normal reduction yields a clear solution from which salt solution precipitates the sodium hydroqeiz salt of the amido-acid NH2*~,,H4(OH)(S0,H)-SO3Na in snow-white prisms or small aggre- gates of prisms. It is much more stable than its isomeride and although it shows all the reactions given by the a-derivative yet the decompositions take place so much more slowly as LO afford a means of distinguishing between the two for example with silver salts the reduction only commences some minutes after the solutions have been mixed.Derivutives of P-Naphth ylamine. - The azo-dyes derived from P-naphthylamine are known to give a-/3-orthonaphthylenediamine on reduction. The aniline-azo-derivative formed by t h e action of diazobenzenesulphonic acid on /zI-naphthylanline on normal reduction yields the hydrochloride of this diamine which crystallises from the warm solution in slender white needles and is characterised bF forming naphthaphenanthrazine when treated in aqueous solution con- taining acetic acid and sodium acetate with an aqueous solution of the bisul p hi te compound of phenanthraquinone. Nap ht haphtmr n t hrazi ne crystnllises in yellowish-white sparingly solnble needles and dissolves i n sulphuric acid with B blackish-violet colour which becomes yellow2 74 ABSTRACTS OF CHIEAIICAL PAPERS.on dilution. The azo-dyes obtained from phenpl-P-naphthyl~miii~ and the toluyl-/3-naph thylsmines have alreadv been shown to yield azincs on treatment with acids (Abstr. 1867 590). Derivatives of p-N~phthill~mine~u~p?~oiiic Acids.-(1.) The B-naph- thvlamine-a-sulphonic acid (Badische acid) reacts with diazobenzene- sulphonic acid but yields a yellow diazoamido- and not an azo- compound which on normal reduction is converted into phenyl- hydrazine and unchanged Badische acid. (2.) Orf honaphtkylenec.Jiar~r~e-p-szLlph onic acid CI,Hj (NH,),.S 0,H - “ Gold brown,” the aniline-azo-derivative of /I-naphthylamine-p- mlphonic acid (Rronner’s acid) on normal reduction yields crystals which separate from the hot solution and can be puyified by solu- tion in aqueous sodium acetate and precipitation with acetic or hydrochloric avids.It forms slender pointed needles is very sparingly soluble in water and in alkaline solution becomes rapidly brown on exposure to the air ; an excess of soda. however precipitates a sodium salt in silvery scales. Potassium ferricysnide produces a brown colour with the alkaline solution which subsequently changes t o a pure yellow and ferric chloride forms a dull green precipitate in the aqueons solution. The acid is chnracterised bv yielding the cityon- yellow sodium napht~a~~enanthraxinesulpphontcte C21H17N2.S03Na when its solution in sodium acctate and acetic acid is treated with an aqneons solution of the bisulphite compound of phennnthraqiiinone.This salt dissolves in snlphuric acid with a reddish-violet colour and on fusion with potassium hydroxide is converted into a eurhodol which is obtained in brown,.gelatinous flocks on acidifying the solu- tion of the melt dissolves in sulphuric acid with a pure ultramarine colour and is slowly precipitated as a cherry-red sulpbate on addition of water to the solution. (3.) OrthonaphthylPnedinmine-8-su7ho?iic Acid -The aniline-azo- dye obtained from B-na.phthylamine-8-sulphonic acid (F-acid) on normal reduction. yields a clear solution which deposits only a few flocks on standing. An indistinctly crrstalline precipitate is obtained by adding salt solution and hydrochloric acid and this when purified by solution in sodium acetate and precipitation with hydrochloric acid forms a rey powder which dissolves in water more readily than the p-acid.kt its behaviour with alkalis potassium ferricyanide and ferric chloride it resembles the p-acid. but excess of soda does not precipitate a crystalline sodium salt from its solution. The cor- responding sodium naphthaphennnthrazinesulphonate crystallises from dilute alcohol in Plender needles and dissolves in su1phuric acid with a reddish-violet colour and the eurhodol foriiis a pure violet solution with snlphuric acid which on dilution yields a brownish-red precipi- tate of the sulpbate. (4.) Oi*thonaphthylenediamine-ysulphonic Acid. -The aniline-azo- derivative of P-naplithylamine-y-sulphonic acid (Dahl’s acid) on normal reduction yields this acid which crystallises from the hot solution and can be purified by solution in sodium acetate and pre- cipitation with hydrochloric acid.It crystallices in ~himmeriug brown scales is more soluble i n water th?n the @-compound reduces silver salts and in aqueous solution yields a deep green coloration0 R GXNIC CHE MIS’IXY. 2 7.i with ferric chloride the solution subsequently depositing a dark- green precipitate. The alkaline solution slowly assumes a brown colour. The corresponding sodizirn n~phfhaphenanthrazinesulph~niite dissolves in sulphuric acid with a violet colour which on dilution becomes orange and the eurhodol dissolves in sulphuric acid with A black-violet colour and the solution on dilution with water first becomes cherry-red and afterwards deposits the sulphate in dark-red flocks. Derivatives of ~3-~~aphtlzylaminedisulpphonic Acids.-The P-naphth,yl- amine-ydisulphonic acid (amido- G-acid) according to Schultz (]OM not combine with diazo-compounds.The aniline-azo-derivative of 6-naphthylamine-a-disnlphonic acid (amido-R-acid) on normal reduction ? ields a clear solution on cooling from which hydrochloric acid precipitates the sodeum hydrogen sult S0,H.CloH,(NH,)2.S03Na. This can be purified by dissolviiig it in water and precipitating with salt solution and f timing hydroclilncic acid. When obtained by precipitation with hydrochloric acid i t forms a sandy powder consisting of well formed and often twinned prisms whilst salt solution precipitates it in the form of slender pointed needles.It is readily soluble in water a n d the solution fluoresces green in the absence of mineral acids yields sparingly soluble pre- cipitates with barium and calcium chlorides and becomes coloured deep green on addition of ferric chloride. It resembles orthonaph- thylenediamine-1-sulphonic acid in its behaviour with alkalis and silver salts. The corresponding sodium na~hthaphr~nantl~ruzinedi- su7phonntr form8 a transparent citron-yello w gelatinous mass which could not be crystallised and dissolves in sulphuric with a very characteristic bluish-magenta coloration which on dilution becomes first yellow and then orange. The eurhodol is insoluble in water and yields a deep greenish-blue solution in sulphuric acid which on dilu- tion becomes first violet and then bordeaux-red ; further dilutiou precipitates the eurhodol itself in yellowish-brown flocks.Constitution of @-Naphthol-a-Sulphonic Acid. w. P. w. By 0. N. WITT (Ber. 21 3489-3492).-When amido-P-naphthol-a-sulphonic acid (see preceding Abstract) is heated with concentrated hydro- chloric acid a t 120” for 4-5 hours it yields a dihydroxynaphthalene which on oxidation with ferric chloride is converted into B-naphthx- quinone. It follows therefore that nmido-B-naphthol-a-sulphonic acid has the constitution [NH, OH SOAH = 1 2 21 and consequently Bayer’s P-naplit~ol-a-snlphonic acid cannot have the constitution Note by Abstractor.-Throughout the paper the author regards Armstrong as the authority for the 1 2 formula hitherto frequently assigned to Bayer’s acid; this however is due to a misconception (compare Arnistrong Proc.1889 8). The acid has been shown to be heteronucleal by Armstrong and Wynne (Proc. 1888,104 ; 1889 T). Action of Fuming Sulphuric Acid on Bronner’s 6’-Naphthyl- amine-P-Sulphonic Acid. By S. FOESLING (Ber. 21 3495-3499). [SO,H OH = 1 21. w. P. w. w. P. w.276 ABSTRACTS OF CHEMICAL PAPERS. When Bronner's p-naphthylamine-6-sulphonic acid dried a t lC;O" is heated with 3 to 4 parts of fuming sulphuric acid a t about 110" until a test specimen dissolves in water a mixture of P-naphthyl- aminedisulphonic acid together with a small quantity of a second acid is obtained ; the yield of the latter is increased by allowing the sulphonation to proceed a t a higher temperature for a longer time.~-~-aphthylamir~edisulphoi~lzic acid NH2*CloH,( SO,H) cannot be obtained by acidifyiug the solution of a normal salt since the corre- sponding acid salt is thereby formed. It can be prepared however by treating the barium salt with sulphuric acid and crystallises in white needles which are extremely soluble in water but only sparingly in alcohol. The potassium salt crystsllises with 2 mols. H20 in large yellow crystals ; the potassium hydrogen salt with 1 mol. H20 in long white slender needles; the sodium salt in long white needles; the sodium hydrogen salt with 2 mols. H,O in long white slender needles ; the animoirium salt with 1 mol. HaO in large red triclinic crystais and the ammoni7hm h?/drogm salt in anhydrous slender white needles ; the burium and cnlc-ium salts are also described. The normal salts are readily soluble in water the acid salts on the conti*ary are somewhat sparingly soluble in cold water.When diazotised in alcoholic solution with nitrous acid the acid salts of the acid are converted into the corresponding diazonaphthalenedisulpho- nates which are relatively stable and can be boiled with absolute alcohol without decomposition ; the potassium and ammoniuin sat ts crystsllise in microscopic yellow rhombio tables the sodium salt in needles. The potassium salt OP p-chloronnphthalenedisulphonic acid is obtained by heating potassium diazonaphthalenedisulphonate with cuprous chloride and hydrochloric acid. It crystallises in white needles and is only sparingly soluble in cold water. The disulpho- chloride CIoK5C1( SO,CI) crystallises from benzene in thick tables and from chloroform in small colourless prisms melts a t 1245" and is very sparingly soluble in light petroleum.The trichZo?nnaphtlraZene C,,H5CI c q stallises in dendritic aggregates of slender needles melts at 91" and is sparingly soluble In alcohol but readily soluble in chloroform. w . P. w. Filicic Acid. By E. LUCK (Bey. 21 3465-3468).-A reply to the criticisms of Daccomo ( H e y . 21 2962 this vol. p. 54). Pure filicic acid melts at 184-5" but if the specimen is allowed to solidify and the melting point again taken it is found to sinter at about 130" and melt a t 150-160". w. P. w. Transformation of Terpilene into Menthene. By G. Bou- CHARDAT and J. LAFONT (Cumpt. rend. 107 916-918).-When terpin is treated with concentrated hydriodic acid i t yields a crystalline terpilene dihydriodide identical with that obtained from tereben- thene.The terpin is mixed with hpdriodic acid saturated at O" and as soon as the temperature is raised the liquid separates into twoORa ANIC CHEMIbTRY. 277 layers and iodine is liberated which indimtes that hydrogen has cwmbirred with the hydrocarbon. The mixture waq heated a t 1OOOfor 20 to 2% hours the weight of hydriodic acid varying from 16 to 60 times thRt of the terpin. The principitl reaction i q represented by the equation CioHifi,2HI + 41 = C1,H,,HI + I? whilst part of the terpilene is polyrnerised. The principal product is isomeric if not identical with menthene hydriodide CloHIgI but it cannot be isolated from the accornpanjing diterpilene since i t decomposes even at a somewhat low temperature.If the free iodine and acid are removed and the hydi-iodide is heated a t 100" with potassium acetate potassium iodide is depoqited and an oily liquid is obtained which is lighter than water. When distilled it separates into two fractions one of which boils a t 210-225" under a pressure of 30 mm. and consists of diterpilcne mixed with hydrides of similar boiling point whilst the other has the composition CIOHiA and boils a t 167-li0" under ordinary pressure ; sp. gr. at 0" = 0.837. The latter hydrocarbon combines very slowly with hydracids anti differs in this respect from terpilene. If heated at 100" for 10 hours with 6 to 8 volumes of hydrochloric acid saturated a t O" combination is complete but only a monohydrochloride is formed. This is an oily liquid lighter than water.It has an agreeable odour does not. solidify a t -GO" and boil. without decomposition a t 105-110" under :I pressure of 30 mm. Under ordinary prescure it decomposes into hydrogen chloride and the hydrocarbon. When treated with alkalis the hydrochloride yields the hydrocarbon but there is no appreciable formation of any oxygen compound. All its properties agree with those of a menthol-derivative and the hydrocarbon is identical or isomeric with Oppenheim's menthene. It is evident also that there is it close relation between terpilene and menthene. C. H. B. Essential Oil of Daucus Carota. By M. LANDSBERG (Chen7. Centr. 1888 1273).-.By. means of fractional distillation this oil was divided into two principal fractions the one boiling at 159-161" and the other at 240-360".The former contains no oxygen and is a terpene of the formula CIoH,,. It is dextrorotatorg; a column 100 mm. long rotating the plane 32.3"; sp. gr. = 0.8525 at 28". With bromine i t forms an addirive compound C,,H,,Br ; from this cgmene was obtained by boiling its alcoholic solution with an aqueous solution of potassium cyanide. On heating the ttrpene in a closed tube at 280" it is split np into two terpenes the one boiling at 178-182" and the other not distilling a t 300O. Both combine with bromine to form additive conipcunds ; that from the former Cl,,H,,Br4 melts a t 123-125" ; t h a t from the latter has the formula C,,H1,Br2. They may be considered a s polymerides of the original terpene which belongs to the group of pinenes.The second component of the essential oil (boiling point 240-260") proved to be a monohydrated terpene of the formula C,,H,,O. When heated to 280" it loses the elements of water and the residue consists of the same polymeric terpene of high boiling point as is obtainod by heating +,he first-named terpene a t 280'. The behaviour of the mono- VOL. LVI. %2 i 8 ABSTRACTS OF CHEMICAL PAPERS. hydrated terpene with bromine and with hvdrogen chloride or bro- mide proved it to be identical with Wallach's cineole. J. w. L. Constitution of Quassin. By V. OLrvERr (Gazzetfa 18 169- 170).-In a prei-ious communication (Abstr. 1888 1312) the author pointed out that quassic acid contained two ketonic groupr since it gave rise to a dioxime of the formula C28H,,O,(C:NOH),. I h seemed however desirable to establish that these CO-groups existed also in quassin and for this purpose the author prepared the compound of quassin with phenylhydmzine.Quassin ( 3 grams) and phenylhydr- aziiie hydrochloride (4 grams) were dissolved i n the smallest possible quantity of alcohol a solution of sodium acetate added (6 grams iii 15 C.C. water) and the whole heated at 100" for an hour. The yellow amorphous deposit formed on dlowing i t to remain for a day was thoroughly washed with water and aLtempts made to obtain i t in it crystalline state but wit,hout success. 4 n analysis showed that it hat1 tlle composition C,,H4,08( CH-NHPh),. It is formed from phenyl- Iiydrazine and quassin with elimination of tlie elements of water thus C,,H*oO,(CO) + 2NH,*NHPh = C,,Z,oO,(CIL'*NHPh) + 2HzO.C. E. G. Methysticin. By C. POMERANZ (Moriatsh. 9 862-864).-Methy- sticin is a non-nitrogenous non-volatile neutral substance which occurs in the alcoholic extracts from the roots of Maci*opiper methy- sticunz. I t crystallises in long silky needles melting a t 131" sparingly soluble in hot water ether and light petroloum readily soluble in alcohol benzene and chloroform. It contains about 65.4 per cent. carbon and 5.1 per cent. hydrogen. When fused with potash it gives chiefly protocatechuic acid. Heated with 30 tinies the amount of 10 per cent. potash solution it complt4ely dissolves arid from the solution which smells strongly of piperonal hydrochloric acid precipitates a yellowish compound which separates from alcohol in small white crystals melting at 180".This compound which contains 64.26 per cent. carbon and 4 85 per cent. hydrogen is readily soluble in alkaline carbonates and yields piperonylic acid on oxidation with perman- ganate. H. C. Note.-No reference i s made to Davidoffs researches on this subject (compare Abstr. 1888 1207). Andromedotoxin. By P . C. PLUGGE and H. G. DE ZAAYE~~ {di-ch. Pharrit. [3] 26 997-998 from Arch. yes. Physiol. 40. See Abstr. 1883 349).-Plugge first obtained nndromedotoxin which he tlxtracted from Androw eda japotr ica A. polifoliu A. catesbaci and A. ca 1 y c w l a t a. The aqueous extract of Rhododendron powticum leaves was treated successively with norrrial and basic lead acetate.From the filtrate the lead was separated by hydrogen sulphide and the liquid was con- centrated by slow evaporation in the air and treated repeatedly with considerable quantities of chloroform. The residue left on evaporating the chlorofoi~m was purified by re-solution in chloroform (or alcohol)ORGXSIC CHEJIISTRY. 2 59 and precipitation by the addition of a considerable amount of ether. This treatment several times repeated finally yielded well formed crystalline needles which melted at 228-229O. A t 125O water dis- solves 2.81 per cent. ; alcohol (of 94 per cent.) 11.1 ; amyl alcohol 1-14. ; chloroform 0.26 ; ether 0.07 ; benzene 0.004. The solutions in water alcohol and amyl alcohol are lmrorotatory whilst that in chloroform is dextrorotatory.Andromedotoxin CslH,,O, is an indifferent non- nitrogenous compound ; its solution in indifferent liquids has a neutral reaction and it is not precipitated by any of the so-called general iblkalo'id rzagents. Its reaction with dilute and concentrated mineral acids is characteristic as with them it gives intensely red decom- position-products. Concentrated sulphuric acid gives a dark reddish- brown which becomes deeper red on warming and turns light mulberry-red on dilution with water. The addition of alkali removes the colour. which reappears on acidifying. Evaporation with dilute (1 5) sulphuric acid gives a beautiful rose-red colour. The pure material gives off no odour during this evaporation but if uot com- pletely purified a strong and very characteristic odour of ericinol is evolved. Evaporation with dilute hydrochloric acid gives a residue somewhat rliore violet-red in tint.Evaporation with phosphoric acid give,. a mulberry. red residue clezrly pyrcepti ble with very minute qu mtities as in the case of the other acids. The fatal dose for small animals has becn found to vary from 0.1-0.45 mgrm. per kilo. body- weight. No chemical antidote is known a s pet. I n investigating poisoning cases Dragendorff's process is recommended ; but no acid should be used for extraction as the so1ubilit)p of the poison is not thereby increased. After extraction and purification by evaporation taking up in alcohol &c. the substance may be agitated with light petroleum then with chloroform and to the residue left by the chloroform the characteris tic tests given above may be applied.T m tJ. 1. Chlorophyll. By E. SCHUNCK (Proc. Roy. Soc. 44 448-454; compare Abstr. 1887 972).-Crude chlorophyll from grass is treated with boiling alcoholic soda and hydrogen chloride passed into the solu- tion until i t is strongly acid. Ci*ystals separate which after purifica- tion form a semi-metallic purple mass which softens a t 2M0 and shows the absorption-spectrum of phyllocyank-derivatives. This com- pound is an ethyl ether. On treating it with boiling alcoholic soda a dark-green sodium salt is obtained which when decomposed by acetic acid anci crystallised from ether gives purple crjstals of a new sub- stance phyllotuoni?t melting a t 184" and insoluble in water but soluble in boiling alcohol and ether.The solution shows the same bands as phyllocyanin but i f the smallest quantity of acid be added the third band from the end becomes fainter and the fourth and fifth bands split into t w o I t forms a compound with acetic acid. Phyllotaonin forms compounds with potassium sodium copper iron and silver. With tin and hydrochloric acid it gives a red cam- I)' und similar to that produced from phyllocyanin with the same rtiagents. A compound similar to the ether mentioned above may be obtained by treating phyllotaonin with ethyl iodide and potassium u 2280 ABSTRACTS OF CHEVICAL PAPERS. hydroxide ; it is a black substance whose solution gives an absorption- spectrum similar to that of the above ether. When chlorophyll is treated with alkalis and then with acids it probably yields phyllo- taonin which in the nascent state in contact with alcohol and hydro- chloric acid undergoes etherification. Crystallographic measurements of phyllotaonin are given.Hydroxyhydroquinoxalines. By 0. HTNSUERG (Anrialen 248 71-84) .-The author has repeated the experiments of Plochl (Abstr. 1886 351) and of Leuckwrt (ibid.) on the reduction of nitrotolyl- glycin by tin and hydroc;hloric acid and finds that the product is identical with the dihydrohydroxytoluquinoxaline which is formed by the action of ethyl chloracetate on toluylenedihmine. This substance rapidJy oxidises forming hydroxytoluquiiioxaline which Plochl and Leucknrt mistook for dihydrohydroxytoluquinoxaline. The substancu described by Leucknrt and Hermann (Abst,r.1887 38:3) as chlcro- dihydrotoluquinoxnline is also a derivative of hydroxytoluquincxaline. Ethyl a-chloropropionake acts on toluylenediamine forming an unstable compound which oxidises on exposure to tlie air yielding hydrmxy X:C (OH) meth yltotuyuinoxnline C7H6<K:CMe->. The substance is crys- talline and melts at 238". It is probably a mixture of two isomeric q uinoxalines. Dimethyloxy dihydrotoluquii.l.oxalin e C,H,< ~ ~ ~ ~ ~ prepared by the action of ethyl bromisobutyrate on toluylenediamine is a stable crystalline compound soluble in alcohol and ether. It melts a t 227" and yields a crystalline acetyl derivative Cl1HlJN20Ac melting a t 206". The nifroso-derivative C,H,,N,ONO melts at 153-1 54O with decomposition. The dinitro-compound melts at 280".Dimethyl- oxydihydrotoluquinoxaJine does not like its apparent homologues lose 2 atoms of hydrogen on oxidation but undergoes a deeper change. I t s whole behaviour shows that it does not belong to the class of H. K. T. hy droxyquinoxalines. w. c. w. Metabrornoquinolines. By A. CLAUS and G. N. Vrs ( J . tw. Chem. [a] 38 387-394) .-The metabromoquinoliiie nitrate (m. p. 163") previoiisly obtained by Claw and Tornier (Abstx. 1888 163) is really a mixture and the oil obtained from it is not pure metabromo- quinoline as then described b u t a mixture of both bromoguinnlines and generally contains some unaltered metabromaniline. When this nitrate is further fractionally crgstallised a nitrate melting a t 185" (u~icorr.) is obtained ; the base separated from this crystallises in beautiful colourless needles melting a t 48" (uncorr.) and as it has a higher melting point than the bromoquinoline previously described as annbromoquinoline (Ahstr.1888 163) it is doubtless t,he real n.nnbromoquinoZinP. Moreover this bromoquinoline cam be obtained from ana-amidoquinoline by converting it into ananitroquinoline and treating the latter by Sandemeyer's method. The other bromoq uinoline previonsly described as anabromoquino- line (Abstr. 1888 lti3) whose true melting point is 3 4 is the realORGASIC CHEMLYTRT. 2s 1 metubronzoquinoline ; its nitrate melts a t 19V ; il,s wwthiodide forms anhydrous yellow needles or prisms melting a t %4Uc ~unoorr.). When metabromoquinoline (1 part) is nitrated with a mixture (5 parts) of 2 parts of sulphuric acid and 1 part of nitric acid two nitro-derivatives are obtained.a-Nitrometahromopui?toli~e crptallises in large transparent prisms which melt at 192" (uncorr.) ; its platinochloride is bright-red and decomposes a t 240". a AmidoinetnbromuquirLoZLize forms coluurless needles which melt at 62" (uncorr.). /%Nitronaetabrornoquinolins crystallises from alcohol in white aggre- gates of needles which melt at 141" (uricorr.) and has feeble basic properties ; its ylatinochloride forms small golden-yellow anhydrous lam in%. 'l'he methiodlde of anabrornoquinoline crystallises from hot water in yellow needles melting a t 203" (iincorr.). Two nitro-derivatives are obtained by iiitratiiig annbrornoquinoline a-nitrarcubromo- qihinoZine which crystnllises in slender nearly colourless needles and melts at 146" (uiicorr.) and fi-nit~-unabromoquin dine which also forms nearly colourless needles ; i t melts at 126" (uncorr.) and is a stronger base than the a-compound.The platinochloi ides of both are described. A. G. B. A Cerium Qainoline Nitrate. By G. WILLIAMS (Chew. News 58 199-200) .-'When moderately concentrated so 1 u tions of ceric and quirioline nitrates are mixed glistening orange-red rhombic plates of the double nitrate Ce(N0,),.(C,H,N,HN0,)2 form. The air-dried salt is amorphous and melts rendily giving off nitrous fumes and an odour of nitrobenzene. 011 ignition it frequently deflagrates. D. A. L. Additive Product of Papaverine with Orthonitrobenzyl Chloride. By E. v. SEUTTEB. (Monatsh. 9,857-862).-20 grams of papaverine and 12 grams of orthonitrobenzyl chloride finely powdered and mixed together are heated for five hours on a water-bath.The product is extracted with water excess of the chloride removed by agitation with ether and the additive product obtained from the solut,ion in light yellow crystals. These contain varying amounts of water according to the method used in drying them The anhydrous product gives numbers f o r the chlorine and nitrogen wliich point to the composition ~,,,H,,NO,,C,H,NO,C;1. The nhrate picrate a i d dichroniate are described as also the platinoohloride. Constitution of the Cinchona Alkaloids. By Z. H. SKKAUP (Morzatsh. 9 783-827).-This paper contains the details of' the in- vestigation of the sjrupy oxidation product of cinchonine and quinine (Abstr.1887 164). 'l'hc syrup after removal of chromium by means of ammonia is treated with barium chloride and extracted with alcohol and is t h u s separated into two portious one which is insoluble con- taining the whole of the barium and the other free flom barium which is soluble. The barium salt of the organic acid present in the insoluble portion H. C.282 ABSTRACTS Ok' CUERIIC'AL PAPKRS. is converted into a lead salt and this on analysis has the composition (C8H12N01)PPb. It is the salt of the inoriobasic acid C,H,,NO mentioned in the former paper to which the name cincholeuponic acid is now given. By heating the lead salt with acetic anhy- dride a t 120-130" one o€ the hydrogen-atoms of this acid may be displaced by acetyl. Distilled with zinc-dust a mixture of J > ~ I idirie and its higher homologues is obtained together with a large quantity of a non-volatile resin.The action of nitrous acid yields ;Imong a variety of other products a bibasic acid of the composition C,H,,14'?O5. On treatment with hydrogen chloride this acid loses nitrous acid and becomes converted into the compound C,H N04,HCI a change which shows that the acid C,H,,N,O is N citroso- or isoni- troso-derivative. On removing the hpdrogen chloride from the above hydrochloride by means of silver oxide cincholeuponic acid may be obtained in crystals. This acid although monobasic probi>bly con- tains two carboxyl-groups one of which only becomes active in the acetyl- and nitroso-derivatires. That portion of the original syrup which is soluble in alcohol coil- t i n s the three bases mentioned in the former paper.Of these the last which is of doubtful origin and whose composition should have been given as C,3H16N0. hams been snbniittod to no further examina- tion. The base C9H17NO? separated by means of its crjstalline compound with gold chloride is here named cinchoieupone. It forms a crystalline coniponnd with 1 mol. HCI; this has a slight optical rotatory power. When oxidised with chromic acid cincholeuponic acid is obtained along with a number of basic substances. Heated with zinc-dust it gives $-ethylpyridine as the chief product but no qninoline is formed. By means of acetic anhydride one hydrogen- atom may be displaced by acetyl ; the derivative thus obtained has the properties of a monobasic acid.By the action of alkyl iodides 1 atom of hydmpn rnss be displaced by an alcohol radicle. The nitroso-derivative C,H,,N,OJ produced by the action of' nitrous acid has likewise the properties of a monobasic acid. The third base present C,H,NO which is separated by means of its plntinochloride is here identified with kpurine. The author discusses the above results with reference to the con- stitution of cinchonine. He looks on cincholeupone as a secondary amine being most likely a /3-ethylpyridine-derivative and considers it pmbable that cinchonine contains a quinoline-ring connected by a t least two of its carbon-atoms with an etliylated pyridine-ring. H. C. Colchicine. By G. JOHANNY and S. ZEISEL (Monatsh. 9,865-881). -The view put forward by one of the authors (Abstr.1888 613) that colchicine is niethylatecl colchiceine and this latter an acetyl- derivative of trirnethylcolchicinic acid is supported by synthetical evidence. By the action of methyl iodide on sodium colchiceine col- chicine is produced as also by passing hydrogen chloride through a solution of colchicelne in methyl alcohol. I n the first of these re- actions a substance is also formed which appears to be naethylcodchicine CLLH24NMt06 ; this when boiled with dilute hydrogen chloride yieldsORUAKIC CHJC!IlIST RV . 283 methylcoIchice'ine. Colchiceine is produced by the action of acetic anhydride on tiime t h y 1 colch i cinic acid. Trimetliylcolchicinic acid is found to crystallise with 2 mols. MeOH. When heated with sodium metahoxide and methyl iodide i n mole- cular proportions a substance is obtained which the authors call tl-imet hy 1 co 1 chidi?msth lnic a c i d C 0 0 E€*C i5H9 ( 0 Me) B*N Me2 in w h i c h the hydipoperi-atoms of the amido-group in the original acid have been substituted by methyl-groups.By the action of a further quantity of ruetliyl iodide the methiodide of t h s methyl s a l t of the above acid is obtained. This substance on treatment with si!ver oxide gives oE trimethylamine thus showing that it contains the NMeBIL group. H. C. It melts at 126". Action of Acid Chlorides on the Methyl Salt of Ecgonine Hydrochloride. By A. EINHORN and 0. KLEIN ( B e y . 21,3335-3338). -The methjl salt of ecgonine hydrochloride C,B,4NO-C00%Ie,HCl + HzO is obtained by saturating a solution of ecgonine hydrocbloride it1 methyl alcohol with hydrogen chloride and heating the product in a reflux apparatus for an hour.It crystailises from alcohol i n beau- tiful transparent prisms and melts a t 212" with decomposition. The methyl salt of benzoylecgonire o r cocaine C17H21Y04 can be prepared by heating equal weights of the methjl salt of ecgonine hydrochloride aiid benzoic chloride at 1C'O" for some hours until hjdrogen chloride is no loilger evolved. The hase obtained by adding a n alkali to the product has all the properties of the natural alkaloid (compare Lie1,erniann and Giesel this vol. p. 168). The methyl salt of isovccle?.yZe~gllnine C,,H,,NO,. is formed by heilting equal weights of the methyl salt of ecgonine hydrochloride and isovaleric chloride at 100" f u r 15 minutes.The base is ax oil and could not be crystallised although i t s hydroc.hloride hydro- bromide and hydriodide crystallise well. The ylatinochlor-ide. (C15HziNO~)~,H,PtCI forms large scales. The methyl salt of ~ h e n y Z n c e t ~ Z e / ~ ~ o n i r i e C1sH'L3NOir is obtained by heating equal weights of the methyl salt of ecgoiiine hydrochloride and phenylscetic chloride a t 100" for some hours. It is a n oil which could not be crystallised although its hydrobromide and hydriodide crystal!ise well from absolute alcohol. The platinochloride (C18 H 2,PU'0,)2,H,PtCI is crystalline. The diniethyl salt of oi-fho~htlLtrZyZdieI.gonilie C2RH36N208 is prepared nnder like conditions from the methyl salt of ecgonine hydrochloride and orthophthalic chloride. It is crystalline and jields a hydr- iodide crystallising from alcohol in scales.The pZati)mchZvyide Cz8H36Nz08,HzPtC1 crystallises in scales. w-. P. w. Cinnamylcocahe. By C. LIEBERMANN (Ber. 21 3372-3376) .- C'innanzyZecgoni?t e CgHiO-C9H14N03 is prepared by heating a mixture of ecgonine (1 mol.) and half its weight of water with cinnamic anhydride (1 mol.) on a water-bath for an hour grinding the product with 6-@ times its weight of water filtering from unattacked cinnamic anh?dride and from ciunamic acid extracting the filtrate wit11 ether to284. ABSTRACTS OF CHEMICAL PAPERS. remove all cinnamic acid and finally concentrating to the crystallising point. I t crystallises in beautiful vitreous spenr-like anhydrous needles melts at 216" with decomposition is readily soluble in alcohol and is precipitated from the alcoholic solution by ether.When boiled with hydrochloric acid i t is readily converted into cinnamic acid and ecgonine and on treatment with dilute potassium permangarlate solution it is at once oxidised an odour of benzaldehyde being pro- duced a t the pame time. The azwochZoride C9H,0*CgH,4N03,HAuCI~ is anhydrous. Cinnamylcocuine CgH,0*CgH,,MeN03 is obtained when a concen- trated solution of cinnnmylecgonine in methyl alcohol is treated with hydrogen chloride and allowed to remain in the cold for 24 hours in a closed vessel. It separates from a mixture of benzene and light petrcT- leum in beautiful crystals with vitreous lustre showing many faces melts a t 121" and i u insoluble i n water but soluble in alcohol ether acetone chloroform and benzene.The hi/droch7oride crystallises in colourless needles and the platinochloride. (C,gH,,N04),,H,PtCl crys- tnllises in microscopic needles melting a t 217". w. P. w. Imperialine. By I(. FRAGNER (Ber. 21 384-3287) .-1/npericd- ine C3aHG0B504 occur5 in the bulbs of F?'ittiZiw;cz imperialis and can he obtained i n the pure state as follows:-The crushed bulbs are rubbed up with lime the mixture dried a t loo" and extracted with hot chloroform. The extract is shaken with water acidified with tartaric acid tho alkaloid precipitated from the concentrated aqueous solutioii with sodium carbonate washed and recrystallised from alcohol. TIie yield is 0.08-0.12 per cent. I t crystallises in shott colourless ueedles turns yellow when heated a t 240' brown a t 248" and melts a t 2.54".It is very readily soluble in chloroform riioderately in hot alcohol more sparingly in ether benzene light petrolrlum and amyl alcohol aud very sparingly in water; the solutions have a bitter taste and the specific rohtory power in chloroform solution is [a]= = - 35.4". The hydrochZorir?e C,,H,,NO4,HCI separates froni alcoholic hydrochloric acid in large crystals and i s readily soluble in water and alcohol. A yellowish- red p Zatin och Zoride ( C3,H,,N04) 2 H2P t C1 6r and a yellow aurochloridp C35H60N04,HAuC14 are precipitated in oily drops when ether is added to a n alcoholic solution of the hydrochloriue and platinic or auric chloride ; after having been washed with ether both salts separate fi*orn hot dilute hydrochloric acid in a crystalline condition.The sulphate is very hygroscopic and was not obtaiiied in a crystalline condition ; the oxalafe crystallises only from very con- centrated solutions. Nost of the usual reagents for alkalo'ids produce precipitates in solutions of the salts. The free base turns pale yellow when treated with sulphuric acid and when previously mixed with suqar it first becomes yellowisli-green then pnle-green flesh colour cl erry-red and alter a long time dark violet. Frohde's reagent colours it greeuish-Fellow and with Mandelixi's reagent it gives an olive-greeii coloration which passe's through reddish-brown and becomes dark brown. When mixed with potassium nitrate or potassium chlorate and then moistened with aulphuric acid i t turns 0 mge-yellow ; if however the mixture is previously warmed it t u r n sORGANIC CHENISTRY.283 dark reddish-yellow. The solution in hydrochloric acid fluoresces becomes brownish-green when warmed and turns brownish-red when the heating is continued for a long time. Bg 3'. HOPPE-SEYLER (Zed. physiol. Chew . 13 66-121).-0~ the death of plants or parts of plants substances of a brown coloiir are formed which are called hunious substances. Wood however often remains white for years. I n dry air or a t a high tempeiaturz plants can be dried without browning. The bt owning of the surface of a cut apple may be taken as a very rapid example of the process. Bacteria do not seem to be concerned in this change. This brown coloration does not occur to any extent in dead ariinial tissues.It is not however due to the chlorophyll of plants as it occurs equally quickly in plants which contain no ohlorophy11. The almost universal distribution of tannic acid and carboliydrates and especially of cellulose suggests that these may be sources of the liumous substance o r i t may come from the hydrocyanic acid phenol m d nitrogenous compounds of plant tissues. Pure cellulose when mixed with mud containing micro-organisms ferments and yields carbonic anhydride and methane in the absence of uxygm but no humous substance is formed (Abstr. 1886 923) ; in the presence of oxygen the cellulose (filter-paper) still 1 emainh quite white; all sorts of mud being used in the experiments. By heating with water a t 188-200" or with caustic alkalis humom substances are formed.Water in glass tubes produced a brown residue and the liquid was found to contain formic acid catechol arid pi otocatecliuic acid ; when platinum tubes were employed there was a brown residue but the other products obtained in glass tubes were absent as they are due to the decomposition of the humons sub- stance produced by a small quantity of alkali dissolved out from the glass at the high temperature to which the tubes were subjected. Other experiments were performed with strong alkalis and the result- ing gases as well as the residue were annlysed. The fermentation of wood-gum was found to be similar to that of cellulose ; and it is supposed that the lignic acid may be in. t rurnental in the formation of humous substances in turf.peat &c. Tannin red obtained from certain plants by extracting with water and the phlobaphen of Stahelin and Hofstetter an amorphous brown substance are apparently derivatives of tannic acid and may be included under burnous substances. The preparation and properties of a large number of these substances are described. They are formed by the action of alkalis on various carbohydrates (dextrose lactose cane-sugar glycuronic acid &c.) ; from various aromatic substmces ; and those obtained from various vegetabie sources are also described. They are amorphous differing in percentage com- position mostly containing nothing b u t carbon hydrogen and oxygen. A few contain nitrogen like those described by Udr6nszky in urine (Abstr. 1887 1133 ; 1888 180).A derivative of humous substances c.alled huuiic acid is described and various names are given to sarious other members of the group. The originai paper must be consulted for details concerning their I?. S. K. Humous Substances.286 ABSTRACTS OF CliEJllChL PAPERS. preparation and analysis ; the following summary will however indicate the methods adopted in their separation. Hunious substances fall into three gi'oups the first includes those which are boluble neither in caustic alkalis nor in aIcohol but uiiite with alkalh forming a slimy mass. This group includes the hnmin and ulmin of Mulder. The second group consistc; of those which are completely soluble in alkalis aud precipitahle from such solutions hy acids ; tl\e precipitate formed is voluminous and jelly-like and is illsoluble in alcohol.A part of the tannin reds arid of humic and ulmic acids be1or;g to this group. The substances in the third group resemble hhose in the second with regard to their solubility in alkalis ; but the precipitate produced by acid is easily soluble in alcohol. Phlobaphen a part of humic and ulmic acids and the brown arids included under the name hymntomelanic acids (which are formed from the members of the first two groups by heating with caustic alkalis) belong to the third group. Cholamide and Hippuramide. Bp G. PELLIZZARI (Chem. Cenfr. 1888 1350-1352 from L'Orosi 11 233-235) .-By heating glyco- cholic acid €or one day at 16O-1iO0 with alcoholic ammonia under pressure a residue was obtained on evaporating the liquid which when recrystallised from aqueous alcolrol appeared as I G I I ~ silkj very deliquescent needles.'these are insoluble in acids and alkalis little soluble in boiling water readily soluble in alcohol and ether and melt about 125". The composition corresponds with that of Hufner's cholamidr. C,,H,,O,.CONH,. Isoglycocholic acid reacted with ammo- nia i n a similar way. Hippuric acid when heated with alcoholic ammonia for four hours at 210-210" reacted with formation of hippuramide mt~lting a t 183". Ry heating a t 260° a further change took place ethyl benzoate and benzamide being formed. W. D. H. J. W. L. Chinethonic Acid. By V. LEIIMANN (Zeit. yiiy.&Z. Chem. 13 181-186) .-Pheneto'il leaves the body partly in union with glycuro- nic acid i n the urine. After administration of this substance a n acid occurs i n the uririe called cbinethonic acid (Kossel Abstr.1881 631). I t may be prepared as follows :- The urine is concentrated acidified w i t h sulphuric acid and extracted with ethyl acetate; this is sepa- rated treated with excess of barium carbonate and distilled off; the residue boiled with water filtered hot and the filtrate evaporated to a small bulk. I n a few days the barium double salt crystxllises out ; this is recrystallised dissolved in hot water and neutral potassium sulphate added as long as a precipitate of barium sulphste forms; this is filtered off the filtrate evaporated to dryness and the residue extrscted with boiling alcohol ; the potassium salt goes into solution a n d on cooling crystallises out ; the potassium salts of the ethereal hydrogen sulphates remain in solution.Some of these latter are formed from the phcnetoil administered. The relation of total sul- phuric anhydride t o that combined as et.bereal hydrogen sulphates was in a dog hefore the experiment = 8-92; r,fter the ac'ministra- tion of 12 grams cf phenetoil it fell to 2.74.PHTSIOLOGLCA I d CHEJIISTI1T. 287 The potassium salt C14H,,0,K + H20 of the new acid occurs in mcmoclinic crystals and the silver salt has the formula C14Hli08Ag + H,O. The free acid C14HIBOR obtained hy treating the potassium salt with sulpliuric acid is crystalline and melts a t 146". When treated with dilute sulphuric acid an oily substance which subsequently crysta liaed was obtained ; it had the formula C,H,,,O that is coil- tained one atom of oxygen more tlrnn plienetoll.The question arises whether the oxygen is united to the benzeite nucleus or is derived from oxidation of the ethyl-group. It was found that on decomposing chinetlionic acid with hydrogen iodide quinol is formed xnc-l with oxidising agents quinone is formed easily. 'lhe constitntinu of chinethonic acid is therefore OE~.C~HI,.C~H&. M7. D. H.226 ABSTRACTS OF CHEMICAL PAPERS.0 r g a n i c Chemistry.Mineral Matter in Natural Petroleums. By J. A. LE BEL(Bull. SOC. Chiin. 50 359-361).-Bitumen was extracted from abituminous limestone from Lobsann in Alsace by means of lightpetroleum ; the greater part of the light petroleum was then distilledoff and the rest treated with amyl alcohol which precipitated ablack resin. This was again dissolved in light petroleum precipitatedwith amyl alcohol and the solid precipitate washed with ether whichremoved a reddish resin. The asphaltene so obtained contains 5.4 percent.of ash. The latter contains 13 per cent. of silica 17 per cent. offerric oxide with traces of manganese and the rest consists chiefly oflime and calcium sulphate.Asphaltene from the natural oil of Colom6a in Galicia contains onlytraces of mineral matter. N. H. M.Oxidation of the Hydrocarbons C,H2,-,. By G. WAGNER(Bw. 21 3343-3346 ; comp. Abstr. 1888 665).-When diallyl isoxidised with potassium permanganate in dilute aqueous solution i tyields in addition to a trace of an aldehyde a mixture of two hexyl-erythrols C6Hlo( OH)4 which can be separated by fractional crystalli-sation on adding SuccesEive quantities of ether to their solution inabsolute alcohol.The less soluble hexylerythrol crystallises inaggregates of colourless lustrous right-angled tables melts at55.5" and is spwingly soluble in cold alcohol almost insoluble inether and readily soluble in water ; its taste is slight but sweet andcooling. The more soluble hexylerythrol is very hygroscopic anORUANTC CHEMIS'l'RY. 227more soluble in alcol?ol and ether-aicohol than the preceding com-pounds ; its taste is slight but sweet and cooling.The production of two isomeric. hexylerythrols in this way rendersit very probable that diallyl is not a homogeneous compound butconsists of two isomerides CH,:CH*CH,-CH,*CH:CH andCHMe:CH*CH:CHMe and additional evidence in favour of this viewis to be found in the results obtained by Sabaneeff (Abstr.1885,495) in brominating and by Sorokin (Abstr. 1878 962 ; 1880 370)in oxidising the hydrocarbon.Neither diallyl dioxide nor its first hydrate could be detected amongthe oxidation prodncts of diallyl and inasmuch as PEibytek has shownthat diallyl dioxide is not completely converted into the correspou dingerytirrol by heating with water a t 100" for 40 hours (Irzairg. Diss.,St. Petemburg 1887 33) the author concludes that the he~yler~ythrolsare obtained directly by the Oxidation of diallyl without the forma-tion of the corresponding oxides as intermediate products.Hydration of Methylarnylacetylene E thy1 Amy1 Ketone.By A.BI~HAL (BulZ. SOC. Chiin. 50 359).-EthyZ ainyl ketone C,H,,O,is obtained when the product of the hydration of methglamyl-acetylene is treated with sodium hydrcgen sulphite and kept for10 days. The product is then pressed in a calico filter the liquid whichruns off consisting of an aqueous and an oily layer separated and theoil washed dried and distilled. It boils a t 164-166" has a penetrat-i n g odour is insoluble in water and does not combine wit,h hydrogensodium sulphite. Sp. gr. = 0.8502at 0". N. H. M.Preparation of Ethylene Cyanide. By A. FAUCONNIER (Bull.Xoc. Chim. 50 214).-Ethylene bromide (300 grams) and alcohol(500 grams) are boiled in a reflux apparatus and a saturatedaqueous solution of potassium cyanide (200 grams) is gradually added.Thereaction is completed in less than two hours when the product isallowed to cool and the liquid decanted and evaporated in a vacuum.The residue is then dissolved in absolute alcohol and the solution dis-tilled first from a water-bath then in a vacuum over a flame.It boilsat 147" under 10 mm. pressure and solidifies to a colourless mass some-times crptalliiie and somet'imes amorphous. The yield is 75 to 80per cent. of the theoretical.Perthiocyanic and Dithiocyanic Acids. By P. KTASON (J. pr.Chern. [ a ] 38 366-337. Compare Abstr. 1887 1025).-The iso-perthiocynnic acid prepared by mixing a solution of ammonium thio-cyanate (1 kilo. in 6.50 c.c.) with hydrochloric acid (1 litre of 35-40per cent.) contains 10-15 per cent.of dithiocyanic acid even afterfractional crystallisation from 60 per cent. acetic acid. The pure acidis best obt,ained by decomposing the barium salt with hjdrochloricacid and recrystallising from a solution in 60 per cent. acetic acid.Isoperthiocyanic acid is very sparingly soluble in water alcohol andether bat crgstallises from acetic acid in beaut'ful yellow dichroicprisms which are the better formed the freer they are from dithio-cyanic acid ; its constitutional formula according to Glutz isw. P. w.N. H. M228 ABSTRACTS OF CHEMICAL PAPERS.CS*NH<NH.CS> S. When treated with alkalis it is partially decomposedinto dithiocyanic acid and sulphur ; but a recombination takes placebetween some of the dithiocyanic a,cicl which is converted into thenormal acid by the action of tho alkali and the sulphur giving risetso a salt of normal perthiocyanic acid ; thus the final result of the actionof an alkali on isoperthiocyanic acid is a mixture of the alkaline saltsof dit hiocyanic acid and normal perthiocyanic acid.Normal perthiocyanic acid is best prepared as follows :-lo0 gramsof barium hydroxide 50 grams of crude isoperthiocyanic acid and300 grams of water are gently warmed together until the sulphur atfirst separated has mostly redissolved. The mixture is then concen-trated and cooled when the barium perthiocyanate crystallises out,and is decolorised and recrystallised.If a fairlv strong solution ofthis salt is mixed with hydrochloric acid the iso-acid crystallisesout ; but if the solution is weak and is cooled to 0" nothing crystallises ;if the cooled solution is shaken with ether the normal acid is ex-tracted and is obtained together with some of the iso-acid when theethereal solution is evaporated at a low temperature.It is colourlessand easily soluble in water and in ether ; it easily passes into the iso-acid and its constitution is probably expressed by the formula<N:c(sH)>S its properties indicating the presence of two SH-groups.When a solution of iodine is added to a solution of a perthiocyanate,the colour of the former disappears and a white precipitate is after-wards formed but it is too nnstable for analysis. Potassium permm-gantte is also bleached by a perthiocyanate 1 mol.of the acidabsorbing 8 atoms of oxygen ; this would account for the oxidationof two of the sulphur-atoms to siilphuric acid and the formation ofan acid of the formula <N:C(OH)>S ; but this has not been ob-tained in a state fit for analysis.A solution of potassium perthiocyanate gives a green precipihtewith copper sulphate a yellow one with lead and bismuth salts and awhite one with silver nitrate-all insoluble in excess of the perthio-cyanate ; the precipitntes formed with cadmium zinc mercury cobalt,nickel and ferrous salts are all soluble in excess of the perthiocyanate.Ferric chloride gives a black precipitate which gradually becomeswhite. Barium perthiocyanate crystallises in slender needles contain-ing 4 mols. H,O three of which are lost a t 110" and the fourth at 150" ;it is easily soluble forming an alkaline solution which is convertedinto barium thiocyanate and sulphur when heated for 12 hours on thewater-bath.The neutral aud acid potassium salts the calcium lead,and silver salts are also described. The ethyl salt Et,C2N,S3 is astrongly refract,ive colourless oil of the consistency of olive oil ; itssp. gr'. is 1.2544 a t 18"; i t has a faint sweet smell and boils in avacuum at about 190". When heated with strong hydrochloric acid,i n which it is soluble in a waled tube it is decomposed with forma-tion o f ammonia carbonic anhydride hydrogen sulphide. ethyl hydro-sulphide and ethyl polysulphide. Alcoholic potassium hydrosulphideC(SH):NC(0H):ORGANIC GHlC X I ISTRY.229converts it into ethyl 11 ydrosulphide and potassium perthiocyanate.The ethyl and siilpliur thus appear to be directly united.Perthiocyairoglycollic m i d C,N,S( S-CH,*COO H)2 is obtained whenisoperthiocyanic acid (1 mol.) is first shaken with a solution of potas-sium hydroxide (2 mols.) for some time and a solution of sodiumchloracetate (2 mols.) then added. This mixture is heated on thewa ter-bath and hydrochloric acid added when the free acid crystallisesout on cooling in long slender obliquely cut colourless tables. Itmelts with decomposition a t 177" and is nearly insoIuble in cold buteady soluble in h u t water. I t s solution gives white precipitates withlead acetate and silver nitrate and a yellow one with ferric chloride.When heated with hydrochloric acid in a sealed tube thioglycollicacid is formed among other products.Tbe potassium blnriuliz (with3 mols. H,O) calcium (with 3.5 mols. H,O) zinc cadixiurn and coppersalts are described. The ethyl salt cannot be distilled; the atnideforms slender prisms which melt at 125".The dithiocyanic acids were first described by Fleischer ; the iso-acid is always obtained along with isoperthiocyanic acid when athiocyanate is decomposed by an acid; but the author has neverobtained i t in the puye state.The normal dithiocyanates are colourless not yellow as Fleischerhas stated; the author has not obtained them free from perthio-cyanates from which they differ in that with ferric chloride theygive a dark-red coloration which rapidly changes to yellow and finallyto a greyish-white precipitate.When it is attempted to prepare theethyl salt ethyl thiocyanate is obtained; nor can the hydrogen inthe acid be displaced by any organic radicle without decomposing themolecule with formation of a thiocyanic derivative. A. G. B.Platinum Compounds of Methyl Sulphide. By C. ENEBUSKE( J . pr. Chem. [Z] 38 358-365).-Three isomeric chlorides of thegeneral formula PtC12,2Me,S are obtained by the action of potassiumplatinosochloride on methyl sulphide. The a-plufosonzethylaulphinechloride Pt(S.Me,),CI crystallises from chloroform i n citron-yellow,transparent monosymmetrical crystals melting a t 159" ; after melting,i t dissolves in chloroform with formation of both the a- and p-chlo-rides.The P-chloride forms quadratic tables which contain 1 mol. ofchloroform ; i t melts a t 159" and gives both chlorides after melting.A red pulveralent chloride is tirst formed when potassium platinoso-chloride acts on methyl sulphidc and this becomes yellow and floccu-lent at a temperature of 50"; both forms are insoluble in chloroform,and are stable towards reagents ; the author regards this a s a doublechloride of the formula Pt ( S MeL C1.C 1. P t*SMt,. SMe,C 1)2. Platoso m et hy E-sutphine bromide P ~ ( S M ~ B Y ) ~ forms bright yellow monoclinic crys-tals ; the iodide forms ruby-red crystals which decoinpose at 172" ;the sulphrtte Pt:( SMe,0)y:S02 + 2H20 forms yellowish crystals,easily solnbIe in water ant1 melting a t 91" ; the nityate nitrite chromateand hydroxide are also described.The author has obtained saits of the radicle yllrtosomethyldisu~~hine,Pt ( S M e2) 4.'l'he platiriic derivatives are obtained from the platinous derivativesVOL.LVI. 230 ABSTRACTS OF CHEMICAL PAPERS.by treahing their chloroform solutions with the halogens. Plativo-nrethylsulphine chloride PtCI,( SMe,Cl) is a yellow crystallinepowder decomposing a t 21 8" without melting. The bromocldoride,bromide iodochloride iodobromide and iodide are also described.A. G. B.Action of Hot Manganese Dioxide on Alcohol Vapour. ByE. DONATH (Chem. Zeit. 12 1191-1192).-Carbonic anhydride,acetone and small quantities of some higher boiling products areobtained when alcohol vapour is exposed to the action of manganesedioxide heated to temperatures varying from 150" to 360" the latterbeing reduced to manganese sesquioxide Mn,O?.Barium is frequentlypresent a8 an impurity and in combination with the manganese andsuch compounds give rise mainly to barium and manganese acetates,but also to salts of these metals with the higher homologous acids insmall quantities. Mixing with lime did not increase the yield ofacetic acid; but soaking the dioxide with sodium hydroxide anddrying well was more successful in this respect. D. A. L.Platinum Compounds of Ethyl Sulphide. By C. W. BLOM-STRAND ( J. pr. Chern. [2] 38. 352-358).-a-Platosethylsulpl~inechloride PtC1*SEt2*SEt,C1 is directly obtained by the action of potns-sium platinosochloride on ethyl sulphide.It melts a t 81". Thecrystals are bright yellow and inonoclinic [a b c = 1.3876 1 1.2610;= 86" 4'1. The /?-chloride Pt(SEt,Cl) is formed from thea-chloride and ethyl sulphide. It crystallises in greenish monoclinictables melting a t 106" [ a b c = 1.5567 1 1.2961 ; /? = 82" 44'1.The browbide Pt (SEbBr) forms yellowish-red monoclinic crystalsmelting at 118" [ a b c = 1.5072 1 0.98239; 6 = 87" 2.5'1. Theiodide P t ( SEtJ) forms large dark red monoclinic crystals whichmelt at 136" [a b c = 1.4714 1 0 9885; p = 89" 43'1.Platosethy lsulphine ylatinosochloride P t ( SEtzCI),,PtCl is obtainedby heating platinous chloride for some time with ethyl sulphide(1 mol.) ; i t is a yellow powder insoluble in alcohol.Platoseth y lmethylsulphzne chloride SEt,Cl-Pt*SMe,Cl is formedwhen platinous chloride acts on a mixture of ethyl and methyl sul-phides; it is a heavy oil with a Low freezing point.PlittosethyZ-propylswlphine chloride SEt2C1*Pt*SPr,C1 is a syrup which solidifiesslowly ; the iodide is precipitated by alcohol from a chloroform solu-tion in small lustrous y~llowish-red crystals.Platosethylsulphine nztrite Pt(SEt,*O.NO) is obtained by theaction of fuming nitric acid on the sulphate (see below) ; it crystnl-lises from chloroform in large rhombic pure white crystals whichare sparingly soluble in cold water. The sulphute is formed fromthe chloride and silver sulphate it is very soluble and crystallises inlarge short and thick crystals which have the formula Pt(SEt20),SOz + 7&0.The plaosFhate nitrate chrornate and oxalate have beenobtained and also b j treating the sulphate with barium hydroxide astrongly alkaline solution of the hydroxide.The platinic derivatives are obtained by dissolving the platinousderivatives (preferably in chloroform) and acting on the solution withthe halogen. Platinethy lsulphine chloride PtCl,( SEt,Cl) crystalliseORGANIC CHEMISTRY. 231in small bright-yellow tables and prisms which are triclinic and meltwith decomposition at 175"; the bromide forms red monoclinicprisms p = 88" 30' ; the browtochloride forms yellowish-red crystals,and the iodide crystallises from chloroform in pretty dichroic prismsmelting at 1O4" dark-red by transmitted and dark-blue by reflectedlight. A.G. B.Oxidation of Unsaturated Compounds. By G . WAGNER (Ber.,21. 3347- 3:155 ; compare Abstr. 1888,665).-When ethyl vinyl car-binol (b. p. = 114-114.5") is oxidised with a dilute aqueous solutionof potassium permanganate it is converted into a series of compoundswhich can be partially separated by steam distillation. The neutralproducts volatile with steam in addition to unaltered ethyl vinylcarbinol consist of propsldehyde and a small quantity of a pungentsubstance distilling below 1 lo" which yields a reddish-brown oilcontaining nitrogen with phenylhydrazine and is most probablyethyl vinyl ketone. The neutral product not volatile with stearn(yield 63 per cent. of that theoretically possible) is p e n t e n y Zglycerol,OH.CHEt-GH(OH).CH,*OH a sweet thick and very hygroscoprcsyrup which boils a t 192" under 63 3 mm.pressure has a sp. gr. =1.0851 a t 34" (water at 0" = l ) and is soluble in all proportions in we erand alcohol and also soluble to some extent in ether. Its t r i a c e f u t e i\ asyrup with a Faint alliacenus odour boils a t 177' under 52 mm. pressure,and at 261-26.5" under the ordinary pressure has a sp. gr. = 2.122 a t0" and = 1.103 at 18" (water a t 0" = l ) and is soluble in the ordinarysolvents. The acids volatile with steam consist of a mixture of formicand propionic acids and the non-volatile acids comprise oxalic avidand a compound which from the analysis of its zinc salt and behavionrwith phenglhgdrazine is almost certainly propionylformic acid.Toonly a limited extent therefore under these conditions is ethyl vinylcarbinol oxidised as a secoiidary alcohol to the corresponding ketone ;on the contrary it undergoes oxidation as though it were an olefine(Abstr. 1888 665 j yielding pentenylglycerol which by further oxi-dation yields on the one hand probably propionic and oxalic acids onthe other formic and propionylformic acids the last by its decomposi-tion forming carbonic anhydride and propaldehyde.Methyl allyl carbinol when oxidised in like manner yields as chiefproduct (82 per cent. of that theoretically possible) pentenylglycerd,OH-CMeH*CH,.CH(OHj*CH,*OH which boils a t 180" under 27 mni.pressure has a sp. gr. = 1.135 at O" and = 1.120 a t 22" (water a t 0"= l) is somewhat more mobile than its isomeride and has a sweetbut burning taste.Its triacetate has a cucumber-like odour and asp. gr. = 1.120 at 0" and = 1.101 a t 20" (water a t 0" = 1). Theneutral product volatile with steam is acetaldehyde and the acidsvolatile with steam are formic and acetic acids traces only ofnon-volatile acids being present. Inasmuch as no trace of a ketonecould be found methyl allyl carbinol under these conditions seems tobe oxidised exclusively as an olefine.Ally1 alcohol under like conditions yields glycerol acraldehyde andformic acid and therefore forms oxidation products characteristic bothof an olefine and of a primary alcohol.r 232 ABSTRACTS OF GEERIICAI PAPERS.Unsaturated aldehydes are known to yield the corresponding acidson oxidatiori and herice behave like the saturated compounds.Un-s;1 turated ketones however probably yield the corresponding hydr-oxyketones ; thus the production of hydi oxpisohutyric and acetic acidsby the oxidation of mesityl oxide (Pinner Abstr. 1882 941) is mostprobably prereded by the formation of the dihydroxyketone.I n the author's view hydroxy-compounds are the primary oxidation-products of unsaturated hydrocarbony alcohols and ketone9 when theoxidation is effected not only by dilute aqueous potassium perman-ganate b u t also by any substance which exerts a purely oxidisingaction these primary products subsequentlg undergoing variousfurther changes under the different ronditions obtaining in eachoxidation. The view hitherto gene~ally accepted that unsaturatedcompoucds on oxidation break up a t the point of the '' double bonds,"is no longer tenable even in those cases wliere decomposition iseffected by fusion with potassium hydroxide sirice this reaction findsits most probable explanation in the view that for example an acid,CHR:CR'*COOH (where R = C1zH2n+l and R' = H or CnHPn+l) is firstoxidised t o the compound CHR( OH).CR'(OH)COOH which thenundergoes reduction to the /I-ketonic acid R.CO*CHR'.COOH whichin the presence of the alkali hydrolyseu in the usual way into theacids R-COOH and CH,R'-COOH.w. P. w.The Part played by Water in the Oxidation of UnsaturatedCompounds. By G. WAGNER (Ber. 21,3856-3360) .-The author'sexperiments (Abstr. 1888 665 ; preceding Abstract) show that un-saturated compounds when oxidised i n the presence of water cannotcombine directly either with oxygen or water but invariably yieldcompounds formed by direct union with hydroxyl. Water therefore,plays a very important part in the oxidation and the reaction isprobably represented in the case of ethylene by the equationC,H + 0 + H,O = C,H,(OH)?.Therniochemical data show that theformation of glycol by the oxidation of ethylene according to thisequation involves the liberation of 58.4 cal. whereas the produc tivnof acetaldehyde by the action of oxygen on the hydrocarbon wouldPreparation of Epichlorhydrin. By A FAUCONNIER (BdZ. SOC.Chim. 50 218-214).-Dichlorhydrin is best obtained by the actionof hydrogeu chloride on glycerol a t 120-130" (Abstr.1888 244).Water and acid with traces of the symmetrical dichlorhydrin (h. p.176") distil over. The fractionboiling at 50-120" contains the two dichlorhydrins and the fractionboiling at 120-150" the two monochlorliydrins. The monochlor-hydrins with the addition of more glycerol are again treated withhydrogen chloride. With 3 or 4 kilos. of glycerol the operation takes30 to 40 hours.Ep ichlorhydrin is prepared by treating the crude dichlorhydrinwith very strong potash or soda following Reboul's method. Theproduct is decanted and distilled in a I acunm ; the epic*hlorhydrindistils over below 75" ; the fraction boiling a t 75-120° is nil-require an absorption of 33 cal. w. P. w.The product is distilled in a vacuum0 ROANlC CHEIIISTRY.233changed dichlorhydrin. The crude epichlorhydrin is washed withwater and distilled without previously drying i t ; the fractionboiling a t llti-118° is redistilled in a vacuum. The yield is verygood and with little trouble 1500 to 2000 grams can be prepared in aweek. N. H. M.Benzoic Acetals of Mannitol By J. MEUNIER (Compt. rend,107 910-911 ; compare Abstr. 1888 950).-The benzoic acetal ofmannitol is very readily obtained by dissolviiig mannitol in sulphurioor hydrochloric acid adding the requisite quantity of benzaidehyde,and agitating wfieii the mixture becomes completely solid. Puremannitol is uot necessary. The acetal is insoluble in water acids,alkalis and cold alcohol &c. and hence is easily purified by washing.It is readily reconverted into mannitol and benzaldehyde and hencemay be utilised to separate mannitol from mixtures such as plantjuices in which it occur9 along with albuminoids glucose &c.When the benzoic acctal is perfectly free from benzaldehyde it resiststhe action of acids as well as alkalis and is not decomposed even byprolonged boiling with acidified water.If however a small quantityof the aldehyde is present t,he acetal i8 readily decomposed the rate ofdecomposition increasing with the quantity of aldehyde. I n fact,decomposition will take place when it is treated with sulphuric acidof only 1 per cent. C. H. B.Sugar obtained from Plantago Psyllium. By R. W. BADE&(Annulev 248 140-144).-l'he carbohydrate obtained from theepidermis of PqZlium gallicum by boiling the aqueous extract withdilute sulphuric acid is xylose.It was identified by its melting point,rotatory power and by its compound with phenylhydrazine. w. c. w.Amylene Nitrosate and its Derivatives. By 0. WALLACE(Annulen 248,161-1'75).-Am,~lene nitrosat,e N0,*O*CMe2*CMe:NOH,is prepared by the action of nitric acid (sp. gr. 1.385) on a mixture ofnmyl nitrite amylene and glacial acetic acid. The best yield isobtained with an amylene boiling at 36-38". The crude productdecomposes in closed vessels but is tolerably stable when exposed tcSthe air. It is purified by recrystadlisation from warm benzene andafterwards from ethyl acetate ; if the solvent is rapidly evaporated,the nitrosate is deposited in needles but on slow evaporation finemonoclinic crystals resembling cubes in appesra nce are deposited ;axial ratios a b c = 0.977 1 1.4485 ; /? = 8:3" 32'.By the actionof potassinm cyanide on amplene nitrosate (Abstr. 1888 38) thepitrile CN.CMe,*CMe:NO H is formed. This substance melts at99-100" and boils at 230" with partial decomposition. It is freelysoluble in water aicohol ether and benzene. On saponification i 4yields an amide CONH,-CMe*CMe:NOH and the hydroxylamitie-derivative of dimethylacetic acid or ketoximedimeth~jlacrtic avid,OH.N:CMe.CMe,*COOH. The acid is freely soluble in alcohol,benzene and water. The silver salt is deposited from aqiieous oralcoholic solutions in needles. The acid nielts at 96-97> with de234 ABSTRACTS OF CHEMICAL PAPERS.oomposition yielding carbonic anhydride and the ketoximo of methylisopropyl ketone CHMe,-CMe:NOH.The synthesis of ketoximedi-mei hylacetic acid from amylene nitrosate shows that this compoundis derived from trimethylethylene.,inzyZens~itl.o~i;f,e,.idide C5NH,,*CMe2*CMe:iSOH is best preparedby the action of amylene nitrosate on an alcoholic solution of piperi-dine. It is deposited from alcohol in glistening prisms. Hy theaction of boiling dilute sulphuric acid it is converted into the keto-base,C,NH,,*CMe2*C014e a colourless liquid boiling at 219-220" sp. gr.0.934. The hydrochloride is very hygroscopic but the platino-Aldehyde and Acetone Sulphites of Organic Bases. By H.SCHIFP (AnmaZen 248 14&146).-Not only primary monamines butalso secondary and tertiary amines and diamines have the power ofuniting with aldehydosulphites t o form crystalline compounds.Sulphines.By G. PATEIN (Hull. SOC. Chim. 50 201-206 ; com-pare Abstr. 1888 664).-When the compound SEt2Br2 prepared byCahours by the action of bromine on methyl sulphide is dissolved inwater (8 mols.) i t is decomposed with liberation of hydrogen bromide.When the alcoholic solution is treated with zinc the solution evapo-rated and the viscous product dissolved in water and treated withmercuric chloride the compound SMe,,HgCl + SMez,ZnBr2 is obtainedas a white precipitate.The iodide SMeJ prepared by the action of iodine on the sulphide,is crystalline and resembles iodine in appearance; it dissolves inalcohol ether and benzene but not in water and has an unpleasantodour.It is conrerted by anhjdrous alcoholic ammonia into iodo-form and a compound of iodoform with methyl suphide. Whentreated with silver cyanide silver iodide cyanogen iodide and methylsulphide are formed.chloride ( CI,HI9N O),,H,PtCl forms fine crystals. w. c. w.w. c. w.N. H. M.Symmetrical Dibromacetone. By E. HJELT andV. 0. SIVEN(Her. 21 3288-3289) .-Dibromacetone (symmetrical) can be pre-pared by oxidising dibromhydrin (50 grams) with a mixture ofpotassium dichromate (25 grams) sulphuric acid (40 grams) andwater (40 grams) and purifying the product by means of the sodiumhydrogen sulphite compound (compare Aschan this vol. p. 31).The yield is 20-25 per cent.of the dibromhydrin employed. It is ttcolourless liquid with a pungent odour (compare Volker Abstr. 1878,781). The hydrogen sodium sulphite compound C,H,0Br,,NaHSS03 + 1hH20,. crystallises in nacreous plates and emoresces on exposureto the air. Dibromacetone yields a very unstable compound,C3H40Br,,N H3 with ammonia and it also reacts with phenylhydr-azine. The oxime crystallises in slender needles. When the acetoneis heated with Fehling's solution the latter is reduced and when it isdlssolved in baryta-water or potassium carbonate solutions are obtainedwhich probably contain dehydroxgncet,one as they reduce Fehling'ssolution when warmed with it and jield a sjrupy liquid when evapo-rated and extracted with alcohol. B. S. KORGANIC CHEMISTRY.235Preparation of Ketones. By J. HANONET (Bull. SOC. Chim. 50,355-358) .-Propione COEt is prepared by digesting propionicchloride (1 mol.) with ferric chloride (1 mol.) using a refluxapparatus. The mixture is at first cooled and afterwards heated atabout 60". The product is poured into a little well-cooled wat'er andthe oil washed with water and distilled. Theyield is about 34 per cent. of the theoretical.Butyrorze COPr2 is obtained by heating butyric chloride (4 mols.)and ferric chloride (1 mol.) at 45" or 50"; the black oil is washedwith alkaline water before being distilled. It is lighter than water,and boils at 142-1U".It boils at 101-102".Qhanthylone was prepared from heptylic chloride.Diethoxyacetone.N. H. M.By E. GRIMALJX and IJ.LEFAVRE jCompt. rend.,107 914-916).-Ethyl ethoxyaceto-ethoxyacetate is allowed toremain 48 to 72 hours at the ordinary temperature with a sufficientquantity of a 2.5 per cent. solution of potassium hydroxide to convertit into the potassium salt. The liquid is then acidified with sulphuricacid which liberates the free acid and the latter at once decomposeswith evolution of carbonic anhydride. The liquid is extracted withether and the ethereal solution dried and distilled. The greater partof the residue boils at 193-196" and the yield is 20-25 per cent. ofthe original ethereal salt.Dietkoqacetone CO (CH,*OEt) boils at 195" and is a colonrlessliquid with an aromatic odour and a sweet burning taste ; sp. gr. at17.8" = 0.980 ; vapour-density 4.95.It dissolves in alcohol and ether,and is slightly soluble in water; it volatilises in steam. Diethoxy-acetone combines with sodium hydrogen sulphi te with great develop-ment of heat forming a very soluble compound. Its reducing poweris very much greater than that of an equal weight of glucose. Itreadily reduces Pehling's solntion and yields a mirror with am-rnoniacal silver nitrate even at the ordinary temperature.Whentreated with sodium ethoxide an energetic reaction takes place withformation of brown resinous products insoluble in water but solublein alkalis.Diethoxyacetone is remarkable in having the properties of bothketones and ethereal derivatives of glycols.Action of Copper Acetylacetone on Carbonyl Chloride. ByTHOMAS and LEF~VRE (Bull.Xoc. Chim. 50 293-194).-When thepowdered copper-derivative is heated at 60-70" with carbonyl chloridedissolved in benzene the product filtered and evaporated crystals areobtained which are recrystallised from ether. The new compoundmelts at 120-121". When heated a sublimate of large yellowneedles is obtained which seems to be a different substance. Itdissolves in alcohol ether and benzene very readily in chloroform ;warm water seems to decompose it. When heated with ammonia itdissolves at once and yields a compound melting at 250". The com-positiou of the compounds has not yet been determined.It cannot be converted into symmetrical dichloracetone.C. H. B.IS. H. M236 ABSTRACTS OF CHEMICAL PAPERS.Arrangement of Atoms in Space.Geometrical Constitu-tion of the Crotonic Acids and their Halogen SubstitutionProducts. By J. WISLICENUS and in part E. TEISLER and H.LANGBEIN (Annulen 248 281-35s) .-a-/3-Dichlorobutjric acid andits derivatives have already been described by the author (Abstr.,1887 6Fj5). a-p-Isodichlorobutyric acid is prepared by saturatinga mixture of isocrotonic acid and carbon bisulphide with chlorine.After removing the solvent by passing a current of dry air throughthe product a small quantity of a-p-dichlorobutyric acid is depositedin crystals but the a-p-isodichlorobutyric acid remains as a non-crystallisable oil. a-P-Isodichlorobutyric acid yields d-chlorocrotonicacid when it is treated with &n excess of an aqueous solution ofsodium hydroxide and an aqiieous solution of i t s sodium salt decom-poses at 80° yielding carbonic anhydride and a-chloropropylene(b.D. 36"). \ A I CH,*C*H,H.b.Cl is easily attacked by alkalis at 100" a-Isoc hloropropylene,H-C.CHsand converted into allylene. a-Chloropropplene H,b,CI is lessreadily attacked.In the preparahion of a-P-dichlorobutgric acid by the action ofchlorine on a solution of solid crotonic acid in carbon bisulphide aqoily bye-product is obtained It consists of a mixture of a-p-isodichloro-butyric acid with the normal isomeride. ?'he amount of this bye-product is increased by raisixig the temperature a t which the reactiontakes place.the action of bromine on isacrotonic acidmixed with carbon bisulphide is a-P-isadi bromobutyric acid.A smallquantity of solid rt-p-bromocrotonic acid is also formed. a-G-Isodi-bromobutyric acid is decomposed by an excess of alkali yielding a t theordinary temperature a-bromocrotonic acid b u t a t 100" a mixture ofa-isobromopropylene (b. p. 39-60d) and a new a-bromopropylene(b. p. 63-64'). The lqttep is more conveniently prepared by con-verting a-isobromopropylene (from a-@-dibrornobutgric acid) intot,ribromopropane by the action of bromine. The asp-tribromo-rJroDane is mixed with alcohol and treated with zinc-dnst.The chief productA L H*C'CHB ig not easily attacked by alkalis but H & ~ B ~ a- Brow oprop 9 1 ene,CB,*C)*HH*E,ur ' is converted into allylene. a-is0 brom opropy lene,One part of potassium bromocrotonate dissolves in 493.4 parts of99.5 per cent.alcohol a t 21". Under similar conditions potassiumisobromocrotonatt! only requires 10.8 parts of alcohol.a/3-Dichlorobutyric acid is partly converted into ap-isodichloro-butyric acid by expodure to a temperature of 100-285" and chloro-arid bromo-cratonic acids are always farmed in small quantities when&-isochloro- 01' bt-omo-crotonic adds are distilled in a current ofsteam. Exposure to a mall quantity of hydrogen chloride a t 100"partially converts isocratonic into crotonic acidORGANIC CHEJlISTRT. %37a-Isobromocrotonic acid is completely converted into crotonic acidby the action of sodium amalgam in alkaline solution but in an acidsoliition isocrotonic acid is formed as well as crotonic acid.The nnthor concludes by replying to the criticisms of Michael(Abstr.1888 1147 and 1176). w. c. vcr.Action of Phosphorus Sulphides on Dibromosuccinic Acids.By I. OSSTPOFF ( J . RIW. C'hen2. Soc. 1880 20 245-2,>4).-if as isgenerally admitted dibromosuccinic acid is a derivative of fumai icacid and isodibromosuccinic acid of maleic acid the first ought to beconvertible into thiophen or its derivatives. The author finds,however that dibromosnccinic acid when heated with phosphorustrisulphide o r pentnsulphide under the ordinary pressure a t 140° doesnot give R thiophen cornpound. In sealed tubes with phosphorus tri-snlphide nothing but thionialic acid was formed. No better result v asobtained whea the sodium salt of dibronlosuccinid acid was eniployedor with isodibromosuccinic acid or its anhydride.These results are notin accordance with the equations Kues and Paal give (Ber. 19,555) as representitig the format ion of thiophen.The E€hereal Salts of Fumaric and Maleic Acids. ByI. OSSIPUFF ( J . %ss. Cheni. Xoc. l888,20,254-267).-Silver fnrnaratewas treated with isobutyl iodide i n the presence of ethyl ether huthardly any reaction took place. Silver maleate with isobuhyl OFisdamyl bropide gave no better results; the same is the case w i t hthe iodides of higher alcohol radicles.Ethyl and isopr(opyl maleates *ere found to have a normal vaponr-density. The same is the case with isopropyl fumarate but theisobutyl salt is found to decompose under these circumqtances ; evenisnpropyl fumarate which shows the normal vapour-density a t theboiling point of arhyl benzoate decomposes at the boiling point of,&naphthol (28.5-290").The mono-silver salt of male'ic acid (acid silver maleate) gave withethyl iodide hydrbgen ethyl maleate and from this the sodiumsalt C,H,O,EtNa was obtained.This after decomposition with sul-phuric acid gives free ethylmaleic acid which is not identical withethylfumaric acid.With acetic chloride the above sodium salt gives a compound whichwould seem to be the acetyl-derivative of ethylmale'ic acid as whenit is treated with ethyl alcohol at the ordinary temperature it yieldsethyl acetate and ethyl maleate. When male'ic anhydride is heatedin a sealed tube with benzyl dt!ohdl 8 mixture of substances isobtained consisting chiefly of sodium benz+ylmaleate.Phehol givesno reaction with male'ic anhydride.Comp6unds of Dibromopyruvic Acid With Hydrazines.By 0. NASTVOGEL (Annaleir 948 85-92). -Phefiylosazonglyoxalcarb-ozylic acid N,HPh:CH:C( N,HPh)*COOH i d deposited in orange-coloured crystals on mixing aqueous solutions of phenylhydrazineand dibromopyriivic acid. It melts at 201-203" with decomposition,and is soluble ih acetone acetic acid and in boilihg alcahoi or ben-B. B.B. B238 ABSTRACTS OF CHEMICAL PAPERS.zene. The sodium potassium and ammoniuni salts are crystalline,and are sparingly soluble in water.Paratol2/ZosazoneglyoxaEcarboxyl ic acid C,,EI,,N402 melts at 186-188Owith deconiposi tion and dissolves freely in warm alcohol acetone,benzene and acetic acid.The sodium potassium and ammoniumsalts are much more soluble in hot than in cold water.a-Naphthylosazoneg1yoxaIcarboa:ylic acid forms cherry-red crystalsand melts at 196". (3-Naphthylhydrazine and di bromopyruvic acidunite together forming a hydrazide probablyC,H,*N,H CH*C 0.C (0 H) :N,H.C loH7.This substance i s insoluble in alkalis and is decomposed by boilingwith an alcoholic solution of potassium hydroxide.Dibmnwmth y lh ydroaytoluquinoxalin~ C7H6<N:C(oH) -> isformed when a mixture of orthotoluylenediamine and dibromopyruvicacid in molecular proportions is boiled. It melts with decompositionat 235" and is reprecipitated on adding an acid to its solution ina1 kal is. w. c. w.N:C ( CHBr,)Tricarballylic Acid.By P. DAUMICHEN (Chem. Centr. 1888,1347-1348).-1n the preparation of ethyl malonate from monochlor-acetic acid and potassium cyanide an oil of high boiling point(286-287") was obtained as a bye-product. Its behavionr withbarium hydroxide and hydrochloric acid its elementary analysisand the analysis of its silver and copper salts shored it to consist oft rieth yl tricarball ylat e.No well-characterised substance is obtained from tricarballylic acidby subjecting it to distillation.Bmzy I tricarballylate prepared from the sodium salt and benzplchloride consists of lustrous pearly leaves soluble in alcohol,sparingly in ether insoluble in water. It may be prepared morereadily by neutralising the alcoholic solution of tricarballylic acid withpotash distilling off the greater portion of the alcohol and boilingwith benzyl chloride in a reflux appayatus.Acetyl tricarballylic anhy-dride ClaHloOll prepared by boiling carballylic acid with excess ofacetic chloride melts a t 128-129"; when exposed to moist air itbecomes hydrated with formation of acetyl tricarbaliylic acid. Tri-carballylanilic acid Cl2HI1NO4 prepared by heating '1 gram of tricarb-allylic acid with 3.18 grams of aniline forms lustrous pearly scales,and melts at 137". Tricarballylrparatoluic acid crystallises with1 mol. H,O and melts at 174". These two acids take up water whendissolved in it and pass into the bibasic derivatives; their silversalts are amorphous as also the copper salts of the toluyl-derivative.The tricnrballylparaditolzLic acid was also obtained ; it melts a t 174",is monobasic and with the heavy metals forms salts which are amor-phous TricarbnllylparatoZuidide was also found as a product of theaction of toluidine on tricarballylic acid ; it melts at 253'.Tricarb-ullylparaditoluyl is formed by dissolving paratoluidine and tricarb-allylic acid in alcohol ; it melts a t 178" anti when boiled with alkalispasses into $he paraditoluic acidORGANIC CHENISTRT. 239Tricarbd Zy Zamid e is prepared by treating ammonium tricarbally 1 atein ammoniacal solution in a sealed tube or bv protracted agitation ofthe triethyl salt with ammonia ; it melts a t 218" with decomposition,ammonia being evolved and trica? ballylamideimide remains ; thismelts at 172-173".J. W. L.By J. KRGTWIG ( Z e d .physikal. Chem. 2 787-795).-The author doubts the generality ofthe conclusions arrived a t by Dreyfus (Abstr. 1888,24) and gives thedetails of an investigation on the oxidation of tartaric acid by meansof potassium permanganate under different conditions. He showsthat the rate of oxidation increases with the amount of tartaric acidpresent and that it also proceeds more rapidlj without than with theaddition of sulphuric acid. The reaction takes place much morereadily in sunlight than in the dark and tlhe addition of excess ofsulpburic acid up to a certain point has an accelerating influence as hasalso the presence of manganese sulphate in the solution.Alloxan Sulphites of Organic Bases. By G.PELLIZARRI(Annalen 248 146-152).-The following compounds were pre-pared by adding an aqueous solution of alloxnn to solutions oforganic sulphites saturated with sulphurous anhydride :-Alloxonethylamine sulphite C2H7N,S03Hz,C~H2N204 + H,O forms colourless,monoclinic crystals ; a b c = 0.8341 1 1.2462 ; p = 1OU" 40' 20".Alloaan aniline sulphite CsH7N,S03Hz,C4HzK20~ + 2Hz0 crystallisesin large quadratic plates. The methylaniline compound,C7H9N,8O3Hz,C4H2NzOa + 2H,O forms small yellowish prisms.AZloxan dimethylaniline suZphite CBHIIN,SO3HP,C4H2NZO4 + 4H&,forms monoclinic plates ; a b c = 1.33'19 1 0.3394 ; 13 = 99" 22' 40".The benzidine compound forms triclinic prisms containing 3 mol.HzO. Tolidine and amidobenzoic and aspartic aclds yield similarcompounds.Alloxan pyricline sulphite is triclinic. The crystals areanhydrous. Anhydrous crystalline compounds are also obtained withquinoline picoline morphine and cinchonine. The strychnine com-pound crystallises with 1 rnol. H20 and the brucine compound withI& niol. H20. Alloxan ammonium sulphite forms triclinic crystals ;a b c = 0.6648 1 0.7121 ; a = 71" 11' 20" /3 = 99" 47' 20" andy = 80" 40'. The aqueous solution decomposes on boiling forming asmall quantity of murexide ; in presence of ammonia or ammoniumRate of Oxidation of Tartaric Acid.H. C.carbonate ammonium thionurate is produced. w. c. w-.Glycocine-derivative of a-Thiophenic Acid. By M. J A F F ~and H. LEVY (Ber. 21 3458-3461).-a-Thiophenic acid is notpoisonous and can be given to rabbits in the form of sodium salt i ndaily quantities of 2 grams by subcutaneous injection.It is excretedin the urine as a-thiophenuric acid the glycocine-derivative of a-thio-phenic acid.a- Thiophenuric acid C7H,NS03 crystallises from water in colourless,transparent strongly refractive thin prisms closely resembling thoseof hippuric acid nielts a t 171-1 72" and is very sparingly soluble inether but readily soluble in alcohol and hot water. When boiled withbary ta-water it hydrolyses almost quantitatively into a- thiophenic aci240 ABS I'RXCl'S OF CHEMICAL PAPERS.and qlycocine but when hydroljsed with hydrochloric sc'd if yields onlysmall quantities of a-thiophenic acid although the yleld of glycocineis quautitative.The siZcer salt C7HsNS0.3Ag crgstallises in colour-less microscopic needles dissolves sparinglv in water and is un-affected by exposure to light ; the bariurn salt (2 mols. H?O) crystal-lises in colourles4 slender needles and is readily soluble in water butinsoluble i n alcohol ; the calciurrz salt (? 5 mols. H,O) crystallises inthick prismatic needles and is extremely soluble in water.Influence of Light on the Action of Halogens on AromaticCompounds. By J. SCHRAMM (Monafsh. 9 842-853).-Tbe pre-sent) work a contiriuntion of the author's investigations (Abstr. 1885,4,51) was conducted with the object of ascertainidg the behaviourto wards the halogens of aromatic compounds containing side-chainswhich are not iiormal.Isoprop!lZbenzene.-In the dark or in pr'esence of iodine bromineenters the benzene nucleus a small quantity in the first case also dis-placing; hydrogen in the side-chain.The product boils a t 217-219"under a pressure of 739 mm and on oxidation yields a mixture of para-arid ortho-brombenzoic acids chiefly the former. In direct snnlight,bromine (1 mol.) acts rapidly the product being a clear liquid whichsolidifies a t -20". On distillation this gives off large quantities ofhydrogen bromide and about one-half of the original isopropylbenzeneis recovered. I t appears in this latter case that substitutiou i n theside-chain takes place a di bromisopropylbenzene being formed whichdecomposes on distillation.IsnbutyZbelzzene.-In the dark or in presence of iodine bromineenters the benzene nucleus a bromisobutyZbesLzene being formed wliichboilr a t 232-5-2333" under a pressure of 739 mm.and solidifies at-18". On oxidation i t yields parabrombenaoic acid. In directsunlight bromine rencts to form a compound which on distillatiotiloses hydrogen bromidr and yields a hydrocarbon boiling a t 180-185".This lather combines with bromine to form an oily bromide but inother respects does iiot resemble Perkin's isobutenylbenzene.Secondary butylbenzene when tpeated with bromine in the dark ori n presence of iodine gives a brornobutylbenzene boiling at 235.5-237".It is not readily oxidised but yields parabrotnbenzoic acid wheh heatedfor seven days with a concentrated solution of alkaline permanganate.The action of bromine in sunlight is rapid but the product was notexamined.By the action of bromine in the dark or in presence of iodine ter-tiary butylbenzene (trimethylphenylmethane) is converted iiito zbbr-ornobutylbensene boiling a t 230-230.5" under a pressure of 736 mm.,and of sp.gr. 1'2572. This compound cannot be oxidised unless withdichromate and excess of sulphuric acid when it is destroyed. It is %remarkable thing that tertiary butylbenzeiie is dot attacked by brominein sunlight even when the solution is heated to the boiling point. Assubstitution of bramine i n the side-chain alwajs takes place withelimination of the hydrogen-atom attached to the capbun nearestl thebeuzene nucleus the absence of such a hydrogen-atom in tertiarybutylbenzene may perhaps explaifi this behaviour.w. P.wORQAKlC CHEBIISTHY. 2-1-1I n the dark or in presence of iodine isoamylhenzene yields withbromine a bl.oinisoamylbenzerte boiling a t 253-255" under a pressure of736 mm. and of sp. gr. 1.2144. On oxidation it gives parabrombenzoicacid. Isoamylbenzene is readily acted on by Fromine in directsunlight the product being a liquid Eromisoamylbenzene which decom-poses on distillation into hydrogen bromide and phenylisoamylene.Tre;rted with another molecclar proportion of bromine in the dark ityields a dibromisoamylbeiizene melting at 128-129".It appears from the author's researches that the action of halogens onaromatic hydrocarbons in the dark and in direct sunlight may be com-pared in its results to action a t low and a t high temperatures.By thefirst substitution in the benzene nucleus takes place with formationof an ortho- or para-bromo-derivative whereas by the second substitu-tion in the side-chaiii is effected. H. C.Aromatic Cyanates and their Polymerides. By W. FRENTZEL(Chem. Cwtr 1888 1361-1 362).-Ethyl pseudocum!jlr.arbamate pre-pared from pseudocumidine and ethyl ch'orc carbonate dissolves readilyin alcohol and melts a t 91.5". Phosphoric anhydride eliminates1 mol. H,O from it with formation of pseudocurnylc~aiiate boiling a t221". Triethylphosphine and more readily potassium acetate,change the cyanate into its polymeride the cyanicrafe melting at234". Dlcuni y l c a d a m i d e prepared from the cyanate me1 ts a tFrom unsymmetrical metaxylidine [Me NH =1 3 41 the curb-amatr melting at 57" and from this the c.!/anci,te boiling at 205".wereprepared and b7 means of potassium acetate the cyanurate meltinga t 162" was obtained.From the symmetrical metaxylidine [Me NIT = 1 3 51 thecarbamate melting at 77.5" the cyanate boiling a t 208.5" and bymeans of carhonyl chloride dizylylca barnitie melting at 275" wereprepared. ~ ~ ~ n o z y l y l c a r b a n i i d e melting a t 162" was prepared fromthe last-mentioned compound by eveporating the aqueous solntion ofthe hydrochloride with potassium cyanate.New General Method for the Synthesis of Aromatic Corn-pouads. By C. FRIEDEL and J. M. CRAFTd ( A n n . Cltim. Phys. [ci],14 43;3-472).-When dry air or oxygen is passed into cold benzenein presence of aluminium chloride a very small quantity of phenol isformed but when the mixture is heated almost t o its boiling pointthis compound is produced in much larger quantities.After passingthe gas for some time the mixture is poured iiito water the super-natiint oil separated and the phenol obtained in a perfectly pure stateby extracting the acidified aqueous solution with ether and evaporat-ing. The oily product contains unaltered benzelle and red compounds;the latter are soluble in ether benzene and carbon bisulphide butinsoluble in alcohol acetic acid and watrtr and cannot be distilled.Metacresol can be obtained from toluene in like manner. In thisreaction also oily bye-products are formed ; these compounds arebrown soluble i n toluene and cannot be distilled.When benzene and powdered sulphur are heated together at 75-80'2tj0-270".J.W. L2 t2 ABSTRACTS OF CHEMICAL PAPERS.i n presence of aluminium chloride until the evolution of hydrogenchloride and hydrogen sulphide ceases the mixture poured into waterand the supernatant oil fractionated the following compounds togetherwith unaltered benzene are obtained (I) Phenyl mersaptan boilingat 170-173" ; (2) plien-jd sulphide boiling at about 288"; and ( 3 )diphenylene disulphide boiling at 364--366" (compare Stenhouse,AnnaZen 149 252 and Graebe this Journal 1874 469). A com-pound C12H8Sz02 is obtained when diphenylene disulphide (1 mol.) isoxidised with chromic acid (18 mol.) in glacial acetic acid solution(compare Graebe Zoc.cit.). It cryst~llises from benzene in smallprisms melts at 241" is readily soluble in glacial acetic acid sparinglyin cold benzene and dissolves in concentrated sulphuric acid with aviolet-red coloration.Benzoic acid is produced with evolution of hydrogen chloride,when a stream of dry carbonic anhydride is passed for some daysthrough a mixture of benzene and aluminium chloride heated almostto its boiling point.Phenylsulphinic acid is obtained by passing sulphurous anhydrideinto a warm mixture of benzene and aluminium chloride until theweicht of the hydrogen chloride evolved i s about half that of ?healuminium chloride employed and then gradually pouring the wholeinto cold water. If the reaction is continued too long or if themixture is allowed to cool a crystalline aluminium salt separates.The filtered aqueous solution is acidified with hydrochloric acid andthe product extracted with ether.When aluminium chloride is gradually added to a warm mixture ofbenzene and pb thalic anhydride hydrogen chloride is evolved andorthobenzoylbenzoic acid is formed.ParatoZtLolrZlorthobenzoic acid C6H4Me*C0.CcH4*COOH is obtainedwhen aluminium chloride (14 parts) is added in small portions at atime t o a mixture of phthalic anhydride (+part) and toluene (1 part).The whole is then poured into a large quantity of water and afterkeeping for some time the crystalline product is separated.Furtherquantities can be obtained by e-raporating the toluene. It crystallisesfrom boiling toluene in white prisms melts at 146" is very readilysoluble in benzene and alcohol more sparingly i i r ether and verysparingly in boiling water. Dilute aqueous solutions of the acid andsolutions of many of its salts have a sweet taste.The ammoiiiitm saltcrystallises from boiling water in which it is very readily soluble i nsilky needles. The sodizm salt crystallises in small needles and isrery readily soluble in water but more sparingly in alcohol. Whenheated with soda at about 340" it is decomposed almost quantita-tively into sodium benzoate and sodium paratoluate. The bariumsalt (+ 4 mols H20) crystallises from water in prisms or needles andloses its water at 110". Most of the salts of the heavy metals aresparilzglg soluble in water.Orthoduroylbenzoic acid CGHMe4*CO*C,H4*COOH obtained in likemanner crystallises from glacial acetic acid in plates melts above260" and is readily soluble in alcohol ether acetone benzene andtoluene but insoluble in water.The potassium salt crystallises inmicroscopic needles and is readilj soluble in cold water. The sodiuORGANIC CHEMISTRY. 243salt is sparingly soluble in alcohol and separates from the solutionagain only partially i n the form of small plates. The ammoniumsalt crystallises in needles. The barium salt (+ 1 mol. H,O) crys-tallises in slender needles and is moderately soluble in alcohol butsparingly in water. The culciihm salt (+ 1 mol. H,O) crystallisesfrom water in needles. The lead silver and copper salts are insolu-ble in water.Acetophenone is formed when benzene is treated with acetic anhy-dride in presence of aluminium chloride.When pure dry ethylene is passed into a mixture of benzene aridaluminium chloride heated at about 70-90" ethyl- diethyl- and triethyl-benzene are produced together with other higher boiling compounds.Aluminium phenyl is formed when mercury phenyl is heated withaluminium foil at 123-130".This compound will be fully describedin a subsequent paper. It melts a t about 2:30" and absorbs moisturewith great avidity but only absorbs oxygen very slowly when ex-posed to dry air. It yields diphenylmethane when treated withbenzyl chloride but it does not react with chlorobenzene a t 100" inbenzene solution. Yheuol is formed when oxygen is passed througha benzene solution of aluminium phenyl and when a xylene solution isheated with sulphur dipheriylene disulphide phenyl sulphide andprobably also phenyl mercaptan are produced.These results showthat aluminium phenyl behaves like a mixture of benzene andaluminium chloride and the authors consider that this fact isevidence in favour of the view t h a t an organo-metallic compound,probably C6H6*Al2Cl5 is temporarily formed in all reactions similarto those described above and those already described (Ann. Chirn.Phys. [6] 1 449) in which aluminium chloride is employed.Gustavson (Abstr. 1885 363) considers that the brown liquid,which is formed when aromatic hydrocarbons are placed in contactwith aluminium chloride or bromide has a definite composition which,i n the case of benzene is A1C1,(C6H6) or A1Br,(C6H6) and that itis this compound which reacts with the chloride bromide or iodide ofthe alcohol radicle.The authors find that when pure aluminiumchloride or bromide is mixed with dry benzene or toluene this liquidis not formed or only produced in very small quantities and that inthe case of aluminium chloride a considerable quantity remains un-dissolved in presence of excess of the hydrocarbon. When hydrogenchloride or bromide is passed into the mixture as recommended byGustavson it was observed that the liquid was formed in some casesbut not in others; when however a small quantity of water wasadmitted the liquid was always produced Analyses of the liquidobtained in various experiments showed that it was a complexmixture perhaps consisting of a compound of the hydrocarbon withalumiiiium chloride or more probably with a chlorhydroxide ofaluminium the organo-metallic compound C6H5*Al2CI5 excess of thehydrocarbon and hydrochloric acid.F. S . IC.Influence of the Presence of Halogens and Alkyl-groups onthe Replacement of Oxygen in Quinone-derivatives by theIsonitroso-group. By F. KEHRMANN (Bey. 21 3315-3321).244 ABSTRACTS OF CHEMICAL PAPERS.Chloroquinone melting at 54" and bromoquinone melting at 55-56"react with hydroxylamine hydrochloride in alcoholic solution a t theordinary temperature. The monoximes obtained have the constil u-tion [SOH X 0 = 1 3 41 and are unstable decomposing whenheated for a long time a t 80-90".They are not easily obtained inthe pure state crystdlise in small bright-yellow needles and arevery readily soluble in alcohol and ether but only moderately so inbot water arid very sparingly in boiling benzene light petroleum,acetone and carbon bisulphide. When reduced with tin and hydro-cliloric acid they yield halogen amidophenols [NH2 X OH =1 3 41 and when treated with cold concentrated nitric acid theyare converted into orthochloroparoximidoquinone decomposing at140" and orthobromoparoximidoquinone decomposing a t 24'2" respect-ively. They are with difficulty converted into halogen dioximes[(NOH) X = 1 4 31 when boiled f n r a long time with excess ofhy d roxy Inmine hydrochloride in aqueous solution.The dioximes crystalhe in small greyish-yellow needles aresparingly soluble in boiling water aloohol and ether moderately soin benzene and are converted into halogen dinitroso-derivatives whenoxid ised with alkaline potassium ferricyapide solution or warm dilutenitric acid.The halogen dinitroso-derivatives are yellow crystalline com-pounds with a smell resembling both that of qninone and iodoform.They are readily volatile with steam and dissolve in fuming nitricacid from which they are precipitated unchanged on adding water,but are only very sparingly soluble in ordinary solvents.They yielddiamines which are readily oxidised to quinones when treated withcllrornic acid or ferric chloride.Me tadichloroquinone nielting a t 120-121° metadibi-omoquinonemelt,ing a t 130-131" and metadi-iodoquinone melting at 1713" [O X,= 1 4 2 61 do not form dioximes.The monoximes are yellow,crystalline conipounds a lid me readily soluble in alkalis alcohol andether but sparingly in boiling water benzene and carbon bisulphide.The ch loro-derivative decomposes a t 140" the bromo-derivative at145". These oximes are readily converted into metadihalopenpara-nitrophenols when treated with cold moderately concentrated nitricacbid (compare Fischer and Hepp Abstr. 1888 456). Their consti-tution is therefore [ 0 NOH X2 = 1 4 2 61.P~radichloroquinone (m. p. ltil-162") parachlorobromoquinone(m. p. 171-172") and prtradibromoquinone (m. p. 188-189")[O X = 1 4 2 51 react with hpdroxylamine hydrochlorideunder the conditions described above forming both monoximes anddioxirnes which can be separ<ited by means of alcohol or benzene.Ptrrctd~chloro~ai~oximidr,quinone crjstallises in bright yellow needles,decomposes without melting when heated a t 138" and is readilysoluble in alcohol and ether but only sparingly in hot water benzene,and carbon bisu'phide. It is slightly volatile with steam but resini-fies when boiled f o r a long time with water.[OH C1 NO = 1 2 5 41 ob-tained by dissolving the oximidoqninone i n well-cool( d concentratednitric acid crystaliises from hot water or dilute a-lcohol in colourlessPa,.adichloropnranl'trophi nolORQANIC CHEMISTRY.245needles and from absolute alcohol in short thick quadratic prismsmelting at 115-116".It does not taste bitter and is somewhatvolatile with steam. I t yields an amine which is converted intoparadichloroquinune melting at 161-162" when oxidised with ferricchloride.Paradichl~roquinonediozime separates from benzene in greyish-yellow granular crystals and is readily soluble in boiling benzene,b u t sparingly in alcohol and ether and insoluble in boiling water.Puradichloroparadsnitrosohenzene prepared by dissolving the di-oxime in fuming nitric acid crystallises in citron-yellow needles,explodes when heated at 120-130" and is insoluble in the ordinaryfiolvents. It is not oxidised when boiled with nitric acid. Thsamine obtained by reducing the dioxime or the dinitroso-cornpound,is converted into paradictiloroquinone when treated with ferricchloride.Trichloroquinone and tribromoquinone yield dark brown resinousproducts when treated with hydroxylamine hydrochloride in alcoholicsol ut4ion and no crystalline compound except tetrachloroquinol wasobtained.Chloranil and bromanil are gradually reduced to the correspondinqquinols when boiled with hydroxylamine hydrochloride in alcoholicsolution.Trichlorotoluquinone tribromotoluquinone metadiclilorometaxylo-quinone [O Me C1 = 1 4 2 6 3 51 dichlorothymoquinone,@p-dichloro- and dihromo-a-naphthaquinone do not combine withhydroxylamine under the conditions described above.It seenis,therefore that the quinone-derivative cannot yield an oxime whenthe hydrogen adjacent to the CO-group is displaced by halogens oralkyls.Parachlorotoluquinone yields both a monoxime and a dioxime butbromotoluquinone LO Me B r = 1 4 2 61 and dibromotolu-quinone LO2 Me Br = 1 4 2 3 51 only yield monoximes.F.S. K.Dihydroxythiobenzenes. By G. TASSINART (Chem. Centr. 1888,1354 from Rend. Acad. dei Lincei [4] 4 ii 47-51).-The authorconsiders that the componnds he has obtained as well as theii- homo-lopes have a symmetrical constitution. Several isomeric corn-pounds were never obtdined a t the same time. The reaction is muchinore violent when the compounds are prepared from phenols in whichthe para-position to the hydroxyl-group is free and the derivativesso prepared have a higher melting point than their isomerides.I n the action of parabromophenol on sulphur dichloride con-siderable quantities oE each of the reacting substances remain u1i-changed.The acetyl-deriv:i tive of the dihydroxythiobenzene (Abstr.,1888 805) melts at 86 -87". From this the acrtylhydroxysul~hoiruwas prepared by oxidation; it forms colourless crystals which aresparingly soluble in cold alcohol and insoluble in water ; it softens a t160' and melts at 186-18i'. B y dissolving it in a little alcoholicpotash and re-acidifying a hydroxysulphone hydroays7ili)honebenzid,C,,H,,O,S was obtained which must be either a di-meta- o r a di-VOL. LVI. 246 ABSTRACTS OF CHEMICAL PAPERS.ortho-derivative. It is white crystalline melts at 186-187" and issoluble in alcohol little soluble in water and in acetic acid.Theacetylhydroxysulphone becomes readily soluble in potassic hydrateafter heating to 187" ; it is therefore probable that the acetyl-groupbecomes separated by heating.I n order to determine the constitution of the dihydroxythiobenzenemelting a t 150" Annaheim's hydroxysulphonebenzide was nitrated,in order to obtain the di- and tetra-nitro-derivatives. Picric acid wasformed as is also the case when the nitro-derivatives of hydroxy-sulplionebenzid are boiled with nitric acid.The acety 1 -derivative of orth odirnethy l d i h y drox y thiobenzene crys-tallises from alcohol and melts a t 44". When oxidised with potassiumpermanganate the corresponding benzide C11H1104S is formed whichmelts a t 132-133" is insoluble in water but soluble in hot alcohol.Bysaponifying with alcoholic potash dimethylhydroxysulphonebenzidemelting at 263" is formed; i t dissolves in alkali hydroxides andcarbonates and is reprecipitated from these solutions by carbonicacid.Diacety 7parad irnethy Zdihydroxy fl~iobenzene melts a t 83-84' andwhen oxidised yields the corresponding benzid melting a t 206-208" ;the latter is little soluble in hot alcohol. Saponification with alco-holic potash gives pwradimethylhydroxysulphonebenzide which is rathersoluble in alcohol and acetic acid and melts a t 209" ; it dissolves ina1 kali hydroxides and carbonatds and is reprecipitated from suchsolutions by carbonic anhydride.The acetyl-derivative of dihydroxythionaphthnlene melts a t 200° islittle soluble in and decomposed by hot acetic acid.Fluorescein.J. W.L.By R. MEYER and 0. OPPELT ( B e r . 21 33i6-33i8).-When fluorescein is heated for eight hours with aqueous ammoniaa t 180-200" a basic compound C2,H,,N30 is formed which on cool-i n g cry stallises in the tube in large thick reddish-yellow rnonoclinicprisms and tables. The hydro-chloride crystallises in tufts of reddish-yellow prisrnq and from itsrery dilute and boiling solution ammonia precipitates the base inscales of bronze-like lustre ; under the microscope these are seen toconsist of extremely characteristic X-like interpenetrating twins.The authors point out thatl the constitution assigned to fluoresceinby Knecht (Annale?z 215 83) is very improbable and proposeinstead the formulaIt is a direct yellow dye for wool.< ~ ~ b > C < C 6 H 4 ( o H ) > 0 C,H*( OH) [C OH 0 = 1 4 61,that of the derived base being <cfio.~>C<c6H4(NH,) C H C6Hk(NH2)>NH.Thebase must contain a t least one NHz-group inasmuch as its hydro-chloride yields a diazo-compound when treated with nitrous acid. Ontreatment with cold aqueous soda the lactone-ring is readily brokenup and the base yields a sodium salt crystallising in slender needles ;the solution when acidified and then precipita ted by ammonia is at oncereconverted into the original base. Eeduction with zinc-dust in thORGANIC CHEMISTRT. 247alkaline solution converts the sodium salt into a colourless compound,which is not precipitated on treatment first with hydrochloric acidand then with ammonia.Orcinphthalein when heated in like manner with aqueous ammonia,yields a base similar to that just described ; the chief product how-ever is a colourless crystalline neutral compound containingDesmotropy in Phenols.By J. HERZIG and S. ZEISEL (Monatsh.,9 882-899).-An examination of the indifferent oil obtained in thepreparation of pentethylphloroglucinol (Abstr. 1888 822) has beenundertaken. It was subjected t o the action of hydrogen iodide theproduct dissolved in ether and then extracted with potash. Thegreater part is taken up by the potash but a portion is not attackedand remains dissolved in the ether.If the potash solution is acidified and the product again dissolvedin ether and crystallised a crystalline mass is obtained one portionof which is sparingly soluble in alcohol and melts a t 209-212" whilstthe other is more readily soluble in alcohol melts at 91-93" and isin every way identical with the pentethylpliloroglucinol already de-scribed.The sparingly soluble portion has the coniposition of afetl.eth~lphZorogZieeinoZ. One atom of the hydrogen is replaceable bya metal and it is converted by the action of ethyl iodide into a mon-e t h \ l salt and by the action of acetic anhydride into a rnonacetatemelting about 60-62". It readily exchaiiges one atom of hydrogen forbromine the product being probably a mixture of several isomerides.A similar reaction with bromine is found to occm in the case of pent-ethyl phloroglucinol.The portion of the original product which is insoluble in potash,consists chiefly of a secoiidary hexethylphloroglucinol which as it isunattacked by hydrogen iodide must be regarded as hexethyltriketo-hexamethylme isomeric with the ethyl salt of the bi-secondary pent-nitrogen.w. P. w.ethylphloroglucinol already described. H. c.Derivatives of Parabromobenzyl and Parachlorobenzyl Al-cohols. By G. EBRERA (Gazzettu 18 236-243) .-Parabromobenzylchloride cannot be obtained by the bromination of benzyl chloride orby the action of chlorine on parabroinotoluene but the author hassucceeded in preparing it from parabromobenzyl alcohol. The latterwas prepared by Jackson and Lowery's method (Abstr. 18i8 64)of boiling parabromobenxyl bromide with water for several hours,using a reflux condenser operating on small quantities at a time(4 to 5 grains) and using abundance of water (500 c.c.).Themixture bumps very much but a metal vessel cannot be used as itacts on the bromide in fact when the latter is boiled with zinc-dust,nothing but pal-adibromobenzyl (m. p. 114') is formed; the chloride isacted on in like manner.The authors find that besides parabromobenzyl alcohol,C6H4Br*CH2*OH,the corresponding ether is also formed; tbe two however can bes 248 ABSTRACTS OH' CHEMICAL PAPERS.easily separated by crystallisation from water in which the latter isinsoluble. The alcohol crystallises from water in long flattenedneedles melting a t 75" ; Jilckson and Lowery give 77" the highermelting point being probably due to the presence of some of theether.Purabromobenzyl chroride C6HJ3r*CHC1 is obtained when thealcohol is treated wit)h phosphorus pentachloride but as otherproducts are formed at the same time it is far better to heat thealcohol with fuming hydrochloric acid a t 150' in closed tubes forthree to four hours.The reaction is complete and tbe chloride isobtained in a pure state by once recrystallising the product fromalcohol. It forms lustrous colourless needles which melt at 38-39'.It is very soluble in hot alcohol and its vapour attacks the eyes butmuch less than that of the bromide. It is isomorphous with para-chlorobenzyl chloride and with parachlorobenzyl and parabromobenzylbromides.Yarabroinobenxyl ether (C6H,Br.CH,),0.-As stated above thisether is formed at the same time as the alcohol when parabronio-benxyl bromide is boiled with water and is left as an insoluble residuewhen the product is treated witli hoiling water.It may be purifiedby repeated crystallisation from boiling alcohol. It can also be pre-pared by the action of dehydrating agents such as sulphuric acid,boric anhydride or zinc chloride on the a,lcohol; the two first-mentioned do not yield satisfactory results but with zinc chloride theyield is almost theoretical. The ether crystallises from alcohol inlong flattened needles which melt a t 85-86". It is insoluble inwater and only sparingly soluble in alcohol even when boiling. Ifthe ether is boiled for some time it is decomposed splitting up intoparabrornotoluene and parabromobenzaldehyde ( CaH,Br*CH,)20 =CsH4Br*COH + C6H,Br°CH ; these can be easily separated by distil-lation.The ether is attacked by nitric acid with formation of para-bromobenzaldehyde and other products but the amount of materialat the author's disposal was too small to allow of a complete investi-gation of the r( action.Purachlorober 8yZ Ether ( C6H4C1*CH2),O.-When parachlorobenzylbromide is boiled with water or dilute soda solution it does notbehave like the bromine-derivative as no trace of the ether isproduced. The latter can be easily obtained however by boiling thealcohol with zinc chloride. It crystallises from alcohol in needles orplates which are much less soluble than parachlorobenzyl alcohol. It,melts at 54-55" and when boiled splits up into parachlorotolueneNitrobenzyl Ethyl Ethers.By G. ERRERA (Guzzetta 18,232-235).-This is a continuation of former work (Abstr. 1887,1 103).Paranitrob enz y 1 Et h y I Ether 0 E t C H C H4*N0,. -T he gen era1method for the preparation of the substituted benzyl ethyl ethers,that is the action of alcoholic potash on the corresponding derivativesof benzyl chloride is not applicable in the cilse of paranitrobenzyl ethylc ther as paranitrobenzjl chloride under these circumstances is con-and parachlorobenzalde hyde. c. E. GORGAXIC CHEMISTRY. 249verted into paradinitrostilbene. I n order to prepare it the cl-iloride isheated for a long time with ordinary alcohol in a clo,e vessel in a boilingbrine bath as a higher temperature cannot be employed. The product,even after long heating still contains much unaltered paranitrobenzylchloride and in order to remove it a few drops of alcoholic potash areadded to the liquid whilst i t is still hot; this at once converts theunattacked chloride into dinitrostilbeue which being almost insolublei n alcohol is precipitated arid can be removed by filtration.The potashis then neutralised with hydrovhloric acid and the product distilledwith steam when the ether passes over with the aqueous vapour andsolidifies on cooling. Paranitrobenzyl ethyl ether is pale yellow andvery soluble in alcohol and in ether sparingly in light petroleum,from which i t crystallises in needles and insoluble in water. It meltsat 24-24*S0 and a t a higher temperature distils but is a t the sametime partly decomposed.Treatment with fuming nitric acid convertsit in to paranitrobenz aldehyde.21Zefanitrobeizzy 2 Ethyl Ether.-This is prepared by heating meta-nitrobenzyl chloride with a slight excess of alcoholic potash on thewater-bath and when the reaction is complete neutralising the liquidwith hydrochloiic acid and distilling the product with a current ofsteam. This ether is a yellow oil which solidifies to a crystallinemass in a mixture of snow and hydrochloric acid (melting point notgiven). It resembles the para-derivative in its behaviour to solvents,and yields metanitrobenzaldehyde when treated with nitric acid.Orthonitrobenzyl Ethyl Ether.-The orthonitrobenzyl chloride em-ployed for the preparation of this ether was obtained by the nitration ofbenzyl chloride.The liquid product when cooled by a freezing mixture,deposits para- and ortho-nitrobenzyl chlorides which can be easilyseparated by fractional cry stallisation. This may be much acceleratedbF introducing a crystal of one or other chloride into the super-saturated alcoholic solution when crystals of the same speciesseparate at once while the other chloride remains in solution and isdeposited later. It can then be obtained in a pure state by one re-crystallisation. The ort honitrobenzyl ethyl ether prepared like thepara-derivative is a yellow liquid which gradually becomes brown onexposure to the light. It does not solidify when cooled in a mixtureof snow and hydrochloric acid and is converted into orthonitro-benzaldehyde by the action of nitric acid.Derivative of Tetrole and Synthesis of Tribenzamidophloro-glucinol.By L. RUGHEIMER (BPY. 21 3325-3331).-When ethylhippurnte (5 parts) is gradually heated with dry sodium etlioxide sothat in the course of about three hours the temperature rises to about160-170" alcohol distils and on adding water to the residue twosodium salts are formed one of which is only very sparingly solublein dilute soda.Dibenzavzidod ih y droz y tetrole CleH ,,N,O is obtained by separatingthe sparingly soluble sodium salt dissolving it i n boiling water andRdding hydrochloric acid t,o the warm filtered solution. It can also bepreparad by heating ethyl hippurate with sodium at 160-170".Itcrptallises from hot alcohol in needles containing $ mol. H,O losesC. E. G250 ABSTRACTS OF CHEMICAL PAPERS.its water at 108-llO" the anhydrous crystals melting at 137-138".It is very readily soluble in hot benzene and alkalis but onlymoderately so in alcohol ; the alcoholic solution gives a violet colora-tion with ferric chloride. The bariurri salt is readily soluble in water.The silver salt is very unstable and rapidly darkens. The ethyl-derivative was obtained in an impure state as an aromatic smellingoil ; the acid seems to yield an acetyl-derivative when treated withacetic anhydride. When boiled for a long time with dilute hydrochloricacid or better with eight times its weight of a mixture of equalparts of concenti-ated sulphuric acid glacial acetic acid and water itis decomposed into benzoic acid and diamidoacetone.Its constitutionis probably either COPh*NH*C<C(oH)>C.NH-COPh orC(OH)C 0Ph.N H*C H < > C H*NH*C OP h .Diamidoncetone platiwchlorida C3H8N20,H2Pt GI crystallises insmall orange plates and turns bright yellow when warmed on thewater-bath.Tribenzarnidophloroglucinol C27HZ1N3O6 is formed when the readilysoluble sodium salt obtained in the reaction described above is decom-posed with hydrochloric acid. It crystallises from water in smallneedle3 containing 1+ mol. H20 and melting a t 153.5-158.5'. It isvery readily soluble in alcohol but only very sparingly in hot water,and insaluble in ether ; the alcoholic solution gives a blue colorntioriwith a small quantity of ferric chloride but on adding more of thereagent the colour changes to green.It is decomposed with libera-tion of benzoic acid when heated at a comparatively low temperature.The lead salt (C27H,8N30,),f?b3 is sparingly soluble in water but thecalcium barium and silver salts are readily soluble. The copper salt,( C27H,8N30,)2C~ is bright green.By J. V. JANOVSKY (Monatsh. 9 828-841).-Parazotoluene is best prepared by adding to 100 parts of 20 per cent.aqueous soda heated to loo" 100 parts of paranitrotoluene and thenadding slowly and with constant agitation 100-110 parts of zinc-dust. An orange-coloured oil is formed which should at once beseparated from the solution and left to crystallise. One recrystxllisa-tion from glacial acetic acid is sufficient to obtain pure parazotoluenemelting at 144".It crystallises in rhombic needIe8 soluble in alcohol,ether benzene and light petroleum and also in boiling hydroct~loricacid. When oxidised with chromic mixture it gives an orange-coloured crystalline compound melting a t 132".The acetic acid mother-liquor from the parazotoluene containsthree other products which melt a t log" 75" and 70" respectively.The last of these is identical with the P-azoxytoluene of Melms andPetrieff whilst the compound melting a t 75" appears to be a peculiarisomeride of the same. Both these compounds yield two bromideswhen treated with bromine (2 mols.) those from the first melting at85" and 57" those from the second a t 92" and 57".By actirag with nitric acid on the bromide of parazotoluene meltingF. S.I(.AzotoluenesORGANIC CHEMISTRY. 251a t 128" (Abstr. 1888 686) a nitrobromo-derivative melting a t 138"has been obtained.The nitration of pnrazotoluene with nitric acid of sp. gr. 1.5 yieldschiefly trinitro-derivatives. Two of these are formed one (a)melting a t 189" and the other ( p ) a t 138". A dinitro-compoundmelting a t 114" is obtained a t the same time. All these compoundsgive sulphonic acids with fuming sulphuric acid. By the furthertreatment of a-trinitrazotoluene with nitric acid a tetr(tnitraaoto1uenemelting a t 198-'200" is produced and p-trinitrazotoluene whennitrated gives the same compound. A mononitrazotoluene is formedon treating parazotoluene with nitric acid of sp.gr. 1.45. It melts a t80" and on further nitration yields the dinitro-compound melting a t114". H. C.Halogen-derivatives of Phenylhydraaine. By -4. N E UFELD(Annalen 248 93-99) .-The preparation of parachloro- and para-bromo-phenylhydrazine from the corresponding aniline-derivat,ives hasalready been described by Elsinghorst (Inau7. Diss. Erlangen 1884).These substances readily unite with aldehydes aud ketones. Acetorze-plrrabromopIienylhydrazone crystallises in glistening plates and meltsat 93". Acetaldehydeparnbromophenylhydraaone forms yellow needlesand melts a t 83".Dibrornophenylhydraaine [N,H Br = 1 2 51 prepared fromdibromaniline by reduction with stannous chloride or sodiumsulphite melts a t 97" and is freely soluble in alcohol ether andbenzene.The hydrochloride is crystalline. Symmetrical tribromo-phenylh?ydraz.cne [N,H Br3 = 1 2 4 61 melts with decompo-sition a t 146". It is soluble in benzene chloroform warm alcohol andhot water. The hydrochloride and sulphate are stable salts. Theacetone compound melts a t 54." TetrabromophenzJlhydrazine,[N2N3 Br4 = 1 2 3 4 61,crystallises in prisms and melts at 167". It dissolves in chloroform,benzene and hot water. The hydrochloride is crystalline. Thecompounds with acetone and acetaldehyde are solid.PariodophenlilhydrazirLe melt9 a t 103" and is freely soluble inalcohol ether chloroform benzene and acetic acid. The acetonecompound crystallises in plates and melts a t 114".Metadi-idophenyl-hydraxine "2H3 T2 = 1 2 41 forms silky crystals which melt at112" and are freely soluble in alcohol ether and benzene. Thehydrochloride melts a t 163" with decomposition. The base unites w. c. w. with acetone and acetaldehyde to form hydrazones.Phenylhydrazones. By 0. RUDOLPH (Amalen 248 99- 105).-~Metntoluylaldehy&ephenylhydrasone is deposited when a solution ofphenylhydrazine in acetic acid is added to toluylaldehyde suspendedin water. The compoiind crystallises in prisms melts a t 87-88.5",and dissolves in ether chloroform and alcohol. CicmaZdehydephenyZ-hydrazone melts a t 127-129". It rapidly turns red on exposure tothe light. D~hen~l~rcetaldehydephe.nylhydrazone is freely soluble inhot alcohol. Metahydroxy benzaldehyde~hen~lh~d~axone prepared fro252 ABSTRACTS OF CHEMICAL PAPERS.metamidobenzaldehyde forms colourless prisms. It melts at1 30-131*5" and dissolves freely in warm alcohol chloroform,benzene or acetic acid.Parahy~rozyhenzaldehydephenylh~drazonemelts a t 17'7-178" and is freely soluble in ether.. Anisaldehyde-y h m y l l y d ~ - a z o n e forms white needles or plates and melts a t 120-121".It is freely soluble in ether and in hot alcohol or benzene. Pijieyonnl-yhrnylhydrazone melts a t 102-103". P-Resorc~ilaldehydephen,yIhydr-alone melts with decomposition between 156" and 160". It dissolvesfreely in the usual solvents. Resorcindial dehy dep hen y 111 y dyazon emelts about 230" with decomposition. It dissolves in warm solutionsof the alkalis.w. c. w.Phenyltrimethylenimine. By L. RALBIANO ( C h e w . Cpntr. 1885,1356 from R e n d . Acnd. d e i Litrcei [4] 4 ii 44-46).-1f dryphenyl trimethj lenediamine hydrochloride is heated over a bare flameuntil the whole of the salt has volatilised and the vapours arecondensed in dilute hydrochloric acid phenyltrimethylenirnlne andammonium chloride are found in the solution. From the solution ofthe distillate after concentrating to a syrup alcohol precipitates thelatter whilst the base is separated from the solution by acidifyingwith hydrochloric acid precipitating with potassiiim bismuth iodide,and washing the red precipitate. After treating with potash anddistilling with steam it may be precipitated as the platinochlorideC,H,:NPh,H,PtCI an orange crystalline compound soluble in hotwater. The hydrochloride could not be obtained in crystals from theaqueous solution J.W. L.Hippuroflavin. By L. R~GHEIMER (Ber. 21 3321-3325)-HippuroJavin C9H5N02 is prepared by gradually heating a mixtureof ethyl hippurate (1 mol.) and phosphorus pentachloride (1 mol.)until the latter is dissolved and then adding a little more phosphoruspentachloride and heating a t 160" for about eight hours. The wholeis poured into alcohol and the crystalline product collected andwashed with alcohol. T t separates from hot nitrobenzene o r hotglacial acetic acid in small yellow crystals partially decomposes butwithout melting when heated a t 3W0 and sublimes with partialtlwomposition in citron-yellow crystals.It is very sparingly solublein glacial acetic acid and nitrobenzene and almost insoluble in water,alcohol and ether. When warmed with alcoholic soda it is decom-posed with evolution of ammonia and when heated at 100" for 8 to!) hours with concentrated ammonia the red solution obtained depositsa colourless crystalline compound. It yields benzoic acid whenwarmed with alkaline potassium permanganate or when heated a t130" with nitric acaid of sp. gr. 1.15 ; and w-hen treated with concen-trated hydrochloric acid at 1 1 O" it is completely decomposed intobeilzene carboil and dark-coloured products. When boiled withzinc-dust and glacial acetic acid i t yields a yellowish substance whichdissolves in soda with a brown coloration but is reprecipitated ingreenish flocks on adding hydrochlaric acid.It is gradually con-verted into a colourless compound when warmel with stannouORGANIC C t1E:JlISTRY. 253chloride and hvdrochloric acid in glacial acetic acid solution. Its/N(COPh)*.C*CO -\*- CO*&(COPh)N/ F. S. K. constitution is probably \Phthalimidine and Methylphthalimidine. By P. RARBIER(Compt. rend. 107 9 18-921).-Phthdimidine is readily obtainedby the gradual addition of small quantities of hydrochloric acid to anacetic acid solution of phthalimide containing the calculated quantityof granulated tin. It forms white needles melting. a t l50" and canbe recrystallised from boiling water it is isomeric with oxindole andis both au amine and an amide. It forms an unstable hyclrochloridewhich can only exist in presence of free acid and loses all its hydro-chloric acid in a vacuum.The hydrochloride is completely decom-posed by water ; the platinochloride ( CsH,N0)2,H2PtC16 and theaurochloride ( CeH7N0,HC1),,2AuC1 are both unstable. A deriva-tive CeH,NOAg is obtained as a white precipitate by adding silvernitrate to a solution of phthalimidine in potassium hydroxidesolution.When a solution of phthalimidine in potassium hydroxide is heatedin sealed tubes a t 100" for six hours with excess of methyl iodide,methylphthalimidine C9HgN0 is obtaitied in slender white needles,which melt a t 120". It forms an unstable hydrochloride and anunstable aurochloride ( CgHgNO) HAuC14. The properties of methylphthalimidine indicate that it has the constitution C6H,<CH,>NMe COCH2*NHand not c6H4<co.cH >.This view is confirmed by the fact that aconcentrated alcoholic solution of methylamine yields methylphthal-imidiire when heated with phthalide a t 220" for 12 hours.C. H. B.Derivatives of Diphenylacetaldehyde. By W. G. M. WEISE(AnnaZen 248 34-56). Hydrobenzoin is most conveniently pre-pared from benzo'in by the method described by Breuer and Zincke(Abstr. 1880 118). It is converted into diphenylacetaldehyde bytreatment with dilute sulphuric acid at 200"; this substance isconverted into a nitrile by adding powdered potassium cyanide andfinally hydrochloric acid to its ethereal solution. When dry hydrogenchloride is passed into a mixture of the nitrile and absolute alcohol(in molecular proportions) crystals of ethyl $-diphrnylimidolat tatehydrochloride CH Ph?*CH( OH) C ( O E t ) :NH,HCl are deposited.Thehydrochloride melts a t 135" with decomposition ; it is also decomposedby dissolution in water yielding in this case ammonium chloride andethyl P-diphenyllactate. The latter is a micro-crystal line powder meltsat 66O and yields a monacetyl-derivative CHPh,.CH(OAc)-COOEt,melting a t 53". P-DiphenyZZactic acid CHPh,-CH(OH)*COOH,crystallises in needles,'and melts at 159". It is freely soluble inalcohol ether and hot water. The salts of this acid do not readilycrystallise. At 170" the acid is converted into the anhydride,COO H*CH (C HPh,).O*CO*CH( 0 H) *C H P h,. Hydriodic acid d ecom-poses P-diphenyllactic acid a t 150" into carbonic anhydride an254 ABSTRACTS OF OEEMlOAL PAPERS.diplienylethane. Jf the reaction takes place at a higher temperature,dtbenzyl is also formed.w. c. w.Passivity of certain Polyketones towards Hydroxylamineand Phenylhydrazine. By J. HERZIG and S. ZEISEL (Ber. 21,3493-3494 ; compare Kehrmaun this vol. p. 243).-Tetrethyl- andpentethyl-phloroglucinol (Abstr. 1888 822) do not react withhydroxylamine or phenylhydrttzine and it would therefore seem thatmeta-diketones no longer give the characteristic ketonic reaction withthese compounds when the hydrogen-atoms in the ortho-positions tothe cnrbonyl-groups are almost completely or completely replacedby alkyl-groups. w. P . w.Nitriles. By J. A. MILLER (Chem.Centr. 1888 1359).-Para-methoxybenzaldehyde reacts with hydroxylamine with formation ofpammethoxybenzaZdoximp OMe*C6Hd.CH:NOH melting at 64". Bythe action of sodium nitrite and hydrochloric acid the aldehydeis regenerated. When heated with acetic chloride the nitrile,OMe*C6H4*CN is formed which melts a t 61-62'. By heating thisriitrtle with hydroxylnmine hydrochloride and soda param,ethoxy-benzen ylumidoxime OMe*C6H,*C(NH,):NOH is formed melting at122-125'. I t s hydrochloride melts a t 1 68". Paramethoxybenzenyl-ainidoxime ethyl ethei- OMe*C,H4.C(N H,):NOEt melting at 51-52",is prepared by heating the amidoxime with sodium ethoxide and ethyliodide.Plnra?.lzefhoxylbenzenylacety lamicloxime OMe*C6H4*C(NH2):N0 Ac isformed when a chloroform solution of the amidoxime is treated withacetic chloride.Puramethox y benzenylethen~~lazoxime OM~C6&'C<&~>C&3 melt-ing a t 68" is formed by heating the acetyl compound or by thedirect action of acetic anhydride on the amidoxime.With acet-aldehyde paramethoxybenzeu y lethylideneimidoxime,melting a t 127.5" is formed. The ethyl carbonate of the amidoxime,OMe*C6H4*C(NH,):N.0.c~oEt melting a t 119-120" i q formed bythe action of ethyl ohlorocarbonate on the amidoxime in chloroformsolution. When treated with solution of soda or potash this car-bonate is changed into pal-amethoxybenzen~li~id~~~mecarboriyl ;this may also be prepared by heatirig the chlorocarbonate with theamidoxime. It melts at 208".Paratnethoxybenzoylbenzenylnmidoxime O~~e.C,H,.C(NH,):N*OBz,melting at 148" is prepared by the action of the amidoxime in alka-line solution on benzoic chloride a t the ordiiiary temperature.Ifheat be employed pararnethoxy b enxeny lazoxim ebenzenyl,N.0 OMe*C6H4.C< - N>C Ph,is formed which melts at 102"ORGANIC CHEMISTRY. 255melting at 140-141" is formed by melting succinic anhydride withthe amidoxime.The salicyl derivatives are formed in a similar manner.Salicylaldoeinze melts a t 57" ; sa7icyzonitrile OH.C6H,*CN meltsat 99-100" ; a polynitrile is formed a t the same time as a secondaryproduct ; it is decomposed on heating with concentrated hydrochloricacid a t '200" into phenol carbonic anhydride and ammonia. SalicyZ-arnidozime OH.C6H4*C(NH2) :NOH melts a t 98.5".Si~1icyZamidoa:inzeethyl carbonate OHoc6H4*c(NH,):N.0.COOEt melts at 96". Salicyl-arnidoximepropenyl-w-carbox?llic acid melts at 116-11 7". Ortho-nzethoxybenzonitrile OMe*C6H4*CN boiling point 255-256" is pre-pared from salicylonitrile by the action of methyl iodide; oytho-rnefhoxybmzenylamidoxirne OMe.C,H,.C'(NH,):NOH melting at Us",is formed from the last-named substance by the action of hydroxyl-amine. By melting this amidoxime with benzoic chloride ortho-inethoxybenzenylazoxi~nebenze~i yl OMe*C,H,*C<-,>C N-0 Ph is formed ;it melts at 117". J. W. L.Derivatives of Metamethylphenylacetic Acid. By M. S ~ N -KOWSKI (Monafsh. 9 854-856).-Methyl metamethylphenylacetale isprepared by saturating a solution of the acid in five times the amount ofmethyl alcohol with hydrochloric acid.It is a liquid of sp. gr. 1.044a t 17.5" boiling at 228-229". The ethyl salt prepared in similarmanner has a sp. gr. of 1.018 a t 17.5" and boils a t 257-238".By dissolving metamethylphenylacetic acid in concentrated nitricacid carefully cooled a product is formed which melts at70-llO" but cannot be obtained of constaiit melting point. Itgives an ethyl salt which is still liquid a t -30". If the nitric acidsolution of the acid is heated for some minutes on the water-bath adz'nitro-derivative ~ 6 ~ ~ e ( N ~ ) * ~ ~ o ~ ~ ~ ~ is obtained melting a t173-174". The salts of this acid are very unstable decomposing i l laqueous solution even a t the ordinary temperature into dinitro-xyleneand carbonic anhydride.The methyl salt prepared by saturating thesolution of the acid in methyl alcohol with hydrogen chloride,crystallises in yellow needles melting a t 41". The ethyl salt similarlyprepared melts a t 68". H. C.Scopoletin. By D. TAKAHASHI ( Chem. Centr. 1888 136%-1365,€rom Mitt. nzed. F a k . Univ. Tokio) .-Scopoletin C10H804 the fluorescentsubstance occurring in Scopoliajaponicu is extracted from the roots bytreatment with alcohol evaporation of the alcoholic solution treat-ment with strong hydrochloric acid drying with admixture of sand,extraction with chloroform and finally recrystallisation several timesfrom absolute alcohol. It consists of colourless needles melting at198-199" little soluble in cold water readily soluble in alcohol,ether and chloroform.AcetyZscopoZdia Cl,,H704Ac melts at I76O256 ABSTRACTS OF CHEMICAL PAPERS.and is little soluble in water but soluble in alcohol. BenznyZscopoZetin,is insoluble in water little soluble in alcohol and melts a t 158".ikIethylsoopoZetin CloH70iMe is prepared by heating a mixture ofscopoletin (1 mol.) methyl iodide (2 mols.) and potassium hydroxide(2 mols.) in methyl alcohol on the water-bath. It foyms long,colourleQs needles melts a t 144" is insoluble in cold water soluble inhot water alcohol. ether benzene and ciirbon bisulphide insoluble inalkalis in the cold. This characteristic together with the pnrt,ialdecrease in the fluorescence in alkaline solution indicate in the sameway as the charatoteristic reactions of coumarin that scopoletin isalso a coumarin-derivative.Since dimebhylaesculetin and methylscopoletin have been proved tobe identical and since also the bromine-derivatives are alike scopoletinmust be a derivative of hydroxyquinol.Methylscopoletilic acid,CllH1,,05 is prepared by heating monobromomethylscopoletin withpotash a reaction which is also similar to those which thedibromo-derivatives of coumarin undergo when heated with potash.If its silver salt is decomposed by carbonic anhydride a colourless,pleasant-smelling oil is obtained which when treated with strongaqueous soda and distilled with steam bscomes converted intodimethoxycaumarin C10Hlo03 melting a t 58".Methy7 tl.imetl27JlcescuZetate C,H2(Me0)3*CH:CH*COOMe is preparedby melting methylscopoletin with potash extracting the mass withmethyl alcohol and heating wibh methyl iodide in a closed flask forthree hours.By recrystallising several times from alcohol the pro-duct remaining after the alcohol has been evaporated off it isobtained as a yellow cr-ystalline substance melting at 102" insolublein water but readily soluble in alcohol and ether ; it yields the freeacid on hydrolysis &c. By reduction with sodium amalgam,t w h e t h o x yph eny lpropionic acid C,H,( OMe) 3*C H,*C H,.C 0 OH isformed from which by oxidation with potassium permanganatetrimethoxybenzoic acid is obtained. From this t'rimethoxyquinol canbe obtained ; the constitution of scopoletin is therefore concluded tobe < H:CH> CdL( OMe) *OH.co-0J. W. I;.Homo-orthophthalic Acid. By M. LE BLANC (Chem. Cpntr.,1888 1352-135:3).- Dipropy Zhom o-orthoph thalimide C9H,Pr,N0,,prepared by the action of propyl iodide on homo-orthophthalimide inalcoholic cJolution melts at 141.5". DipropyZhonzo-orthophthalicanhydride C,H4Pr203 pTepared by heating the h i d e at 240" withfuming hydrochloric acid melts at 88". Di~oi3.'/lhomo-orthoiphthnlicacid CgHGPr201 prepared by treating the anhydride with potash meltsat 127". Homo-orthophthalopropylirrcide prepared by distilling a solutionof homo-orthophthalic acid in propylamine crystallises in leaves whichmelt at 69-7~". Nitrobenzenehomo-orthophthalopropy limide preparedfrom the last-named iruide by treating it with nitrobenzaldehFde,melts a t 119". Xa.Zicylhomo-mtho~ht?~alopropyli~ide prepared in likemanner to the last-named compound melts a t 157".Aldehydes ofthe fatty series such as isovaleraldehyde react in a manner quitedifferent from t h e aromatic aldehydesORffXNIC CHEMISTRY. 257Dibronzo-orthophthalimide prepared by the action of bromine onSynthesis of Dialkyl Phthalides.phthalimide in acetic acid solution melts a t 168.5'. J. W. L.By R. KOTHE (Annalen 248,56-7l).-Dirrteth~jlphtlzalide C6H4<C0 :>O prepared by acting ona mixture OE methyl iodide and phthalic anhydride with zinc-dust,melts a t 67-68" and boils a t 270-271". It is easily obtained inlaage crystals exhibiting the phenomenon of double refraction. Itdissolves in a solution of potassium hydroxide forming the potaqsiumsalt of orthohydroxyvisopropylbeneoic acid.Reduction with sodiumamalgam converts dimethylphthalide into dimethylhydrophthalide,C H 4 < ~ ~ ~ o G > 0 and hydriodic acid reduces it to orthoisopropyl-benzoic acid. Potassium cyanide acts on dimethylphthalide at 250" ;dilute sulphuric acid converts the product into an acid probablyorthoprnpenylbenzoic acid. The acid melts a t GO-61" and forms rhcrystalline barium and silver salt.Diethylphthnlide is an oily liquid boiling at 210-214" under210 mm. pressure. It appears to be identical with the compounddescribed by Wischin (Annalen 143 262).Benzyl chloride acts energetically on a mixture of zinc-dust andphthalic anhydride yielding an amorphous product solcble in etherand benzene.ItCMThis substance melts a t 73" and is non-volatile.does not contaiii oxygen. w. c. w.7-Ketonic Acids. By A. DITTRICH and C. PAAL (Rer. 21,3451-3457).-Ethyl P-benxo!ll-a-eth!llisosuccirtilte (ethyl phenacyl-ethylmalo?/ate) COPh.CH,*CEt (COOEt) is prepared b.y treatingethylic ethylsodomalonate suspended in absolute ether m ith the cal-culated quantity of bromacctophenone (phenacyl bromide). It is anoil which dissolves in the ordinary organic solvents and decomposeswhen distilled in L vacuum. The corresponding acid crystallises frommost solvents in slender white needles or long scales but can beobtained in cruciform aggregates of fairly la~ge four-sided prismswith oblique terminal faces by the slow evaporation of its solution ina mixture of chloroform and light petroleum ; the prisms however,contain chloroform of crystallisation and effloresce on exposure tothe air.The acid melts at 150" with evolution of carbonic an-hydride; is insoluble in light petroleum sparingly soluble in hotwater and benzene and readily soluble in alcohol ether chloroform,and acetic acid. Treatment with phosphorus pentachloride convertsit into the dichloride which is readily decomposed by water. Theammonium potassium calcium (1 mol. H20) and silver salts aredescribed. The hydrazone C,,H,,NaQ3 cystallises in concentrically-grouped slender white needles melts a t 132" is readily soluble inthe ordinary organic solvents and when heated above its meltingpoint loses carbonic anhydride and is converted into a substanceinsoluble i n alkalis or alkaline carbonates.~-nenzo1/l-a-et7Lylpropionic acid (pl2erLacyleth!/lacetic acid),COYh.CH,*CHEtCOOH is formed when ~-benzogl-r-eth~ lisubuo258 ABSTRACTS OF CHEMICAL PAPERS.cinic acid is heated above its melting point.It crystallises fromacetic acid in small aggregates melts at 81-F13O decomposes ondistillation and vields a hydrazone insoluble in alkalis. The calciumsalt (C,2H,30,)2Ca + H20 crystallises in white scales and is in-soluble in absolute alcohol but readily soluble in water; the ethylsalt is a yellowish oil.2 4-Phen~ZethyZt~iophert CAH2SPhEt is obtained by distillingsodium p-benzoyl-a-ethylpropionate or sodium hydrogen/3-benzoyl-a-ethylisosuccinate with phosphorus pentasulphide.It crystallises insmall white scales melts at about 40° and has the characteristic w. P. w.Reissert's Deoxypyranilpyroic Dibromide and Bromodeoxy-pyranilpyroic Acid. By R. ANSCHUTZ and 3'. HENSEL (AnnaZen,248 269-281).-The anthors have previously shown (Abstr. 1888,1092 j that Reissert's diliydropyranilpyroic acid (Abstr. 1888 696) isidentical with the pyrotartaric-anilic acid. On repeating Reissert'sexperiments on the action of bromine-water on dihydropyranilpyroicacid they find that the so-called deoxypyranilpyroic dibromide con-sists of a mixture of tribromaniline and pyrotartaric-parabromanilicacid and the so-called monobromodeoxypjranilpyroic acid is impurepyrotartaric-parabromanilic acid.Pyrotartaric-parabromanilic acid is the chief product ol the reac-tion of bromine-water on sodium pyrotartrate ; no tribromaniline isproduced.Parabromaniline unites with pyrotartaric anhydride in benzenesolution forming the parabromanilic acid of pyrotartaric acid(m.p. 158-158.5'). It is converted into the corresponding para-bromanil by the action of phosphorus pentachloride.Dibromaniline [l 2 41 yields a pyrotartaric-dibromanilic acidmelting a t 139"; but tribromaniline does not combine with pyro-Dyes from Diamidoethoxydiphenylsulphonic Acid. By A.FEER and H. M ~ L L E R (Chem. Cedr. 1888 1358 from BUZZ. Xoc.indust. Mulhouse 1888 488-490).-Diazobenzene and sodium para-phenolsulphonate react together with formation of a dye of theconstitution PhN2-CaH3(OH)*S03Na [ = 1 41 of light-yellow colour,little soluble i n cold water readily so in alkaline solutions.I f this isheated in a sealed tube with ethyl bromide and soda in mole-cular proportion the corresponding ethyl salt of ethozyazobenzenesul-phonic acid is formed. Reduction with stannous chloride in hydro-chloric acid or with zinc-dust in alkaline alcoholic solution leads tothe formation of diamidoethosydi~he,2ylsulphonic acid,odonr of the two known phenylethylthiophens.tartaric anhydride in solution in benzene. w. c. w.NH,.CsH4*CsH4(NH2)(OEtl).S03H [OEt S03H = 1 41.Sodium acetate precipitates the free acid in crystals from its con-centrated solution. By treating the hydrochloric acid solution of thissulphonic acid with sodium nitrite (2 mols.) tetrazoethoxydiphenyl-sulphonic acid is obtained which by treatment with phenol (2 mols.)or amines in dilute alkaline solution yields yellow red and violet dyes OROASIC CHEXISTRP.25 9these dye cotton without the use of a mordant although the dye isnot so fast as when one is used. J. W. L.Indole-derivatives. By L. WOLFF (Ber. 21 3360-3366) .-3 2' ~'-Trin?ethylindoZe CIIHLaN is obtained when p-bromolevulinicacidis heated with three times its weight of paratoluidine.tallises in white scales having a peculiar odour melts a t 121*5" boilsat 297" (corr.) is volatile with steam and dissolves sparingly inwater but readily in alcohol chloroform and light petroleum. Whenallowed to rema.in for a few days it becomes yellow and finally brown,and its acetic acid solution is coloured at first green and afterwardsan intense blue on boiling with a small quantity of ferric chloride.The p i c r a t e crystallises from alcohol in brownish-red needles andmelts a t 189" ; the nitroco-derivative CIIH12N*N0 forms lustrous,golden-yellow needles melts a t i3" and is sparingly soluble in water,readily soluble in alcohol and acetic acid.1 2' 3'-Trirnethylindole prepared in like manner from ortho-toluidine crystallises in white scales melts a t 79" boils a t 282-283",and closely resembles the 3 2' 3I-derivative in its solubility andbehaviour with ferric chloride. The picrate C11Hl~N,C6H2(N02),-OH,crystallises in purple-red needles and melts a t 152".Ethyldzmethylindole [Et Me Me = 1' 2' 3'1 obtained in likemanner from ethylaniline is a yellow oil which boils a t 280-282",has the persistent indole odour dissolves readily in alcohol ether andbenzene and when boiled in acetic acid solution with a small quantityof ferric chloride or potassium dichrornate vields a very characteristic-,intense red coloration. The picrate C d 15N,CsH2( N02),.0H crystal-lises in small dark-red needles melts at 105" and is soluble inbenzene.2'' 3"-Dirneth~j~-~-nap~2thi~ndoZe formed under similar conditionsfrom p-naphthylamine crystallisea from alcohol in colourless brittle,strongly refractive tablets melts a t 132" boils above 360" and is onlyslightly volatlile with steam.It is insoluble in water soluble inalcohol and acetic acid and readily soluble in ether and benzene andits solution in acetic acid is coloured green on boiling with ferricchloride. The picrate crystallisw in lustrous dark- brown needlesmelting at 175".2" 3"-DimPthyl-a-naphthindole prepared in like manner froma-naphthylamine crystallises from alcohol in small white granules orprisms melts a t 150" and is insoluble in water sparingly soluble incold alcohol and acetic acid and readily soluble in ether and benzene.When heated in acetic acid solution with a trace of ferric chloride ityields a beautiful cherry-red coloration whilst with potassium dichro-It crysmate it gives an intense blue.w. P. w.Indoles. By B. TRENKLER (AnnuZen 248 106-113).-~a]er-aldehydephenylhydrazone boils a t 280" under a pressure of 150 mm.I t is converted into 3'-isopropylindole by fusion with zinc chloride.3'-Isopropylindole is a pale-yellow crystalline mass freely solublein alcohol ether benzene chloroform light petroleum and aceticacid.It boils at 287-2288". The picrate crystallises in needle260 ABSTRACTS OF CHEMICAL PAPERS.and melts at 96-99". H!idroisopropyllinaole prepared by the act>ionof zinc-dust and strong hydrochloric acid on an alcoholic solution ofisopropylindole resembles hydroscatole in its properties (Abstr.,1887 957).3'-Pen,fyZindoZe from oenanthaldehydephenylhydrazone bods a t345-347" and is freely soluble in alcohol ether and benzene. Thepicrate is crystalline. 2' .3'-r~~efhyZ~henyZindoZe from methjlbenzyl-lretonephenylhydrazone crystallises in colourless prisms and me1 ts a t59-60". The picrate and tthe nitroso-compound are crystalline.2' 3'-BewzyZphenyZindoZe from dibenzyl-ketone forms six-sided prisms and melts a t 100-101". It is freelysoluble i n alcohol ether benzene chloroform and acetic acid andIt' does not stain pinewood.does not exhibit the pinewood reaction. w. c. w.Decomposition of Benzidine Hydrochlorides by Water. ByP P E w r (Cornpi. rend. 107 839-841).-Benzidine monohydro-chloride is stable in solution and when potassium sulphate is added,an insoluble sulphate (C12H,2N2)2,H2S0 is precipitated but no freeacid is liberated. I n the case of the dihydrochloride dissociationtakes place according to two distinct laws. If the concentration ofthe solution does not exceed 5.4 grams per litre a constant fraction(0-034) of the salt is dissociated into the monohydrochloride andhydrochloric acid.When the concentration exceeds 5.4 grams partof the monohydrochloride formed is precipitated and the quantity ofdihydrochloride decomposed is the sum of two quantities namely,the fraction corresponding with a concentration of 5.4 grams and aquantity proportional to the excess of dihydrochloride over arid above5.4 grams per litre. C. H. B.Similar Reactions of Carbazole and Pyrroline. By S. C.HOOKER (Rer. 21 3299-3301).-Carbazole like pyrroline gives thepinewood reaction a fact which is not in accordance with Fisclier'sconclusion respecting this reaction (compare Abstr. 1886 806).Carbazole gives with isa.tin and concentrated sulphuric acid a deepblue solution from which water precipitates an indigo-blue substance,the colour of which rapidly becomes lighter.When a small quantityof sulphuric acid diluted with one or two volumes of acetic acid isadded to an acetic acid solution of carbazole and quinorie a carmine-red solution is obtained from which water precipitates a red o rreddish-violet substance soluble in ether chloroform and alcohol.(Compare Meyer and Stadler Ahstr. 1884 1045.) A green solutionis produced when oxidising agents such as quinone are added to asolution of carbazole i n sulphuric acid and the colouring matter,which is precipitated by water is insoluble in ether. (CompareGrabe and Glaser this Journal 1872 302.) Pyrroline also yields i lgreen substance when treated with a very small quantity of anoxidising agent in dilute sulphuric acid solution; this green com-pound is rapidly destroyed by strong oxidising agents.(CompareMever and Stdler Zoc. cif.).Pyrroline yields a crjstalliue compound with picric acid ; i t meltORGANIC CHEIIITSTRY. 261at about 71" and is unstable. Phenylpyrroline also combines withpicric acid. F. S. I(.Malachite-green and Derivatives of Paramidodiphenyl-methane. By A. MANNS (Chem. Centr. 1888,1363) .-The leuco- baseof malachite-green when distilled over zinc-dust is reduced to aniline,dimethylaniline and paramidodiphenylm ethane together with hydro-carbons of the fatty arid aromatic sevies.Paramidodiphenylmethane was prepared synthetically from para-nitrobenzyl chloride by means of Friedel-Craf t's aluminium chloridereaction in benzene solution.NitrodipheiLy1,rLethatLe thus obtained melts at 30-31".It isreduced by tin and hydrochloric acid to paramidodipheny lmethane,and from this diazoamidodiphenyl methane C2sH27N3 is prepared bytreatment with nitrous acid. Meth y7paramidodiphenylmethane,CI3HIl*NHMe i R obtained from amidodiphenylmethane by the actionof methyl iodide ; it boils above 360" aud is a light yellow oil. Thehpdriodide melts a t 150". AcetylparamidodiphenyImethni~e melts at127.5" ; the benzoyl-derivative melts at 162a. Diphenylmethalzehydrazine C17H11*NH-NH2 is obtained as hydrochloride by reducingdiazodiphenglmethane with stannous chloride in hydrochloric acidsolution. The free base crystallises in yellow scales melts at 85",and boils above 360" without decomposition.Parabenzy7-a-quinoline C1,H13N7 is prepared from paramidodi-phenylmethane by means of Skraup's reaction ; it melts at 80*5" boilsabove 360" and is characterised by the large number of well-crystnl-lised simple and double s d ts it forms.Di23aradi~henylmetharzethio-carbamide CS(NH.C,,H,,) prepared by the action of carbonbisulphide on nmidodiphenjlmethane crys tallises in yellow scalesand melts a t 147". The sulphur-atom is replaced by oxygen by theaction of plumbic oxide. If however an excess of amidodiphenyl-methane is employed triparadiphenyZrnethanegu(x nidine C40N35N3 isformed melting point 100". Parad~henyImet~ianecarbamide,NH2*CO-NH*C13Hll melting at 160" is prepared from paramidodi-phenylme thane hydrochloride by the action of potassium cyanate.The disubsfituted carbnmide GO (NH*C13H11)2 is prepared by theaction of carbonyl chloride on the base or by fusing the last-namedcarbamide ; it melts a t 226".&'thy1 dipl~en~lmethanecarbainate,C,,H,,.NH*COOEt melts at 65" and is prepared by the action ofethyl chlorocarbonate on the base. J. W. L.Arrangement of Atoms in Space. Part 111. Members ofthe Stilbene-group. By J. WISLICERUS and A. BLANK (Annalen,248 1-34).-After referring to the researches of Grimaux Zinin,Goldenberg Zagoumenny Limpricht and others on the action ofreducing agents on benzoin the authors state the results of their ownexperiments on the action of zinc-dust and acetic acid on an alcoholicsolution of benzoin.The yield of deoxybenzoxn dirninishes if thereduction is carried on for more than three hours; the amount ofdeoxybenzokpinacone increases. Small quantities of stilbene areformed together with a substance crystallising in needles and meltingVOL. LVL. 262 ABSTRACTS OF CHEMICAL PAPERS.a t 172" which proves to be p-deoxybmzohpinacone.and p-pinacones decompose on distillation yielding phenyl bemy1ketone and phenyl benzyl carbinol. The pinacones are optically inac-tive and probably stand in the same relation t o each other as mesotar-taric and racemic acids.for a-tolane dichloride,Both thePh*C*ClPh*h*ClWislicenus suggests the formulaPh*C C1Cl*&Phfor p-tolane dichloride which melts a t melting.at 143" and63". A determination of the molecular weight by Raoult's method,and the vapour-density show that the substances are isomeric.When tolane tetrachloride is reduced by zinc the yield of a-tolanedichloride is increased and that of the /3-dichloride diminished byraising the temperature from 20' to 80" or 130".Ditolane hPxnchloride CPhCI,*C'PhCl.CPhCI*CPhCl i s formed hvdissolving tolane tetrachloride and a-dichloride in molecular pro-portion in boiling alcohol ; on cooling the hexachloride is depositedin rhombic plates soluble in benzene; it melts a t 150'. AlthoughRaoult's method giveq 266 as the molecular weight of this com-pound instead of 568.4 the authors regard it as a definite com-Found and not as a mixture of the di- and tetra-chlorides as i ti s formed by the action of chlorine on a mixture of the a- and p-dichlorides.p-Dichlorotolane will not unite directly with the tetrachloride toform the hexachloride.w. c. w.Nitroparadiphenols. By E. KUNZE (Ber. 21 3331-3335).-~etadinitroparrzd.?lzenol [(NO,) (OH) = 3 3' 4 4'3 is formedwhen the calculated quantity of nitric acid of sp. gr. 1.45 is added t oparadiphenol in glacial acetic acid solution. It separates from glacialacetic acid in brown needles o r nodular crystals melting a t 272".~~etadiamidoparadi~?ienol [ (NH,) (OH) = 3 3' 4 4'1 crystal-lises in colourless plates decomposes when heated and dissolves inqlcoholic ammonia with a green coloration. The hydrochtoridr,C,,H,(OH),(NH,),,~Hcl crystallises in colourless needles.TheacetyZ-derivative Cl2H8N2O2Ac4 crystallises i n colourless needles andmelts a t 225".Dietheizyldiamidodihe~oZ C M e ~ ~ > C H . C 6 H < N ~ C M e 0 0 is ob-tained when the acetyl-derivative is heated above its melting point. Itcrystallises in colourless prisms melting a t 193".TetrazodiphmoZ NGN> C6H,*C6H,<N>N obtained by diazotisingt h e diamidodiphenol dissolves in hydrochloric acid with a red colora-tion but is reprecipitated unchanged when ammonia is graduallyadded to the solution.Dipherboldihydl-azine hydrochloride [(N,H,) (OH) = 3 3' 4 4'1,prepared by reducing the tetrazo-compound with stannous chlorideand hydrochloric acid crystallises in slender needles. When ammoniais added t o the aqueous solution the free base is precipitated in0 ORC,A'ETIC CHEJIISTRT.263mlourless crFstills ; it mcJlts a t 140" with decomposition and reducesFehlin$s and ammoniacal silrer solutions.DiacetonPdiluhe~ioklih2/nraznne Cl,H,,N402 is obtained when acetoneis added to an aqueons solution of the dihydrazine hydrochlorideuntil the mixture commences to become trrbid. It crystallises incolourless rhombic plates melts a t 200" and is readily soluble in soda,but only sparingly in ammonia and insoluble in alcohol and ethw.Analogous condensation-products are obtained with ethyl aceto-acetate pyrnvic acid benzaldehyde and salicylaldehyde.The tetranitrodiphenol whirh is formed when paradiphenol ormetadinitroparadiphenol is nitrated in glacial acetic solution or whenbenzidine is treated with nitric acid (compare Caro; Griess aridSchmidt Schultz Abstract 1881 909) has the constitution[(NO,) (OH) = 3 3' 5 5' 4 4'3.It yields tetramidoparad~lzenolwhen reduced with tin and hydrochloric acid.Tetrnmidoparadiph e H 01 crys tallises in cnlourlew needles and decom -poses but does not melt when heated. It oxidises very readily turnsblue on exposure to the air 2nd is converted into a brownish-blackcrystalline compound C,2Hl,N40?. M hen R stream of air is passed for along time through an ammoniacal alcoholic solution. I?. S. K.New Method of Formation of Benxhydrol-derivatives ByK. ALRRC CHT (Re?.. 21 329'L-3.29~).-Dimefhylnmidobenl.hydrol,OH*CHPh-C6H4*NMe can be obtained by heatinz a mixture ofbenzaldehyde (1 mol.) and dimethylaniline (1 mol.) with 20 timesits weight of concentrated hydrochloi-ic acid a t 100" for 50 hours,neutralising the solution distilling the unchanged compounds withsteam and recrystallising the residue first from alcohol and then fromlight petroleum.It can also be prepared by reducing dimethylanlido-benzophenons with sodium amalgam in alcoholic solution. I t crys-tallises in slender needles melts a t 69-70' and is very readilysoluble in most solvents but only moderately so in ligbt petroleum,and insoluble in water. It dissolves in acids yielding colourlesssolutions which become yellow when warmed. It is converted intoleucomalachite-green when heated with dimethylaniline and zincchloride.NO,-C,H,.CH (0 H).C6H,*NMe,,is prepared by heating a iriixture of paranitrobenzaldehyde (15 I gramsl,dimethylaniline (121 grams) and hydrocliloric acid ( 3 kilos.) for40 hours neutralising the filtered solution washing the precipi-tate and separating the dimethjlaniline by distilling with steam.The yield is 80 per cent.of the theoretical. It crystallises fromdilute alcohol in slender yellow needles melts at 96" and is veryreadily soluble in most ordinary solvents but insoluble in water andlight petroleum. The cold acid solutions are colourless but turnyellow when heated. It yields paranitroleucomalachite-green (m. p.176-177" j when warmed with dimet,hylaniline and zinc chloride andwhen treated with alkaline reducing agents i t is converted into thecorresponding azoxy- azo- and hydrazo-compounds. When heatedwith met,hyl iodide in methyl alcoholic solution a colourless crys-ParanitrodimethriZa?nidobenz hqdm I,t 264 ABSTRACTS OF CHEMICAL PAPERS.talline cornpound,.probably the rnethiodide is obtained it meIts a tabout 175" with liberation of methyl iodide. The salts are all veryreadily soluble and difEcult to obtain crystalline. The platinochloride,(C,,H,,N,O,),,H,PtCl crystallises in needles and is decomposed byboiling water.Dimethy7diamidobenz~?/~rol NH,*C,H,.CH(OH)*C,H(*~Me~ pre-pared by reducing paranitrodimethylamido benzhydrol with zinc andhydrochloric acid melts a t 165" and loses 1 mol. H,O when heatedabove its melting point. It dissolves in acetic acid with a bluecoloration and cr,ystallises from benzene in shininq needles containingbenzene which melt and lose their benzene a t 142".It yields tetra-methylparaleucaniline when condensed with dimethylaniline.The leuco-bases obtained by the condensation of dimethyldiamido-benzhydrol with other aromatic bases yield reddish-violet or blue dyes,whereas those obtained from paranitrodimethylamidobenzhydrol yieldgreenish colouring msttters.Diw ethy Id iamidodiphen!y Zmef harte NH,. C6H1.CHL*C6H4*N Me2 is o b-tained by boiling paranitrodimethylamidobenzhydrol or the corre-sponding diamido-derivative with zinc and hydrochloric acid. It isa colourless crystalline compound melts a t 93" and gives a bluish-violet coloration with chloranil or lead peroxide but not with acids.The condensation of paranitroberizaldehyde and dimethylaniline isbest effected by dilute hydrocliloric acid or dilute sulphuric acid ; tliehydro1 formation only takes place in presence of excess of acid ; ifalcohol is also present the ethyl ether is produced.When only asmall quantity of acid is employed or if it is very dilute nitroleuco-malachite-green is formed. Hydrols are not formed or only in verysmall quantities when phosphoric acid acid salts or organic acids areemployed and with excess of concentrated sulphuric acid the onlyproduct is tetramethylbenzidine which is obtained in small quantities.Dimetbylaniline diethylaniline methylariiline and ethylaniline onthe one hand and paranitro- and metanitro-benznldehyde on the otherhand condense without difficulty and the hydrols formed resembleparanitrodimethylamidobenz hy drol.The ethyl compounds melt a t it lower temperature than the coiw-sponding methyl-derivatives ; the dialkylhydrols melt a t a lowertemperature than the nionalkyl-derivatives and the para-compoundsat a higher temperature than the isonieric meta-bases.Aniline alsocombines with paranitrobenzaldehyde but not so readily as thesecondary and tertiary bases.The amidohydrols dissolve in cold mineral acids and in dilute aceticacid yielding colourless or only slightly coloured solutions ; thediamido-derivatives behave in like manner towards excess of concen-trated mineral acids but dissolve in acetic acid formiug deep bluesolutions especially on warming. The diamido-derivatives also giveblue solutions when an insuficient quantity of mineral acid is added,or when dilute only slightly acid solutions are warmed.The author finds that tetramethyldiamidobenzhydi 01 does notdissolve in alcohol with a blue coloration as stated by Mivhler andDupertius (this Journal 1877 ii 333) but that it dissolves in d lneutral solvents forming colc~ urless solutions.F. S. KORGANIC CHEMCSTRP. 2(i5Formation of Benzamarone. By F. R. JAPP and F. KLINGEMANN(Ber. 21 2934-293;) .-Benzamarone is formed when deoxybenzoynand benzaldrhyde (each 5 grams) are dissolved in cold alcohol treatedwith an alcoholic solution of potash (2 grams) and kept over night.The yield is 5 grams. A small quantity of the compouud was alsoobtained by keeping a mixture of b e n d deoxybenzoin and weakalcoholic potash for some days in a closed vessel; in this case thebenzaldehyde necessary for its forniation is produced together withbenzoic acid (which was found in the product) by the slow decompo-sition of the bend Benzamarone prepared as described above orby Zinin's method (this Journal 1871 639) melts a t 214-215"(not 225").Its mode of formation points to the formula C,,H,,02rather than to the double formula (Knoevenagel Ber. 21 2356).N. H. M.Constitution of oertain Dichloronaphthalenes. By H. E RD-MANN (Bpr 21 3444-3448) .-Orthoparadrchloro~rherc ylparaconic acidcan be prepsred by the action of succinic acid on orthoparadichloro-benzaldehyde and crysiallises from water in white scales melting a t1 6 4 - 5 4 65.5".On d is t,illa tion i t yield 8 ort hoparadich lwoy hen y 1 iso-crofonic acid CsH,CI,*CH:CH.CH2*CO~~H [Cl C1 CH = 1 3 41,which crystallises from carbon bisulpliide in white prisms. When thisacid is heated for some minutes a t its boiling point it decomposes intodichZoro-a-r~a~hthoZ CloH,C1,*OH [Cl C1 OH = 1 3 4'1 whichcrystallises from carbon bisulphide in large prisms melting a t 132".The corresponding d ic h Zoro-a-riap hthy Zamine CloH5Cl ,*NH can beprepared by heatiug the dicbloro-a-naphthol with aqueous ammonia ;it melts a t 116-lli" yields a hydrochloride melting at 204-205",and when diazotised and treated either with alcohol or with stannouschloride and cupric chloride is converted into 1 3 dichloronaphtha-lene which crjstallises in white needles melting a t 60-61".Thea n t h w has therefore now prepared synthetically the t w o dichloro-naphthalenes melting a t about the same temperature one of which ishomo- and the other hetero-nuclesl (compare this vol. p. 150). Theremainder of the paper is devoted to a reply to Armstrong andWynne's criticism of the constitution assigned by Erdmann and Kirch-hoff (7oc. c i t . ) to the heteronucleal diuhloronaplithalenes melting at48" and at about 61.5" (Proc. 1888 104). w. P. w.Note by Abstractor.-The author puts forward as original the dis-covery of the existence of two isomeric dichloronnphthalenes meltingat about 61"; a reply to this and other claims in the paper has beenAction of Chlorine on Phenols. Part 111.,&Naphthol. ByT. ZINCKE and 0. KEGEL (Be?.. 21,3378-3390,%540-3559 ; compareAbstr. 1888 708) .-Cleve has described the preparation oE chloro-@-naphthol [Cl OH = 1 21 by the action of chlorine on &naphtholi n acetic acid solution (Abstr. 1888 597). Experiments show tha,tdichloro-/?-ketonapht balene is simultaneously formed and the bestmethod of obtaining the chloro-P-naphthol consists in treating the@-naphthol dissolved in acetic acid with a slight excess of chlorine andpublished in the Proceedings 1889 p. 5. w. P. w266 ABSTRACTS OF CHEMICAL PAPERS.reducing the dichloro-p-ketonaphthalene formed by addition of anexcess of concentrated stannous chloride. The acetgl compound,CloH6C1*OAc crystallises in thick colourless oblique-angled tables,melts a t 42-43' aiid is very soluble in alcohol.aP-Diclzloro-p-naphthol Cl0H5C1,.OH [Cl OH C1 = 1 2 31 canbe obtained by the reduction of tetrach loro-,&ketohydronaphthalene(see below) but when prepared from this source is always mixedwith 9 larger or smaller quantity of the isomeric ao-dichloro-13-naphthol.It is best prepared however by reducing trichloro-$-ketonaphthalene dissolved in acetic acid either with stannons chlorideor a sulphite. It crystallises in aggregates of sleuder lustrousneedles melts a t 60-81' and is readily soluble in alcohol ether,benzene and acetic acid. The ncetyl-deri vative CloH5C1,*OAc ci-ys-tallises in flat rhombic tables showing a peculiar striation on some ofthe faces melts a t 79-80" and is readily soluble in alcohol andacetic acid.When treated with chlorine in acetic acid solution,a/3-dichloro-P-naphthol is converted into 6-trichloro-p-ketonaphtha-leoe which by further addition of chlorine forms p-pentachloro-p-ketohydronaphthalene. Chromic acid converts it into a yellow,amorphous substance probably a diquinone-derivative but on carefuloxidation with nitric acid (sp. gr. = 1*4) it yields chloro-@naphtha-quinone as chief produck a second quinone-like compound probablyan ap-nitrochloro-p- napht h aquinone being simultaneously formed,which melts at 172" and is characterised by dissolving in aqueousalkali with an intense bluish-green colour and in alcoholic alkali witha deep blue colonr.aa-Dichlol.o-P-na~htho2 CloH5C12*OH [Cl OH C1 = 1 2 41 isobtained together with the a/?-derivative by the reduction of tetra-chloro-@-ketohydronaphthalene with stannous chloride in the cold andis separated from its ieomeride by repeated crystallisation from lightpetroleum. It crystallises in long hard white asbestos-like needles,melts at 123-124' and is readily soluble in ether alcohol and aceticacid.Its acetyl-derivative C,H,CI,*OAc crystallises in small colour-less needles and melts a t 90-91". On treatment of its acetic acidsolution with the calculated quantity of chlorine it is converted intoa-trichloro-P-ketona-phthalene which by the further action of chlorineyields a-pentachloro-6- ket ohy dronaphtb alene ( P). When oxidised withchromic acid it is converted into a yellow amorphous substance whilstwith nitric acid (sp.gr. = 1*4) it yields as chief product alj-chloro-nit ro-p-naphthaquinone a-ch loro- p-naph thaquinone being formedsimultaneously in very small quantities. a~-Chloronitro-~-napl~tha-puinone c6&<ccI.C (No,)> crystallises in red or brownish-redneedles melts at 1%" and is readily soluble in hot benzene or aceticacid sparingly soluble in alcohol light petroleum and cold benzene oracetic acid. It dissolves in concentrated alkali with a n intense greenish-blue and in dilute alkali with a reddish-brown colour. When treatedwith aniline it yields anilidonitronaphthapuinone anilide,co*co -CO-C(NHPh)C6H4<C (NPh) -C( NO2)>ORGANIC CHERIISTRP. 267which crystallises in dark violet scales showing a metallic lustre meltsa t 249-650" and is insoluble in alkalis sparingly soluble in aceticacaid and benzene but more soluble in toluene.The salts of this basew e decomposed by alcohol or acetic acid unless acid is present whenthev dissolve with a violet colour. Ja- Chloro-P-nnphthaqz~inone C6H,< ::;%%> crystallises in red-dish-brown strongly dichroic needles melts a t 136' and yieldsCO-CCOH)> P-h y drox yn aph t haquinone anilide C6H4 < C(Nph).CH 9 On treatmentwith aniline.TriclLloro-a-nnphtiioz C,,H,CI,*OH [Cl OH C1 C1 = 1 2 3 41,is obtained by the reduction of /?- pe II tachloro-/?-ketohydroiiap hthalenewith stannous chloride or sodium sulphite. It crystnllises in colourlessneedles melts at 162' and is less soluble than the diclilorinated deriva-tives.Its acetyl-compound C H4Clj-OAc crystallises from acetic acidin white lustrous needles and melts a t 133.5-134". On treatment inacetic acid solution with chlorine it is converted into tetrachloro-&ketomphthalene. Chromic acid oxidises it to a yellow amorphoussubstance containing probably a diquinone whilst nitric acid(sp. g!. = 1.4) converts it in to orp-dichloro-f3-naphthaquinone.a - ~ z c h l o r o - l j - k e t o n ~ p hthalene (p-naphtlLayuinone chloride) ,CC'l,.CO,C6H4< CJ-JCH / 9is obtained by treating chloro-/?-naphthol or /%naphthol dissolved inacetic acid or chloroform with the calculated quantity of chlorine Itis a liquid and rapidly decomposes on distillation in a vacuum.Whentreated with aniline i t is converted into P-hydroxynaphthaquinoneanilide if dissolved in alcohol but into anilidonap hthaquinone anilide,C6H4< if dissolved in acetic acid. Phenylhydrazinereacts with the compound in a peculiar manner inasmuch as it doesnot convert it into the so-called benzeneazo-/?-naphthol but into achlorinated azo-compound /?-benzenenzo-a-chloronay/Lthalene,CloH6C1*N:NPh [Cl N2Ph = 1 21,which crystallises in slender reddish or pale-orange needles melts a t115" is readily soluble in alcohol benzene and acetic acid and onreduction in acetic acid solution with stannous chloride yields notchloro-/%naphthylamine but a basic compound free from chlorine.A mixture of brown substances is formed by the action of hydroxyl-amine on dichloro-/3-ketonaphthalene.6- Trichloro-p-ketona~htl,alene (I-3-cliloro-/3-naphtfia~u~none chloride),CsHI<CH:cc1> CCl,*CO is formed by withdrawing the elements of hydro-gen chloride from tetrachloro-P-ketohydronaphthalene.It is not,however necessary t o first prepare this compound in the pure state,since the product obtained by treating a well-cooled 10 t o 12 per cent.sotution of &naphthol in acetic acid with an excess of chlorine readilyevolves hydrogen chloride when poured into an equal volume of alcohol268 ABSTRACTS OF CHEMICAL PAPERS.and yields the trichloroketone. It crystallises from alcohol or aceticacid in thick yellow needles which darken in colour on exposure tolight and melt at 95-96'; whilst from ether it separates in larw,monoclinic prisms which show however a marked rhonibic habitif the solution is impure.When finely powdered it dissolves slowlyin dilute alkali and yields in addition to brown resinous substances,PP-chlorh ydroxpapht haquinone,tion is accounted for by supposing that the P-chloro-a-hydroxy-p-naph-thaquinone which would most probably be formed in the first instance,undergoes isomeric change. When heated either with dilute alcohol orwithdilute acetic acid it forms resinous compounds together with somechlorhydroxynaphthaquinone and a compound which crystallises inneedles and seems to be a dichloro-p-naphthol. Stannous chlorideand sulphites reduce it to ap-dichloro-@-naphthol; phenylhydrazinein alcoholic solution reduceq it hydroxylamine converts it into resinousproducts and orthotoluylenediamine reacts with it forniing crystallinecompounds.When the hot alcoholic or acetic acid solution of thetrichloroketone is treated with aniline Plj-chlorhydroxyna~lzthapzcinonsanilide C ~ H I < ~ ~ ~ ~ ~ ~ ~ ~ > is obtained melting at 253" ; if how-ever a cold alcohblic shhtion is used this comDound is formed onlv inrelatively small quantities the chief produ'ct being a&dkhlo&-+hydrox~-a-naph'thy123hsnylamine C,H,<c(~Hph):ccl>. This crys- CCl-C(OH) -tallises from chloroform in colourless transparent hard thick crystals,from acetic acid in slender lustrous needles aud from a mixtureof ether and light petroleum in large prisms melts a t lt;2" anddissolves without decomposition in a1 kalis.Its acetyl-derirati\ e,CIGHIONCI~*OAC crystallises from alcohol or acetic acid in small,lustrous prisms and melts at 164". In one preparation of thiscompound a third substance was once obtained which crystal-lised in small white scales melted at 223" and gave results onapalysis indicating i t to be a chlorhydroxydiphenylnaphthylene-diamine.a-Trichloro-P-ketonaZIhthaZe.ne (a-chloro-P-naphthaqui?~one chloride),c,&<<ccl:cH> is prepared by treating an acetic acid solution ofaz-dichloro-P-naphthol with the calculated quantity of chlorine. Itcrystallises from light petroleum in thick white needles and from amixture of ether ahd benzene in well-formed transparent rhombicprisms melts at 86-87' and is readily soluble in hot alcohol benzene,ether and acetic acid.On treatment with alkali it yields B-hy-droxynaphthaquinone ; aniline converts it in alcoholic solution intop-hydroxynaphthaquinone anilide and in acetic acid solution intoanilidonaphthaquinone anilide ; stannous chloride redures it toaa-dichloro-,~-naphthol and hydroxylamine reacts with it formingan oxime.CCI,*COTetraphloro-P-keton aphthalene (dichloro-&nap hth aquinone chloride),CsH4<CC1:CC1> is obtained by suspending trichloro-P-naphthol iu cc12*cORGANIC CHERlISTRT. 269acetic acid and passing chlorine until the whole has gone into solutionand the liquid has a distinct odour of the gas. It c.rystallises fromalcohol or acetic acid in yellowish scales and melts a t 96-97". Whentreated with concentrated alkali it yields dichlorhydroxyindenecwr-boxylic acid which can be recognised by transforming it into dichloro-ketoindene C6H4<C/C1>CC1 ; alcoholic potash on the other hand con-verts it into the supposed ethyl-derivative of chlorhydroxy-S-naph t hn-quinone,&'3-clilorhydroxynaphthaquinone anilide.COC6H4<C(oH):CCr>.co-co Aniline reacts with it formingTetracldoro-p-ketoh ydronaphthal ene C6~4<C~C].CHC1>' is theCC1,-COmost easily prepared of all the keto-derivatives of &naphthol and isobtained by treating a carefully cooled solution of &naphthol in weticacid with an excess of chlorine and a t once precipitating the productwith water. It is necessary that the chlorination should be completedin one operation since a partially chlorinated solution after rernclin-i n g 1% hours gave on further chlorination a crystalline separationconsisting of thick yellowish needles which had the composition(CloH6Cl,0) melted a t 193" and were sparingly soluble in mostsolvents.Obtained in this way the tetrachlorhydroketone crystal-lises with 1 mol. HzO in white lustrous scales melts at 90-91" andis converted into the anhydrous form by repeated crystallisation fromlight petroleum ; it then crystailises in white lustrous scales meltingat 102-103" white needles melting at 101-102" or occasionally incolourless monoclinic prisms. It dissolves in cold alcohol but onstanding or more rapidly on warming it undergoes conversion intoP-trichloro-@-ketonaphthalene. Stannous chloride and sulphitesreduce i t to a/-l-dichlor0-8-naphthol on warming and to a mixture oftliis with the aa-derivative in the cold ; solution of sodium carhonateconverts it into /3-chloro-@-naphthaquinone aqueous soda dissolves itwith the format ion of @P-c hlorh y drox ynaph thaquinone and anilinereacts with it as with p-trichloro-@-ketonaphthalene.When a-trichloro-/j-ketonaphtbalene is further chlorinated it yieldsa compound crystallising in small forms which resemble rhombic sul-pliur crystals both in colour and shape.Although this compoundalways shows the same melting point it is very probable that it is amixture of tetmcliloro-/3-ketorlaph t halene and hexacti loro-@- ketonap'n-thalene in molecular proportions which cannot be separated by crystal-lisation and not a-pen tachloro-@-ketohydronaphthalene inasmuch asa portion of the finely powdered subLtauce dissolved rapidly in alkali,yielding a solution in which dichlorhydroxyindenecarboxylic acidcould be detected whilst the residue was white and resembled hexa-chloro-6-ketohydronaphthalene in its properties.P-Pentachloro-P-keto h ydronapht h alene CsH4< cc12-c0> HC1.C c is ob-' 2tained by saturating a solution of /?-trichloro-p-ketonaphthalene inacetic acid with chlorine.It crystallises in well-formed colourless,friclinic prisms which melt at 116-117" ; if crystallised from ether,howeb er ir forms very large and appareutly rhombohedra1 crystals2 TO ABSTLtACTS OF CHEJIICAL PAPERS.and when crystallised from benzene yields both transparent forms andcrystals which effloresce on exposure to the air.On reduction withstannous chloride sodium sulphite or less readily witb phenylhydr-azine it is converted into trichloro-/I-naphthol and only reacts withaniline at the boiling point when it yields /3/hhlorohydroxynaphtha-quinone anilide. When treated in alcohdic solution with 25 per cent.aqueous potash the ring is split and o?.thoclich2orovinylJz'chlol.ubenzyI-cnrboxylic acid C2HCl2*CtiH4*CCI2-COOH is obtained which crystal-lises from chloroform in transpareut lustrous forms and from lightpetroleum in thick white needles melts at 130-131" with decomposi-tion and evolution of hydrogen chloride but not of carbonic anhydride,aiid is readily soluble in the ordinary solvents. It dissolves i n aqueoussodium carbonate without decomposition but is slowly converted intothe corresponding benzoylcarboxylic acid by caustic alkalis.Onoxidation itt yields dichlorovinylhenzoic acid. The methyl salt,C9H5C14-COOMe crystallises in slender white needles melts a t 99 -loo" and is readily soluble in alcohol and ether.O~-thodichlorirvinyZZ,enzoyZcarbozyZic acid C2HC12*C6H,-C0.C00H isprepared by dissolving the finely-powdered pentachloroketone in 25per cent. aqneous potash and acidifying. It crystallises from dilutealcohol in long slender yellowish needles melts without decompositionat 106-107" and is readily soluble in alcohol and acetic acid butonly sparingly i n light petroleum.The methyl salt has not beensolidified and no solid compound could be obtained by the action ofhodrosvlamine. J JEexachloro-/3-ketonaphthalene C6H4<<ccl~.&-,l,,> CCl co is prepared byheating the tetrachloroketone with 1 part of rna&mese dioxide and5 parts of fuming hydrochloric acid (sp. gr. = 1.19) at 140-150" for6 t o 8 hours. It cryst'allises in long colourless prismatic needles orin compact seemingly monoclinic and occasionally tabular crystals,melts at 129" and dissolves in ether benzene hot alcohol and hotacetic acid. On reductmion i t is converted into trichloro-/3-naph thol.When treated in warm alcoholic solution with concentrated aqueouspotash the ring is split and orthotl.ichlorovinyldichlorobenzylcarbo.cy licucid C2C1,*CsH,*CC1,*COOH can be obtained from the solution bysaturating it with hydrochloric acid.I t crystallises in colourlessneedles or long thick tables melts at 150" with decomposition and isreadily soluble in alcohol and ether. On oxidation it yields oi-thotri-chlorovinylbenzoic acid. The methyl salt C9H4C1,-COOMe crystallisesin colourless slender needles and melts a t 83-84". When the acidis dissolved in concentrated aqueous soda and afterwards acidified anoil is obtained which coiild not he crystallised and probably consistsof the corresponding ketonic acid. w. P. w.Reduction Products of the Azo-dyes of the NaphthaleneSeries. By 0. N. WITT (Bey. 21 3468-348S).-The azo-dyesobtained by t h e action of diazotised bases on the isomeric mono-and di-snlphonic acids of a- and /+naphthol and naphthylamineare converted by reduction into two aiiiines one being the base fromwhich the diazo-compound was obtained and the second beinORG14XIC CHEMISTRY. 271the amido-compound of the naphthalene-derivative employed.Theactual o r supposed instability of these reduction products has hithertoled to the neglect of this method of determining the constituents ofthe naphthalene azo-dyes but this instability is to be ascribed to thesecondary action of the reducing agent employed the use of alkalinereducing agents such i l ~ j zinc-dust with ammonia or soda or theaddition of alkali to the reduction product leading in all cases todecomposition. The method however is the only one capable ofgiving t’rustworthy r&ults and experiment shows that with a suit-able reducing agent a solution of “ tin salt.” in hydrochloric acid,the reduction products of the naphthalene azo-dyes can be isolated forsubsequent identification. For analytical purposes 1 gram of theazo-dye freed from dextrin sodium sulphate arid like impurities isdissolved in 10 c.c. or in the case of the less soluble dyes 20 C.C. ofboiling water the source of heat is then removed and 6 c c. of a s o h -tion of 40 grams of “ tin salt” i n 100 C.C. of pure hydrocllloric acid(sp. gr. = 1-19> corresponding to 2 grams of. tin salt is added. Theamidonapht hol- or nap h t haleuediamine-sulphonic acid formed mayseparate from the warm or cold solution or not at all according tothe nature of the substance and in the last case precipitation withsodium acetate halt or hydrochloric acid as determined by experi-ment must be resorted to.This process is termed by the author anormal reduction.In order to isolate and characterise the reduction products theaniline-azo-dyes derived from p-naphtfho1 Ij-iiaphthylamine andtheir mono- and di-sulphonic acids were alone employed but theiuet’hod presents no difficulties wlieu applied to those azo-dyes foundi l l commerce which are derivatires of these naphthalene-compounds.Dericatives of P-NuplLthuL-The azo-dyes derived from p-naphtholare known to give amido-/3-naphthol on reduction (Liebermanti,Ber. 14 1310). f3-Nttphtiiol-orange (mandarin) o u normal reductionyields a clear and coluurless solution from which white needles andstellar aggregates of amido-p-naphthol hydrochloride separate oncooling.‘l’his salt dissolves readily in hot water but cannot be pre-cipitated either by alkalis or soda the solution becoming dark browniii colour.. Sodium acetate however precipitates amido-&naphtholfrom the solution in lustrous scales which dissolve readily in ether,and crystallise in smail? quadratic tables on spontaneous evaporationof the solvent. The addition of ferric chloride to the hydrochloride inaqueous solution converts it into /%naphthaquinone.Uerivu tives of the fl-il-ap h t 11 olsulphonic Acids .- ( 1. ) Arnido-,d -niiphtliol-a-sulpholLic acid NH,*C,,H,( OH)*SO,H.-The orange fromdiazobenzene chloride and Bayer’s $-naphthol-a-sulphonic acid onnormal reduction yields arnidonaphtliolsulphonic acid which c r j stablises from the hot solution in small well-formed rectangularlyLitriated .pale rose-coloured scales and can be purified by recrj stal-lisation from a dilute solution of sodium acetate.It is very sparinglysoluble in hot water and in sodium acetate solution ; alkalis and alkalineearths however dissolve it readily and the solutions very rapidlybecome deep orange-brown 011 exposure to air. Oxidising agentscolour bot,h che neutral aud a l k a h e solutions of the acid deep J ello272 ABSTRACTS OF CHEMICAL PAPERS.or brown and silver salts are a t once reduced b.y it and each of thefollowing acids in both acid arid ammoniacal solution.It does notvield a diazo-compound on treatment in acid solution with sodiumnitrite and diazo-compounds do not react with it but decomposewith the evolution of nitrogen and formation of ft brown colour.When treated with nitrosodimet~hylaniline hydrochloride in a 50 percent. acetic acid solution it forms a characteristic violet colouringmatter which in aqueous solution is coloured red on addition ofaqueous soda.(2.) Amicto-P-nn~hthol-P-sul~honic Acid (Meldola Trans. 1881,47 ; Crriess Abstr. 1882 50).-The orange from diazobenzenechloride and Suhaff er’s p-nap11 thol-P-snlphonic acid on normal reduc-tion yields this amido-acid which separates from the hot solution as acrystalline magma. It is insoluble i n alcohol and oannot be purifiedby solution in water Rince decomposition ensues with the formationof brown solutions which on the addition of hydrochloric acid becomeviolet.It is soluble in hot 20 per cent. aqueous sodium acetate inthe presence of acetic acid and is precipitated from the solution onaddition of hydrochloric or dilute sulphuric acid. With oxidisingagents and sodium nitrite i t behaves like the precedigg compound,b u t differs from it in not yielding a colouring matter with nitroso-dimethylaniline hydrochloride. I t is cbarncterised by readily yielding,011 treatment with diazo-compounds beautiful colouring matters,which however do not dye wool ; thus with diazobenzenesulplionicacid a magenta colouriiig matter is obtained whose shade is renderedbluish on addition of hydrochloric acid whilst with tetrazos t i I benedi-sulphonic acid a reddishdviolet colouring matter is formed which onaddition of hydrochloric acid is p~ecipitated in beautiful blue flocksso1iil)le in water to a blue solution.(3.) Amido-/?-?zaplz th ol- 6-sulph o nic A cid .-T he an iline-azo- deri vativeof Casella’s naphtholsulphonic acid F on uornial reduction yields thisaniido-acid which crjstalliaes from the warm solrition in shimmering,rose-red needles. I t closely resembles :tmido-/3-naphthol-~3-sulphonicacid in its properties and reactions but is less sensitive and ischaracterised b.y reacting only with some diazo-compounds and thenbut slowly. Thus addition of the diazo-compound from Bronner’s/3-naphthylaniine-~-sulphonic acid results in decomposition and theevolution of nitrogen whereas amido-13- napht hol-6-sulp honic acidforms with it a reddish-violet colouring matter.Diazobenzene-sulphonic acid produces with it a transitory red coloration followedby decomposition and evolution of nitrogen ; tetrazostilbenedisnlphonicacid however reacts with it forming a dull brownish-violef colouringmatter which is precipitated without change of colour by hydro-chloric acid.(4) A mido-P- nap7i t h ol-ry- suzphonic Acid.-T he aniline-azo-derivativeof /j-naphthol-y-sulphonic acid on normal reduction yields this amido-acid which separates in a crystalline form from the warm solution,and can be purified by repeated solutioii in hot aqueous sodiumacetate and precipitation with hydrochloric acid.I t i s the most sparinglysoluble as well as the most! stable of the isomerides and forms small,rose-red aggregates which are scarcely soluble i n hut water. WitORG-INIC CHEMISTRY. 273alkalis oxidising agents and silver salts i t behaves like its isomerides,and is characteiised by reacting neither with diazo-compounds nor\jrith nitrosodimethylaniline hydrochloride i n acetic acid solution.Derivatives of p-Naphtholdisuli,honic Acids. (1 .) Amido-p-naphthol-a-disulphonic acid.-" Ponceau 2 G," the aniliiie-am-derivative ofp-nap hthol-a-disulphonic acid (R-acid) on normal reduction yieldsa clear solution which after cooling and standing some time de-posihs slender snow- white silky needlerJ ; an immediate separationin the form of satiny needles is however produced by the additionof an equal volume of saturated salt solution directly the reduc-t.ion is complete. The sodium hydrogen salt of the amido-acid,NH,*C,,H,(OH) (SO3H)@SOaNa thus obtained is collected washedwith alcohol and ether and dried but is still impure owing to thepresence of amido-p-naphthol-/3-sulplionic acid obtained from theSchaffer's acid which is always present in the R-acid employed techni-cally ; it can be purified by rapidly dissolving ii; in 10 times its weightof acidified water adding an equal volume of ice-cold alcohol and a tonce immersing the solution in a freezing mixture in order to bringabout rapid crystallisation. In the dry state the compound is stable,hut in aqueous solution it is extraordinarily unstable decomposingat once into what is almost certainly sodium ammonium dihydroxy-napht halenedisu l p honate S03Na*C10H4( 0 H )?-S03NH4 wb ich separatesfrom the solution on addition of salt in grey scales. This compoundis readily soluble in water less so in alcohol decomposes rapidly onaddition of alkalis with the formation of brown solutions and is asalt of the supposed amido-6-naphthol-a-disulphonic acid described byGriess (Abstr.loc. cit.). The amido-acid is rapidly oxidised byalkalis does not react with diazo-compounds and nitrosodimethyl-aniline and immediately reduces silver salts to metallic silver.(2.) Amido-a-na~hthol-(y-dipul~horLic Acid.-" Orange G" theani li ne-azo-deriva tive of /%nap h t h 01-y- d iso Iphon ic acid (pureG-acid) on normal reduction yields a clear solution from which saltsolution precipitates the sodium hydroqeiz salt of the amido-acid,NH2*~,,H4(OH)(S0,H)-SO3Na in snow-white prisms or small aggre-gates of prisms.It is much more stable than its isomeride andalthough it shows all the reactions given by the a-derivative yet thedecompositions take place so much more slowly as LO afford a meansof distinguishing between the two for example with silver salts thereduction only commences some minutes after the solutions have beenmixed.Derivutives of P-Naphth ylamine. - The azo-dyes derived fromP-naphthylamine are known to give a-/3-orthonaphthylenediamineon reduction. The aniline-azo-derivative formed by t h e action ofdiazobenzenesulphonic acid on /zI-naphthylanline on normal reductionyields the hydrochloride of this diamine which crystallises from thewarm solution in slender white needles and is characterised bFforming naphthaphenanthrazine when treated in aqueous solution con-taining acetic acid and sodium acetate with an aqueous solution of thebisul p hi te compound of phenanthraquinone.Nap ht haphtmr n t hrazi necrystnllises in yellowish-white sparingly solnble needles and dissolvesi n sulphuric acid with B blackish-violet colour which becomes yello2 74 ABSTRACTS OF CHIEAIICAL PAPERS.on dilution. The azo-dyes obtained from phenpl-P-naphthyl~miii~ andthe toluyl-/3-naph thylsmines have alreadv been shown to yield azincson treatment with acids (Abstr.1867 590).Derivatives of p-N~phthill~mine~u~p?~oiiic Acids.-(1.) The B-naph-thvlamine-a-sulphonic acid (Badische acid) reacts with diazobenzene-sulphonic acid but yields a yellow diazoamido- and not an azo-compound which on normal reduction is converted into phenyl-hydrazine and unchanged Badische acid.(2.) Orf honaphtkylenec.Jiar~r~e-p-szLlph onic acid CI,Hj (NH,),.S 0,H -“ Gold brown,” the aniline-azo-derivative of /I-naphthylamine-p-mlphonic acid (Rronner’s acid) on normal reduction yields crystalswhich separate from the hot solution and can be puyified by solu-tion in aqueous sodium acetate and precipitation with acetic orhydrochloric avids. It forms slender pointed needles is verysparingly soluble in water and in alkaline solution becomes rapidlybrown on exposure to the air ; an excess of soda.however precipitatesa sodium salt in silvery scales. Potassium ferricysnide produces abrown colour with the alkaline solution which subsequently changest o a pure yellow and ferric chloride forms a dull green precipitate inthe aqueons solution. The acid is chnracterised bv yielding the cityon-yellow sodium napht~a~~enanthraxinesulpphontcte C21H17N2.S03Na whenits solution in sodium acctate and acetic acid is treated with anaqneons solution of the bisulphite compound of phennnthraqiiinone.This salt dissolves in snlphuric acid with a reddish-violet colour andon fusion with potassium hydroxide is converted into a eurhodol,which is obtained in brown,.gelatinous flocks on acidifying the solu-tion of the melt dissolves in sulphuric acid with a pure ultramarinecolour and is slowly precipitated as a cherry-red sulpbate on additionof water to the solution.(3.) OrthonaphthylPnedinmine-8-su7ho?iic Acid -The aniline-azo-dye obtained from B-na.phthylamine-8-sulphonic acid (F-acid) onnormal reduction.yields a clear solution which deposits only a fewflocks on standing. An indistinctly crrstalline precipitate is obtainedby adding salt solution and hydrochloric acid and this when purifiedby solution in sodium acetate and precipitation with hydrochloricacid forms a rey powder which dissolves in water more readily thanthe p-acid. kt its behaviour with alkalis potassium ferricyanide,and ferric chloride it resembles the p-acid. but excess of soda doesnot precipitate a crystalline sodium salt from its solution.The cor-responding sodium naphthaphennnthrazinesulphonate crystallises fromdilute alcohol in Plender needles and dissolves in su1phuric acid witha reddish-violet colour and the eurhodol foriiis a pure violet solutionwith snlphuric acid which on dilution yields a brownish-red precipi-tate of the sulpbate.(4.) Oi*thonaphthylenediamine-ysulphonic Acid. -The aniline-azo-derivative of P-naplithylamine-y-sulphonic acid (Dahl’s acid) onnormal reduction yields this acid which crystallises from the hotsolution and can be purified by solution in sodium acetate and pre-cipitation with hydrochloric acid. It crystallices in ~himmeriugbrown scales is more soluble i n water th?n the @-compound reducessilver salts and in aqueous solution yields a deep green coloratio0 R GXNIC CHE MIS’IXY.2 7.iwith ferric chloride the solution subsequently depositing a dark-green precipitate. The alkaline solution slowly assumes a browncolour. The corresponding sodizirn n~phfhaphenanthrazinesulph~niitedissolves in sulphuric acid with a violet colour which on dilutionbecomes orange and the eurhodol dissolves in sulphuric acid with Ablack-violet colour and the solution on dilution with water firstbecomes cherry-red and afterwards deposits the sulphate in dark-redflocks.Derivatives of ~3-~~aphtlzylaminedisulpphonic Acids.-The P-naphth,yl-amine-ydisulphonic acid (amido- G-acid) according to Schultz (]OMnot combine with diazo-compounds.The aniline-azo-derivative of 6-naphthylamine-a-disnlphonic acid(amido-R-acid) on normal reduction ? ields a clear solution on cooling,from which hydrochloric acid precipitates the sodeum hydrogen sult,S0,H.CloH,(NH,)2.S03Na. This can be purified by dissolviiig it in waterand precipitating with salt solution and f timing hydroclilncic acid.When obtained by precipitation with hydrochloric acid i t forms asandy powder consisting of well formed and often twinned prisms,whilst salt solution precipitates it in the form of slender pointedneedles.It is readily soluble in water a n d the solution fluorescesgreen in the absence of mineral acids yields sparingly soluble pre-cipitates with barium and calcium chlorides and becomes coloureddeep green on addition of ferric chloride.It resembles orthonaph-thylenediamine-1-sulphonic acid in its behaviour with alkalis andsilver salts. The corresponding sodium na~hthaphr~nantl~ruzinedi-su7phonntr form8 a transparent citron-yello w gelatinous mass whichcould not be crystallised and dissolves in sulphuric with a verycharacteristic bluish-magenta coloration which on dilution becomesfirst yellow and then orange. The eurhodol is insoluble in water andyields a deep greenish-blue solution in sulphuric acid which on dilu-tion becomes first violet and then bordeaux-red ; further dilutiouprecipitates the eurhodol itself in yellowish-brown flocks.Constitution of @-Naphthol-a-Sulphonic Acid.w. P. w.By 0. N.WITT (Ber. 21 3489-3492).-When amido-P-naphthol-a-sulphonicacid (see preceding Abstract) is heated with concentrated hydro-chloric acid a t 120” for 4-5 hours it yields a dihydroxynaphthalene,which on oxidation with ferric chloride is converted into B-naphthx-quinone. It follows therefore that nmido-B-naphthol-a-sulphonic acidhas the constitution [NH, OH SOAH = 1 2 21 and consequentlyBayer’s P-naplit~ol-a-snlphonic acid cannot have the constitutionNote by Abstractor.-Throughout the paper the author regardsArmstrong as the authority for the 1 2 formula hitherto frequentlyassigned to Bayer’s acid; this however is due to a misconception(compare Arnistrong Proc.1889 8). The acid has been shown tobe heteronucleal by Armstrong and Wynne (Proc. 1888,104 ; 1889 T).Action of Fuming Sulphuric Acid on Bronner’s 6’-Naphthyl-amine-P-Sulphonic Acid.By S. FOESLING (Ber. 21 3495-3499).[SO,H OH = 1 21. w. P. w.w. P. w276 ABSTRACTS OF CHEMICAL PAPERS.When Bronner's p-naphthylamine-6-sulphonic acid dried a t lC;O",is heated with 3 to 4 parts of fuming sulphuric acid a t about 110"until a test specimen dissolves in water a mixture of P-naphthyl-aminedisulphonic acid together with a small quantity of a secondacid is obtained ; the yield of the latter is increased by allowing thesulphonation to proceed a t a higher temperature for a longer time.~-~-aphthylamir~edisulphoi~lzic acid NH2*CloH,( SO,H) cannot beobtained by acidifyiug the solution of a normal salt since the corre-sponding acid salt is thereby formed. It can be prepared however,by treating the barium salt with sulphuric acid and crystallises inwhite needles which are extremely soluble in water but only sparinglyin alcohol.The potassium salt crystsllises with 2 mols. H20 in large,yellow crystals ; the potassium hydrogen salt with 1 mol. H20 in long,white slender needles; the sodium salt in long white needles; thesodium hydrogen salt with 2 mols. H,O in long white slenderneedles ; the animoirium salt with 1 mol. HaO in large red tricliniccrystais and the ammoni7hm h?/drogm salt in anhydrous slender,white needles ; the burium and cnlc-ium salts are also described. Thenormal salts are readily soluble in water the acid salts on theconti*ary are somewhat sparingly soluble in cold water. Whendiazotised in alcoholic solution with nitrous acid the acid salts of theacid are converted into the corresponding diazonaphthalenedisulpho-nates which are relatively stable and can be boiled with absolutealcohol without decomposition ; the potassium and ammoniuin sat tscrystsllise in microscopic yellow rhombio tables the sodium salt inneedles.The potassium salt OP p-chloronnphthalenedisulphonic acid,is obtained by heating potassium diazonaphthalenedisulphonate withcuprous chloride and hydrochloric acid.It crystallises in whiteneedles and is only sparingly soluble in cold water. The disulpho-chloride CIoK5C1( SO,CI) crystallises from benzene in thick tables andfrom chloroform in small colourless prisms melts a t 1245" and isvery sparingly soluble in light petroleum.The trichZo?nnaphtlraZene,C,,H5CI c q stallises in dendritic aggregates of slender needles meltsat 91" and is sparingly soluble In alcohol but readily soluble inchloroform. w . P. w.Filicic Acid. By E. LUCK (Bey. 21 3465-3468).-A reply tothe criticisms of Daccomo ( H e y . 21 2962 this vol. p. 54). Purefilicic acid melts at 184-5" but if the specimen is allowed to solidifyand the melting point again taken it is found to sinter at about 130",and melt a t 150-160". w. P. w.Transformation of Terpilene into Menthene. By G. Bou-CHARDAT and J. LAFONT (Cumpt. rend. 107 916-918).-When terpinis treated with concentrated hydriodic acid i t yields a crystallineterpilene dihydriodide identical with that obtained from tereben-thene. The terpin is mixed with hpdriodic acid saturated at O",and as soon as the temperature is raised the liquid separates into twORa ANIC CHEMIbTRY.277layers and iodine is liberated which indimtes that hydrogen hascwmbirred with the hydrocarbon. The mixture waq heated a t 1OOOfor20 to 2% hours the weight of hydriodic acid varying from 16 to 60times thRt of the terpin. The principitl reaction i q represented bythe equation CioHifi,2HI + 41 = C1,H,,HI + I? whilst part of theterpilene is polyrnerised. The principal product is isomeric if notidentical with menthene hydriodide CloHIgI but it cannot be isolatedfrom the accornpanjing diterpilene since i t decomposes even at asomewhat low temperature.If the free iodine and acid are removed and the hydi-iodide isheated a t 100" with potassium acetate potassium iodide is depoqitedand an oily liquid is obtained which is lighter than water.Whendistilled it separates into two fractions one of which boils a t210-225" under a pressure of 30 mm. and consists of diterpilcnemixed with hydrides of similar boiling point whilst the other has thecomposition CIOHiA and boils a t 167-li0" under ordinary pressure ;sp. gr. at 0" = 0.837.The latter hydrocarbon combines very slowly with hydracids antidiffers in this respect from terpilene. If heated at 100" for 10 hourswith 6 to 8 volumes of hydrochloric acid saturated a t O" combinationis complete but only a monohydrochloride is formed. This is an oilyliquid lighter than water. It has an agreeable odour does not.solidify a t -GO" and boil.without decomposition a t 105-110" under:I pressure of 30 mm. Under ordinary prescure it decomposes intohydrogen chloride and the hydrocarbon. When treated with alkalis,the hydrochloride yields the hydrocarbon but there is no appreciableformation of any oxygen compound. All its properties agree withthose of a menthol-derivative and the hydrocarbon is identical orisomeric with Oppenheim's menthene. It is evident also that there isit close relation between terpilene and menthene. C. H. B.Essential Oil of Daucus Carota. By M. LANDSBERG (Chen7.Centr. 1888 1273).-.By. means of fractional distillation this oil wasdivided into two principal fractions the one boiling at 159-161"and the other at 240-360". The former contains no oxygen and isa terpene of the formula CIoH,,.It is dextrorotatorg; a column100 mm. long rotating the plane 32.3"; sp. gr. = 0.8525 at 28".With bromine i t forms an addirive compound C,,H,,Br ; from this,cgmene was obtained by boiling its alcoholic solution with an aqueoussolution of potassium cyanide. On heating the ttrpene in a closedtube at 280" it is split np into two terpenes the one boiling at178-182" and the other not distilling a t 300O. Both combine withbromine to form additive conipcunds ; that from the former Cl,,H,,Br4,melts a t 123-125" ; t h a t from the latter has the formula C,,H1,Br2.They may be considered a s polymerides of the original terpene whichbelongs to the group of pinenes.The second component of the essential oil (boiling point 240-260")proved to be a monohydrated terpene of the formula C,,H,,O.Whenheated to 280" it loses the elements of water and the residue consistsof the same polymeric terpene of high boiling point as is obtainod byheating +,he first-named terpene a t 280'. The behaviour of the mono-VOL. LVI. 2 i 8 ABSTRACTS OF CHEMICAL PAPERS.hydrated terpene with bromine and with hvdrogen chloride or bro-mide proved it to be identical with Wallach's cineole. J. w. L.Constitution of Quassin. By V. OLrvERr (Gazzetfa 18 169-170).-In a prei-ious communication (Abstr. 1888 1312) the authorpointed out that quassic acid contained two ketonic groupr since itgave rise to a dioxime of the formula C28H,,O,(C:NOH),. I h seemed,however desirable to establish that these CO-groups existed also inquassin and for this purpose the author prepared the compound ofquassin with phenylhydmzine. Quassin ( 3 grams) and phenylhydr-aziiie hydrochloride (4 grams) were dissolved i n the smallest possiblequantity of alcohol a solution of sodium acetate added (6 grams iii15 C.C.water) and the whole heated at 100" for an hour. The yellow,amorphous deposit formed on dlowing i t to remain for a day wasthoroughly washed with water and aLtempts made to obtain i t in itcrystalline state but wit,hout success. 4 n analysis showed that it hat1tlle composition C,,H4,08( CH-NHPh),. It is formed from phenyl-Iiydrazine and quassin with elimination of tlie elements of water,thus C,,H*oO,(CO) + 2NH,*NHPh = C,,Z,oO,(CIL'*NHPh) + 2HzO.C.E. G.Methysticin. By C. POMERANZ (Moriatsh. 9 862-864).-Methy-sticin is a non-nitrogenous non-volatile neutral substance whichoccurs in the alcoholic extracts from the roots of Maci*opiper methy-sticunz. I t crystallises in long silky needles melting a t 131" sparinglysoluble in hot water ether and light petroloum readily soluble inalcohol benzene and chloroform. It contains about 65.4 per cent.carbon and 5.1 per cent. hydrogen. When fused with potash it giveschiefly protocatechuic acid. Heated with 30 tinies the amount of 10 percent. potash solution it complt4ely dissolves arid from the solution,which smells strongly of piperonal hydrochloric acid precipitates ayellowish compound which separates from alcohol in small whitecrystals melting at 180".This compound which contains 64.26 percent. carbon and 4 85 per cent. hydrogen is readily soluble in alkalinecarbonates and yields piperonylic acid on oxidation with perman-ganate. H. C.Note.-No reference i s made to Davidoffs researches on this subject(compare Abstr. 1888 1207).Andromedotoxin. By P . C. PLUGGE and H. G. DE ZAAYE~~{di-ch. Pharrit. [3] 26 997-998 from Arch. yes. Physiol. 40. SeeAbstr. 1883 349).-Plugge first obtained nndromedotoxin which hetlxtracted from Androw eda japotr ica A. polifoliu A. catesbaci andA. ca 1 y c w l a t a.The aqueous extract of Rhododendron powticum leaves was treatedsuccessively with norrrial and basic lead acetate. From the filtrate,the lead was separated by hydrogen sulphide and the liquid was con-centrated by slow evaporation in the air and treated repeatedly withconsiderable quantities of chloroform.The residue left on evaporatingthe chlorofoi~m was purified by re-solution in chloroform (or alcoholORGXSIC CHEJIISTRY. 2 59and precipitation by the addition of a considerable amount of ether.This treatment several times repeated finally yielded well formed,crystalline needles which melted at 228-229O. A t 125O water dis-solves 2.81 per cent. ; alcohol (of 94 per cent.) 11.1 ; amyl alcohol 1-14. ;chloroform 0.26 ; ether 0.07 ; benzene 0.004. The solutions in water,alcohol and amyl alcohol are lmrorotatory whilst that in chloroformis dextrorotatory. Andromedotoxin CslH,,O, is an indifferent non-nitrogenous compound ; its solution in indifferent liquids has a neutralreaction and it is not precipitated by any of the so-called generaliblkalo'id rzagents.Its reaction with dilute and concentrated mineralacids is characteristic as with them it gives intensely red decom-position-products. Concentrated sulphuric acid gives a dark reddish-brown which becomes deeper red on warming and turns lightmulberry-red on dilution with water. The addition of alkali removesthe colour. which reappears on acidifying. Evaporation with dilute(1 5) sulphuric acid gives a beautiful rose-red colour. The purematerial gives off no odour during this evaporation but if uot com-pletely purified a strong and very characteristic odour of ericinol isevolved. Evaporation with dilute hydrochloric acid gives a residuesomewhat rliore violet-red in tint.Evaporation with phosphoric acidgive,. a mulberry. red residue clezrly pyrcepti ble with very minutequ mtities as in the case of the other acids. The fatal dose for smallanimals has becn found to vary from 0.1-0.45 mgrm. per kilo. body-weight. No chemical antidote is known a s pet. I n investigatingpoisoning cases Dragendorff's process is recommended ; but no acidshould be used for extraction as the so1ubilit)p of the poison is notthereby increased. After extraction and purification by evaporation,taking up in alcohol &c. the substance may be agitated with lightpetroleum then with chloroform and to the residue left by thechloroform the characteris tic tests given above may be applied.T m tJ.1.Chlorophyll. By E. SCHUNCK (Proc. Roy. Soc. 44 448-454;compare Abstr. 1887 972).-Crude chlorophyll from grass is treatedwith boiling alcoholic soda and hydrogen chloride passed into the solu-tion until i t is strongly acid. Ci*ystals separate which after purifica-tion form a semi-metallic purple mass which softens a t 2M0 andshows the absorption-spectrum of phyllocyank-derivatives. This com-pound is an ethyl ether. On treating it with boiling alcoholic soda adark-green sodium salt is obtained which when decomposed by aceticacid anci crystallised from ether gives purple crjstals of a new sub-stance phyllotuoni?t melting a t 184" and insoluble in water butsoluble in boiling alcohol and ether. The solution shows the samebands as phyllocyanin but i f the smallest quantity of acid be added,the third band from the end becomes fainter and the fourth andfifth bands split into t w o I t forms a compound with acetic acid.Phyllotaonin forms compounds with potassium sodium copper iron,and silver.With tin and hydrochloric acid it gives a red cam-I)' und similar to that produced from phyllocyanin with the samertiagents. A compound similar to the ether mentioned above maybe obtained by treating phyllotaonin with ethyl iodide and potassiumu 280 ABSTRACTS OF CHEVICAL PAPERS.hydroxide ; it is a black substance whose solution gives an absorption-spectrum similar to that of the above ether. When chlorophyll istreated with alkalis and then with acids it probably yields phyllo-taonin which in the nascent state in contact with alcohol and hydro-chloric acid undergoes etherification.Crystallographic measurementsof phyllotaonin are given.Hydroxyhydroquinoxalines. By 0. HTNSUERG (Anrialen 248,71-84) .-The author has repeated the experiments of Plochl (Abstr.,1886 351) and of Leuckwrt (ibid.) on the reduction of nitrotolyl-glycin by tin and hydroc;hloric acid and finds that the product isidentical with the dihydrohydroxytoluquinoxaline which is formed bythe action of ethyl chloracetate on toluylenedihmine. This substancerapidJy oxidises forming hydroxytoluquiiioxaline which Plochl andLeucknrt mistook for dihydrohydroxytoluquinoxaline. The substancudescribed by Leucknrt and Hermann (Abst,r.1887 38:3) as chlcro-dihydrotoluquinoxnline is also a derivative of hydroxytoluquincxaline.Ethyl a-chloropropionake acts on toluylenediamine forming an unstablecompound which oxidises on exposure to tlie air yielding hydrmxyX:C (OH) meth yltotuyuinoxnline C7H6<K:CMe->. The substance is crys-talline and melts at 238". It is probably a mixture of two isomericq uinoxalines.Dimethyloxy dihydrotoluquii.l.oxalin e C,H,< ~ ~ ~ ~ ~ prepared bythe action of ethyl bromisobutyrate on toluylenediamine is a stablecrystalline compound soluble in alcohol and ether. It melts a t 227",and yields a crystalline acetyl derivative Cl1HlJN20Ac melting a t206". The nifroso-derivative C,H,,N,ONO melts at 153-1 54O withdecomposition. The dinitro-compound melts at 280".Dimethyl-oxydihydrotoluquinoxaJine does not like its apparent homologues lose2 atoms of hydrogen on oxidation but undergoes a deeper change.I t s whole behaviour shows that it does not belong to the class ofH. K. T.hy droxyquinoxalines. w. c. w.Metabrornoquinolines. By A. CLAUS and G. N. Vrs ( J . tw.Chem. [a] 38 387-394) .-The metabromoquinoliiie nitrate (m. p.163") previoiisly obtained by Claw and Tornier (Abstx. 1888 163),is really a mixture and the oil obtained from it is not pure metabromo-quinoline as then described b u t a mixture of both bromoguinnlines,and generally contains some unaltered metabromaniline. Whenthis nitrate is further fractionally crgstallised a nitrate melting a t185" (u~icorr.) is obtained ; the base separated from this crystallisesin beautiful colourless needles melting a t 48" (uncorr.) and as it hasa higher melting point than the bromoquinoline previously describedas annbromoquinoline (Ahstr.1888 163) it is doubtless t,he realn.nnbromoquinoZinP. Moreover this bromoquinoline cam be obtainedfrom ana-amidoquinoline by converting it into ananitroquinoline andtreating the latter by Sandemeyer's method.The other bromoq uinoline previonsly described as anabromoquino-line (Abstr. 1888 lti3) whose true melting point is 3 4 is the reaORGASIC CHEMLYTRT. 2s 1metubronzoquinoline ; its nitrate melts a t 19V ; il,s wwthiodide formsanhydrous yellow needles or prisms melting a t %4Uc ~unoorr.).When metabromoquinoline (1 part) is nitrated with a mixture(5 parts) of 2 parts of sulphuric acid and 1 part of nitric acid twonitro-derivatives are obtained.a-Nitrometahromopui?toli~e crptallisesin large transparent prisms which melt at 192" (uncorr.) ; itsplatinochloride is bright-red and decomposes a t 240".a AmidoinetnbromuquirLoZLize forms coluurless needles which melt at62" (uncorr.)./%Nitronaetabrornoquinolins crystallises from alcohol in white aggre-gates of needles which melt at 141" (uricorr.) and has feeble basicproperties ; its ylatinochloride forms small golden-yellow anhydrouslam in%.'l'he methiodlde of anabrornoquinoline crystallises from hot waterin yellow needles melting a t 203" (iincorr.). Two nitro-derivativesare obtained by iiitratiiig annbrornoquinoline a-nitrarcubromo-qihinoZine which crystnllises in slender nearly colourless needles andmelts at 146" (uiicorr.) and fi-nit~-unabromoquin dine which alsoforms nearly colourless needles ; i t melts at 126" (uncorr.) and is astronger base than the a-compound.The platinochloi ides of both aredescribed. A. G. B.A Cerium Qainoline Nitrate. By G. WILLIAMS (Chew. News,58 199-200) .-'When moderately concentrated so 1 u tions of cericand quirioline nitrates are mixed glistening orange-red rhombicplates of the double nitrate Ce(N0,),.(C,H,N,HN0,)2 form. Theair-dried salt is amorphous and melts rendily giving off nitrous fumesand an odour of nitrobenzene. 011 ignition it frequently deflagrates.D. A. L.Additive Product of Papaverine with OrthonitrobenzylChloride. By E.v. SEUTTEB. (Monatsh. 9,857-862).-20 grams ofpapaverine and 12 grams of orthonitrobenzyl chloride finely powderedand mixed together are heated for five hours on a water-bath. Theproduct is extracted with water excess of the chloride removed byagitation with ether and the additive product obtained from thesolut,ion in light yellow crystals. These contain varying amounts ofwater according to the method used in drying them The anhydrousproduct gives numbers f o r the chlorine and nitrogen wliich point tothe composition ~,,,H,,NO,,C,H,NO,C;1. The nhrate picrate a i ddichroniate are described as also the platinoohloride.Constitution of the Cinchona Alkaloids. By Z. H. SKKAUP(Morzatsh. 9 783-827).-This paper contains the details of' the in-vestigation of the sjrupy oxidation product of cinchonine and quinine(Abstr.1887 164). 'l'hc syrup after removal of chromium by meansof ammonia is treated with barium chloride and extracted with alcohol,and is t h u s separated into two portious one which is insoluble con-taining the whole of the barium and the other free flom barium,which is soluble.The barium salt of the organic acid present in the insoluble portionH. C282 ABSTRACTS Ok' CUERIIC'AL PAPKRS.is converted into a lead salt and this on analysis has the composition(C8H12N01)PPb. It is the salt of the inoriobasic acid C,H,,NO,mentioned in the former paper to which the name cincholeuponicacid is now given. By heating the lead salt with acetic anhy-dride a t 120-130" one o€ the hydrogen-atoms of this acid maybe displaced by acetyl.Distilled with zinc-dust a mixture ofJ > ~ I idirie and its higher homologues is obtained together with a largequantity of a non-volatile resin. The action of nitrous acid yields,;Imong a variety of other products a bibasic acid of the compositionC,H,,14'?O5. On treatment with hydrogen chloride this acid losesnitrous acid and becomes converted into the compound C,H N04,HCI,a change which shows that the acid C,H,,N,O is N citroso- or isoni-troso-derivative. On removing the hpdrogen chloride from the abovehydrochloride by means of silver oxide cincholeuponic acid may beobtained in crystals. This acid although monobasic probi>bly con-tains two carboxyl-groups one of which only becomes active in theacetyl- and nitroso-derivatires.That portion of the original syrup which is soluble in alcohol coil-t i n s the three bases mentioned in the former paper. Of these thelast which is of doubtful origin and whose composition should havebeen given as C,3H16N0.hams been snbniittod to no further examina-tion. The base C9H17NO? separated by means of its crjstallinecompound with gold chloride is here named cinchoieupone. It formsa crystalline coniponnd with 1 mol. HCI; this has a slight opticalrotatory power. When oxidised with chromic acid cincholeuponicacid is obtained along with a number of basic substances. Heatedwith zinc-dust it gives $-ethylpyridine as the chief product butno qninoline is formed. By means of acetic anhydride one hydrogen-atom may be displaced by acetyl ; the derivative thus obtained hasthe properties of a monobasic acid.By the action of alkyl iodides,1 atom of hydmpn rnss be displaced by an alcohol radicle. Thenitroso-derivative C,H,,N,OJ produced by the action of' nitrous acid,has likewise the properties of a monobasic acid. The third basepresent C,H,NO which is separated by means of its plntinochloride,is here identified with kpurine.The author discusses the above results with reference to the con-stitution of cinchonine. He looks on cincholeupone as a secondaryamine being most likely a /3-ethylpyridine-derivative and considersit pmbable that cinchonine contains a quinoline-ring connected by a tleast two of its carbon-atoms with an etliylated pyridine-ring.H.C.Colchicine. By G. JOHANNY and S. ZEISEL (Monatsh. 9,865-881).-The view put forward by one of the authors (Abstr. 1888 613)that colchicine is niethylatecl colchiceine and this latter an acetyl-derivative of trirnethylcolchicinic acid is supported by syntheticalevidence. By the action of methyl iodide on sodium colchiceine col-chicine is produced as also by passing hydrogen chloride through asolution of colchicelne in methyl alcohol. I n the first of these re-actions a substance is also formed which appears to be naethylcodchicine,CLLH24NMt06 ; this when boiled with dilute hydrogen chloride yieldORUAKIC CHJC!IlIST RV . 283methylcoIchice'ine. Colchiceine is produced by the action of aceticanhydride on tiime t h y 1 colch i cinic acid.Trimetliylcolchicinic acid is found to crystallise with 2 mols.MeOH.When heated with sodium metahoxide and methyl iodide i n mole-cular proportions a substance is obtained which the authors calltl-imet hy 1 co 1 chidi?msth lnic a c i d C 0 0 E€*C i5H9 ( 0 Me) B*N Me2 in w h i c hthe hydipoperi-atoms of the amido-group in the original acid have beensubstituted by methyl-groups. By the action of afurther quantity of ruetliyl iodide the methiodide of t h s methyl s a l tof the above acid is obtained. This substance on treatment withsi!ver oxide gives oE trimethylamine thus showing that it containsthe NMeBIL group. H. C.It melts at 126".Action of Acid Chlorides on the Methyl Salt of EcgonineHydrochloride. By A.EINHORN and 0. KLEIN ( B e y . 21,3335-3338).-The methjl salt of ecgonine hydrochloride C,B,4NO-C00%Ie,HCl + HzO is obtained by saturating a solution of ecgonine hydrocblorideit1 methyl alcohol with hydrogen chloride and heating the product ina reflux apparatus for an hour. It crystailises from alcohol i n beau-tiful transparent prisms and melts a t 212" with decomposition.The methyl salt of benzoylecgonire o r cocaine C17H21Y04 can beprepared by heating equal weights of the methjl salt of ecgoninehydrochloride aiid benzoic chloride at 1C'O" for some hours untilhjdrogen chloride is no loilger evolved. The hase obtained by addinga n alkali to the product has all the properties of the natural alkaloid(compare Lie1,erniann and Giesel this vol. p.168).The methyl salt of isovccle?.yZe~gllnine C,,H,,NO,. is formed byheilting equal weights of the methyl salt of ecgonine hydrochlorideand isovaleric chloride at 100" f u r 15 minutes. The base is ax oiland could not be crystallised although i t s hydroc.hloride hydro-bromide and hydriodide crystallise well. The ylatinochlor-ide.(C15HziNO~)~,H,PtCI forms large scales.The methyl salt of ~ h e n y Z n c e t ~ Z e / ~ ~ o n i r i e C1sH'L3NOir is obtained byheating equal weights of the methyl salt of ecgoiiine hydrochlorideand phenylscetic chloride a t 100" for some hours. It is a n oilwhich could not be crystallised although its hydrobromide andhydriodide crystal!ise well from absolute alcohol. The platinochloride,(C18 H 2,PU'0,)2,H,PtCI is crystalline.The diniethyl salt of oi-fho~htlLtrZyZdieI.gonilie C2RH36N208 is preparednnder like conditions from the methyl salt of ecgonine hydrochloride,and orthophthalic chloride.It is crystalline and jields a hydr-iodide crystallising from alcohol in scales. The pZati)mchZvyide,Cz8H36Nz08,HzPtC1 crystallises in scales. w-. P. w.Cinnamylcocahe. By C. LIEBERMANN (Ber. 21 3372-3376) .-C'innanzyZecgoni?t e CgHiO-C9H14N03 is prepared by heating a mixtureof ecgonine (1 mol.) and half its weight of water with cinnamicanhydride (1 mol.) on a water-bath for an hour grinding the productwith 6-@ times its weight of water filtering from unattacked cinnamic:anh?dride and from ciunamic acid extracting the filtrate wit11 ether t284. ABSTRACTS OF CHEMICAL PAPERS.remove all cinnamic acid and finally concentrating to the crystallisingpoint. I t crystallises in beautiful vitreous spenr-like anhydrousneedles melts at 216" with decomposition is readily soluble in alcohol,and is precipitated from the alcoholic solution by ether.When boiledwith hydrochloric acid i t is readily converted into cinnamic acid andecgonine and on treatment with dilute potassium permangarlatesolution it is at once oxidised an odour of benzaldehyde being pro-duced a t the pame time. The azwochZoride C9H,0*CgH,4N03,HAuCI~,is anhydrous.Cinnamylcocuine CgH,0*CgH,,MeN03 is obtained when a concen-trated solution of cinnnmylecgonine in methyl alcohol is treated withhydrogen chloride and allowed to remain in the cold for 24 hours in aclosed vessel.It separates from a mixture of benzene and light petrcT-leum in beautiful crystals with vitreous lustre showing many faces,melts a t 121" and i u insoluble i n water but soluble in alcohol ether,acetone chloroform and benzene. The hi/droch7oride crystallises incolourless needles and the platinochloride. (C,gH,,N04),,H,PtCl crys-tnllises in microscopic needles melting a t 217". w. P. w.Imperialine. By I(. FRAGNER (Ber. 21 384-3287) .-1/npericd-ine C3aHG0B504 occur5 in the bulbs of F?'ittiZiw;cz imperialis and canhe obtained i n the pure state as follows:-The crushed bulbs arerubbed up with lime the mixture dried a t loo" and extracted with hotchloroform. The extract is shaken with water acidified with tartaricacid tho alkaloid precipitated from the concentrated aqueous solutioiiwith sodium carbonate washed and recrystallised from alcohol.TIieyield is 0.08-0.12 per cent. I t crystallises in shott colourlessueedles turns yellow when heated a t 240' brown a t 248" and meltsa t 2.54". It is very readily soluble in chloroform riioderately in hotalcohol more sparingly in ether benzene light petrolrlum and amylalcohol aud very sparingly in water; the solutions have a bittertaste and the specific rohtory power in chloroform solution is [a]= =- 35.4". The hydrochZorir?e C,,H,,NO4,HCI separates froni alcoholichydrochloric acid in large crystals and i s readily soluble in waterand alcohol. A yellowish- red p Zatin och Zoride ( C3,H,,N04) 2 H2P t C1 6rand a yellow aurochloridp C35H60N04,HAuC14 are precipitated in oilydrops when ether is added to a n alcoholic solution of the hydrochloriueand platinic or auric chloride ; after having been washed with ether,both salts separate fi*orn hot dilute hydrochloric acid in a crystallinecondition.The sulphate is very hygroscopic and was not obtaiiied ina crystalline condition ; the oxalafe crystallises only from very con-centrated solutions. Nost of the usual reagents for alkalo'ids produceprecipitates in solutions of the salts. The free base turns pale yellowwhen treated with sulphuric acid and when previously mixed withsuqar it first becomes yellowisli-green then pnle-green flesh colour,cl erry-red and alter a long time dark violet. Frohde's reagentcolours it greeuish-Fellow and with Mandelixi's reagent it gives anolive-greeii coloration which passe's through reddish-brown andbecomes dark brown. When mixed with potassium nitrate orpotassium chlorate and then moistened with aulphuric acid i t turns0 mge-yellow ; if however the mixture is previously warmed it t u r n ORGANIC CHENISTRY. 283dark reddish-yellow. The solution in hydrochloric acid fluoresces,becomes brownish-green when warmed and turns brownish-red whenthe heating is continued for a long time.Bg 3'. HOPPE-SEYLER (Zed. physiol. Chew .,13 66-121).-0~ the death of plants or parts of plants substancesof a brown coloiir are formed which are called hunious substances.Wood however often remains white for years. I n dry air or a t ahigh tempeiaturz plants can be dried without browning. Thebt owning of the surface of a cut apple may be taken as a very rapidexample of the process. Bacteria do not seem to be concerned in thischange. This brown coloration does not occur to any extent in deadariinial tissues. It is not however due to the chlorophyll of plants,as it occurs equally quickly in plants which contain no ohlorophy11.The almost universal distribution of tannic acid and carboliydrates,and especially of cellulose suggests that these may be sources of theliumous substance o r i t may come from the hydrocyanic acid phenol,m d nitrogenous compounds of plant tissues.Pure cellulose when mixed with mud containing micro-organisms,ferments and yields carbonic anhydride and methane in the absence ofuxygm but no humous substance is formed (Abstr. 1886 923) ; inthe presence of oxygen the cellulose (filter-paper) still 1 emainhquite white; all sorts of mud being used in the experiments. Byheating with water a t 188-200" or with caustic alkalis humomsubstances are formed. Water in glass tubes produced a brownresidue and the liquid was found to contain formic acid catechol,arid pi otocatecliuic acid ; when platinum tubes were employed therewas a brown residue but the other products obtained in glass tubeswere absent as they are due to the decomposition of the humons sub-stance produced by a small quantity of alkali dissolved out from theglass at the high temperature to which the tubes were subjected.Other experiments were performed with strong alkalis and the result-ing gases as well as the residue were annlysed.The fermentation of wood-gum was found to be similar to that ofcellulose ; and it is supposed that the lignic acid may be in. t rurnentalin the formation of humous substances in turf. peat &c.Tannin red obtained from certain plants by extracting with water,and the phlobaphen of Stahelin and Hofstetter an amorphous brownsubstance are apparently derivatives of tannic acid and may beincluded under burnous substances. The preparation and propertiesof a large number of these substances are described. They areformed by the action of alkalis on various carbohydrates (dextrose,lactose cane-sugar glycuronic acid &c.) ; from various aromatic:substmces ; and those obtained from various vegetabie sources arealso described. They are amorphous differing in percentage com-position mostly containing nothing b u t carbon hydrogen and oxygen.A few contain nitrogen like those described by Udr6nszky in urine(Abstr. 1887 1133 ; 1888 180). A derivative of humous substancesc.alled huuiic acid is described and various names are given to sariousother members of the group.The originai paper must be consulted for details concerning theirI?. S. K.Humous Substances286 ABSTRACTS OF CliEJllChL PAPERS.preparation and analysis ; the following summary will however,indicate the methods adopted in their separation.Hunious substances fall into three gi'oups the first includes thosewhich are boluble neither in caustic alkalis nor in aIcohol but uiiitewith alkalh forming a slimy mass. This group includes the hnminand ulmin of Mulder. The second group consistc; of those which arecompletely soluble in alkalis aud precipitahle from such solutions hyacids ; tl\e precipitate formed is voluminous and jelly-like and isillsoluble in alcohol. A part of the tannin reds arid of humic andulmic acids be1or;g to this group. The substances in the third groupresemble hhose in the second with regard to their solubility in alkalis ;but the precipitate produced by acid is easily soluble in alcohol.Phlobaphen a part of humic and ulmic acids and the brown aridsincluded under the name hymntomelanic acids (which are formed fromthe members of the first two groups by heating with caustic alkalis)belong to the third group.Cholamide and Hippuramide. Bp G. PELLIZZARI (Chem. Cenfr.,1888 1350-1352 from L'Orosi 11 233-235) .-By heating glyco-cholic acid €or one day at 16O-1iO0 with alcoholic ammonia underpressure a residue was obtained on evaporating the liquid which,when recrystallised from aqueous alcolrol appeared as I G I I ~ silkj,very deliquescent needles. 'these are insoluble in acids and alkalis,little soluble in boiling water readily soluble in alcohol and ether andmelt about 125". The composition corresponds with that of Hufner'scholamidr. C,,H,,O,.CONH,. Isoglycocholic acid reacted with ammo-nia i n a similar way.Hippuric acid when heated with alcoholic ammonia for four hoursat 210-210" reacted with formation of hippuramide mt~lting a t 183".Ry heating a t 260° a further change took place ethyl benzoate andbenzamide being formed.W. D. H.J. W. L.Chinethonic Acid. By V. LEIIMANN (Zeit. yiiy.&Z. Chem. 13,181-186) .-Pheneto'il leaves the body partly in union with glycuro-nic acid i n the urine. After administration of this substance a n acidoccurs i n the uririe called cbinethonic acid (Kossel Abstr. 1881 631).I t may be prepared as follows :- The urine is concentrated acidifiedw i t h sulphuric acid and extracted with ethyl acetate; this is sepa-rated treated with excess of barium carbonate and distilled off; theresidue boiled with water filtered hot and the filtrate evaporated toa small bulk. I n a few days the barium double salt crystxllises out ;this is recrystallised dissolved in hot water and neutral potassiumsulphate added as long as a precipitate of barium sulphste forms;this is filtered off the filtrate evaporated to dryness and the residueextrscted with boiling alcohol ; the potassium salt goes into solution,a n d on cooling crystallises out ; the potassium salts of the etherealhydrogen sulphates remain in solution. Some of these latter areformed from the phcnetoil administered. The relation of total sul-phuric anhydride t o that combined as et.bereal hydrogen sulphateswas in a dog hefore the experiment = 8-92; r,fter the ac'ministra-tion of 12 grams cf phenetoil it fell to 2.74PHTSIOLOGLCA I d CHEJIISTI1T. 287The potassium salt C14H,,0,K + H20 of the new acid occurs inmcmoclinic crystals and the silver salt has the formula C14Hli08Ag +H,O. The free acid C14HIBOR obtained hy treating the potassium saltwith sulpliuric acid is crystalline and melts a t 146". When treatedwith dilute sulphuric acid an oily substance which subsequentlycrysta liaed was obtained ; it had the formula C,H,,,O that is coil-tained one atom of oxygen more tlrnn plienetoll. The questionarises whether the oxygen is united to the benzeite nucleus or isderived from oxidation of the ethyl-group. It was found that ondecomposing chinetlionic acid with hydrogen iodide quinol is formed,xnc-l with oxidising agents quinone is formed easily. 'lhe constitntinuof chinethonic acid is therefore OE~.C~HI,.C~H&. M7. D. H

ISSN:0368-1769    

DOI:10.1039/CA8895600226

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

PHTSIOLOGLCA I d CHEJIISTI1T. Ph ys i 010 g i c a1 C h e m i s t ry. 287 Digestion in Hydra. By M. GREENWOOD ( J . I”hygsiol., 9, 317- 344).-The paper includes many points of histological interest ; those which relate to digestion ai e suiumarised thus :-(1.) Ttie i1,gestion of solids is performed by slow advance over the prey of lip- like projections of the hydra’s suhstance. Ent omostraca, Nais, beetle larvae, and raw meat prove the most acceptable food ; iiinutritious matter does not act as a stimulus to digestion. (2.) The digestion of enclosed food takes place entiielg outside the endoderm cells which line the enteric cavity, and among these may be distinguished : (u) pyriform cells destitute of large vacuoles, holding secretui-y spherules during hunger, and these empty during digestive activity ; ( b ) ciliated vacuolate c:Blls often pigmented : the water of the diges- tive fluid is probably derived from t,hese vacuoles. (13.) The pigment, occurs as brown or black grains ; its baris is prote’id in nature.The pigment resists solution in most chemical reagents ; it dissolves slowly in nitric acid. It may be expelled into the alimentmy cavity during digestion. (4.) A reserve substance of proteid nature accu- mulates during digestive acts in the basal part of the vacuolated c ~ l l s , and eventually takes the form of’ spheres ; the excretory pigmerit probably takes its rise i u some re%idue from this ill)sol-l)ed proteid ; it IS also possible that fat is similarly formed. ( 5 . ) The medium ill which digestive activity goes on is probaldy not acid.These observations relate to H y d m fuscu. In H. vyridis, which coiitains chlorophyll (the chloroplastids of Rap Lsnkester) the mode of nutrition seems to be different; gland cells do not form a con- spicuous feature in its endoderm, and apparently digestive secretion is less active. W. D. H. Influence of the Consumption of Water on the Alimentation of Animals. By W. HENNEBERG ( B i e d . C‘entr., 1888, 813--Sl8).- ‘I’he author controverts the statements of Maircker and others who288 ABSTHAGTS OF GHEJIIJAL PAPERS. 1 .. .. 2.. .. .. 3 . . .. .. 4 . . .. 5 . . .. .. 6 . . . . . . 7 . . .. .. stttte that about 40 per cent. of the water consumed by animals re- appears in the form of vapour. Makinq use of the statistics of seveial experiments, it is shown that the water which appears as urine and tts dung forms, in sheep 61 t o 92 per cent.of the whole water consumed, and in oxen, 83 to 93 per cent.; consequentlyMarcker’s figure for mporised water, namely, 40 per cent., is much too high ; it should be for sheep on the average 25.8, for cattle 12.6. E. W. P. - - ~ - - C.C. 1746 1317 1246 1720 8x0 987 I 1080 Coagulation of the Blood. By L. C. WOOLDRIDGE (PTOC. ROY. Soc., 44, 282--284).-An answer to criticisms by Halliburton (Abstr., 1888, 974). 3.399 3.255 3.311 3’368 3.494 3-323 3.458 Influence of Ethyl-alcohol on Metabolism in Man. By H. KELLER (Zeit. physiol. Cheni., 13, 128--134).-The experimeut was carried out cn the author’s person, and lasted a week; the daily nourishment consisted of 500 grams of meat, 500 grams of bread, 100 grams of butter, 1500 C.C.of spring water, and 2 grams of common salt. On the 4th day, 150 C.C. of pure 96 per cent. ethyl- alcohol was mixed with the water. The urine was carefully collected, and in it the chlorides, sulphates, phosphates, and total nitrogen mere estimated. The following table gives the results obtained :- 20.9 22.0 22‘2 20’8 23-3 23.1 23.1 I I I I n the Urine. I nay. Volume BodJ- I of urine. I weight. 1 c1. gram. 62800 62250 62250 61400 61850 61905 -- -- 3.919 1-848 I ‘459 1.930 1.416 1.200 1.441 2.956 3’280 3.288 3 *348 2 891 2 *696 3.112 - Remarks. SO3. 1 N. I 150 C.C. alcohol. From this the following conclusions are drawn :- 1. Alcohol acts as a diuretic. This is what previous authors have observed (K.B. Lehmann, Munch.ner med. Wochensch., 1886, No. 51, 1887, No. 23). 2. There is a slight lessening of the nitrogenous oiitput on the day on which alcohol was taken. This is perhaps explicable from the destructive action of alcohol on digestive and absorption processes. T’hc following days showed a slight increase of the total nitrogen i n the urine. 3. The increase of phosphoric acid is too slight, and the length of the experiment too short to draw any certain conclusions concerning it. 4. The increase of chlorine is also very slight, and perhaps depends only on the diuretic action of the alcohol. W. D. H.PHYSIOLOGICAL CHEMISTRY. 289 Metabolism of Acetanilide in the Human Body. By K. A. H. M~RNER (Zeit. physiol. Chem., 13, 12--25).-The urine of patients taking this drug (antifebrin) was, as Muller first observed (Deutsch.mpd. Wochemch., 13.27), red, from excess of urobilin. The amount of ethereal hydrogen sulphates in the urine is increased, and the urine reduces alkaline solutions of cupric oxide and is strongly lsevorota- tory. The urine was evaporated to a syrup, extracted with 90-93 per cent. alcohol ; to the extract, half its volume of ether was added, and then a warm concentrated alcoholic solution of oxalic acid, The potassium ethyl oxalate and the ethereal hydrogen sulphate form a compound which can be crystallised and purified by recrjstallisation. Three preparations were made and analysed, and the numbers ob- tained correspond with the formula NHAc-CGH1.SO4K,C2O4KEt. On taking antifebrin, then, a part of it is oxidised to form parac-et.nmidopbenol, and is excreted as an ethereal sulphate ; whether other similar acids are formed it, is not a t present possible to say. The strongly laevorotatory reducing substance is probably a deriva- tire of glycuronic acid. W. D. H. Metabolism of Furfuraldehyde in Fowls. By M. JAFFB and R. COHN (Ber., 21, 3461-3465).-When furfuraldehyde is given to dogs and rabbits, a glycocine compound of furfurscrylic acid is excreted in small quantity in the urine (Abstr., 1887, 1032). It is possible, however, that this compound is the chief transformation- product, of furfuraldehyde, and that the greater part is further oxidised in the organism, a small proportion only escaping oxidation and appearing in the urine, since experiment shows that rabI)its fed with furfuracrylic acid in quantities amounting to 6 grams, excrete barely 0.5 gram of the glycocine compound of the acid, and about 2 grams of pyrompkuric acid, no less than 60-70 per cent.of the furfuracrylic acid undergoing decomposition in the organisrn. Furfuraldehyde in aqueous solution was given to fowls, partially by the mouth and partially by subcutaneous injection, in quantities of 0-5-1 gram per day. The action was very marked, and resulted in death in the majority of cases after a few days. Pyromucic acid and pyromucornithuric acid were present in the excreta, but no trace of furfuracrylic acid or its derivatives could be detected. Pyrornucornithuric acid, C15H16NZ06, crjst allises in very small, colourless needles or shmt, thin prisms, melts a t 186", carbonises when strongly heated with the evolution of a pungent odour resembling that of acraldehyde, and is sparingly soluble in ether, but readily soluble in alcohol, acetic acid and hot water.When heated with baryta-water, i t hydrolyses quantitatively into pyromucic acid and ornithine (A'ustr., By N. JUVALTA (Zeit. physiol. Chenz., 13, 26--31).-A dog was fed on meat mixed with a known weight, of neutral sodium phthalate ; before and after the experimerit it was fed on bone, so that the feces during the time of experiment could easily be distinguished from those before and after. 1878, 584). w. P. w. Is the Benzene-nucleus destroyed in' the Body? The urine and the feces were examined.290 A RSTRACTS OF CHEMICAL PAPERS. The fseces contained 29.55 per cent., and the urine 12.95 of the salt given; 57.5 per cent.was therefore unaccounted f o r ; in a second experiment 68.76 per cent. was lost. There was no increase in ethereal hydrogen sulphates in the urine, and gl~-curonic acid com- pounds were also absent. Hence, not being able to account for the loss, the author concludes that the substance had been destroyed, and therefore that the benzene-nucleus can be destroyed by the animal boay. W. D. H. By bl. ~rARINd-zUCO (Gazzetta, 18, 199-207).-1n 188;3, Foa and Pallacani nroved the poisonous nature of the extract of the suprarenal capsules, but did not succeed in isolating the compound which gave this property to the extract. The author commenced his researches by confirn:ing this statement as to the poisonous nature of the extract, and found that a few C.C.of it waq sufficient to cause death in a large rabbit when injected hypodermically. If, however, the solution was rendered slightly acid or alkaline, it no longer had any toxic power. After various fruitless attempts to isolate the poisonous substance, the following method was adopted : Some 500 suprnrena1 capsules of the ox were ground u p with about five times their bulk of watfer, and the mixture heated on the water-bath for some four to five hours. When cold, the liquid portion was expressed, and the residue again treated four times successively in the same manner. The extracts were united, and their proteid matters precipitated by adding to the liquid its own volume of alcohol and half its volume of ether.After sepa- rating the precipitate, the alco!iol aud ether were removed by distilla- tion, and acetate of lead added to the filtered solution. The abundant brown precipitate thus formed was removed, and the clear solutioii carefully precipitated with basic acetate of lead, which then threw down a dirty white precipitate consisting of lead ohlo~-icie and organic lcild salfs. The clear solution, after treatment with magnesia or, better, with argentic oxide and filtration, gave precipitates with all the general reagcnts for alkaloids, such as auric chloride, potassium niercuro-iodide, &c. The aurochloride WRS prepared and analysrd, when it was found to have the composition of neuriiie anrochloride, C,HI,ON,HAuCI4, with which it agreed in phjsical properties and in ielding trimrthylamine when decomposed.The platinochloride, (C,H,,ON),,H,P tC1, was also prepared and analysed. The lead precipitate was next examined ; after beinq well washed, it was suspended in water, decomposed by hydrogen sulphide, filtered, and the filtrate treated with baryta-water, which threw down a pre- cipitate of barium phosphate. The excess of baryts was then removed from the solution by means of carbonic anhydride, and the clear liquid precipitated by basic acetate of lead, which t h e w down lead chloride mixed with lead salts of organic phosphatic acids. It was found to be impossible to separate these acids, but the presence of gly- cerophosphoric acid in the mixture was proved. Now, although the presence of neurine in the suprarenal capsules will not of itself account for the powerfnlly toxic action of the Chemical Examination of the Suprarenal Capsules.PHYSlOLOOIChL CHEJIISTRY.291 pT;ti*aCt, it was found tliat if the mixture of organic phosphatic acids iiientioned above is saturated with neurine, a liquid is obtained which, even when very dilute, has all the poisonous properties of the extract itself. Experiments were also made with neurine orthophosphate and glycerophosphate prepared synthetically. It was found that the phosphate is far more poisonous than the hydrochloride ; whilst the glycerophosphate is intensely poisonous, 0.1 of a milligram being sufficient to kill a frog. Tho poisonous principle being a compound of neurine with ail organic phosphatic acid, i t is easy to understand how the action of‘ acids or alkalis by destroying t h i s combination renders the extract innocuous.C. E. G. Sugar and Allantoin in Accitic Fluid. By R. XOSCATELL~ (Zeit. physiol. Chenz., 13, 20L-’204).-In a small number of cases of cirrhosis of the liver, sugar occurs in the urine (Cobrat, L y o n . M,4d., 1875, No. 15: Lkpine, Gaz. m i d . de Paris, 1876, 126; Quincke, Berlin. klin. Tochensch., ”1876, No. 38). In the present case of liver cirrhosis, the urine was scanty, and gave no sugai’ reaction. The ascitic fluid, however, contained 0.15 per cent. of sugar. Coii- firmatory test,s, including the fermentation test, were also successful. A crystalline substance was also separated in small quantities from the same pathological fluid, which chemically and crystallographically was identified as allantoin.W. D. H. This was estimated by Fehhig’s method. Antiseptic Action of Bile Acids. By P. LIMBOURG (Zeit. physiol. C‘hem,., 13, 196-201).-Bile and the bile acids have long been sup- posed to have an antiseptic action in the alimentary canal. The present research is directed to determining more accurately whether this is the case, by means of qnnntitative ~ ~ n a l j s i s . Hirschler (Abstr., 1887, 310) has shown that phosphomol~bdic acid Iirec*ipitntes some of the products of digestion (peptone, propep- tone, $c.), while it does not precipitate certain others (amido-acids) ; these may be respectively termed Groups 1 and 2. Artiticial pancreatic juice was mixed with “ Witte’s peptone,” and infected with bacteria from dog’s faeces.Digestion was then allowed to take place, a solution of sodium cholate being added to a certain number of the specimens. At the end of a certain interval, the following determinations were made :-(1) Total nitrogen ; (2) nitrogen of substances belong to group 2 ; and (3) ammonia. The following tables (p. 292) give the results in percentages in two series of experiments. The quantity of amido-acids and of ammonia in the specimens where the bile salt was present is thus smaller than in those where the salt W;IS absent. I n other words, these experiments performed outside the body fully confirm what one has been accustomed to believe occurs in the alimentary canal, namely, that bile prevents o r w. n. H. hiriders changes of a putrefactive nature there.Time.1 Nitrogen in Group 1. Nitrogen in Group 2. I I With addition of 1 per cent. sodium cbolate. With sodium Without. cholate, Without. 1 per cent. Beginning of Expt. 1 . . . 79 -8 25 *5 After 24 hours APter 48 hours , , . , . . . . 47 -8 33 -7 . . . . . . . . 20.2 46 *7 62 *2 55.6 1 70.5 I I With addition of 0 *5 per cent. 0.25 per cent. sodium sodiuni cholate. cholate. With addition of With- With- out. 0.5 per cent. 0.25 per cent. out. sodium sodium cholate. cholate. Pll'itrogen in Ammonia. With addition of 0.5 per cent. 0.25 per cent. so lium sodium cholate. cbolate. Ei a 2 2 v. With- out. 0.16 I 0.26 1 1-10 Beginning of Expt. 2 . . . After 24 hours.. . . . . . . . 59 *3 40.7 50.7 1 44-6 I,j 49.1 1 55.1 1 66.0PHY SIOLOGICRL CHEMISTRY. 293 Carbohydrates in Normal Urine.By N. WEDENSKI (Zeit. physioZ. Chenz., 13, 122-l27).--Brucke, Bence-Jones, Pavy, Huiziiiga, Abeles, and others have affirmed the constant presence of small quantities of dextrose in normal urine ; while other<-See,aen, Kiilz, Moscatelli, &c., have denied it. The more recent work of UdrAiiszk-y (Abstr., 1888, 180, 863) shows that Carbohydrates are normally present i n small quantities, and Landwehr (Cecntr. Med. Wiss., 1885, 369) prepared animal gum from normal human urine. I n the present research, the urine was shaken with excess of benzoic chloride ; insoluble benzoyl compounds of the carbohydrates are thus formed and crystallise out. Estimation of the carbon and hydrogen in these gave a result intermediate between those obtained by control experiments with glycogen on the one hand and dextrose on the other.This led to the conclusion that probably a mixture of two carbohydrates is present ; this was corifirmed by treatment with sodium hydroxide ; part went into solution and the remainder was undissolved. The insoluble residue was soluble in alcohol and gave the tests for gi-ape-sugav; the soluble part was found to consist of a substance having the reactions of animal gum. W. D. H. Glycogen in Diabetic Urine. By W. LELTBF, (Chem. Centr., 1888, 1278-1279, from V~TC~OW'S Archia, 113,392-393). -In the precipitate obtained by the addition of alcohol to the urine of healthy persons and of those suffering from diabetes insipidus, the author could not find any carbohydrate or glycogen ; in the urine of persons suffering from diabetes mellitus, however, a carbohydrate in varying quantity was detecked which proved to be glycogen. J.W. L. Physiological Action of Paraxanthine. By G. SALOMON (Zeit. physiol. Chem., 13, 187--195).-Recent re+earches on the physiolo- gical action of caffe'ine and allied substances have suggested the necessity of working out the action of paraxanthine which is an isomeride of theobromine. The experiments were made mostly on frogs ; the lethal dose for these animals was found to be a weight equal to 0 15 to 0.2 per 1000 of body-weight when administered subcutaneously. Given by the mouth, larger doses are necessary to produce botli physiological effects and death ; this is even more the case when paraxanthine is given in the solid state-for the crystals are very insoluble.Like xantliine, ttieobromine, and caff'e'ine, this drug has an action both on the central iiervous system and on the muscles ; the action on the muscles occurs when the drug is applied locally t o them. Their excitability is lessened, and ultimately disappears altogether. The muscles become JtaFd, but complete rigor of' the muscles during life is never seen. The action on the central nervous system is seen in abolition of reflexes. The action of all these drugs is thus very similar ; all produce the same creeping movements ; then the disappearance of all spontaneous muscular activity and complete abolition of reflexes without a pre- liminary increase ; the heart remains intact. Respiration is similarly, affected by both theobromine and paraxanthine ; it is first hurried, VOL.LVI. X294 ABSTRACTS OF CHEMICAL PAPERS. then slowed, and after death the lungs are found to be fully dis- tended. Caffe’ine prodnces a rapid rigor of the muscles after death; this is not markedly the case with paraxanthine. A few experiments on warm-blooded animals (mice) gave the fol- lowing results : paresis of the hinder extremities and increase of reflex activity, producing tetanns ; peculiar creeping, dragging move- ments are thus produced. The dose of the poison must be twice to four times as large as for frogs. W. D. H.PHTSIOLOGLCA I d CHEJIISTI1T.Ph ys i 010 g i c a1 C h e m i s t ry.287Digestion in Hydra. By M. GREENWOOD ( J . I”hygsiol., 9, 317-344).-The paper includes many points of histological interest ;those which relate to digestion ai e suiumarised thus :-(1.) Ttiei1,gestion of solids is performed by slow advance over the prey of lip-like projections of the hydra’s suhstance.Ent omostraca, Nais, beetlelarvae, and raw meat prove the most acceptable food ; iiinutritiousmatter does not act as a stimulus to digestion. (2.) The digestionof enclosed food takes place entiielg outside the endoderm cellswhich line the enteric cavity, and among these may be distinguished :(u) pyriform cells destitute of large vacuoles, holding secretui-yspherules during hunger, and these empty during digestive activity ;( b ) ciliated vacuolate c:Blls often pigmented : the water of the diges-tive fluid is probably derived from t,hese vacuoles. (13.) The pigment,occurs as brown or black grains ; its baris is prote’id in nature.Thepigment resists solution in most chemical reagents ; it dissolvesslowly in nitric acid. It may be expelled into the alimentmy cavityduring digestion. (4.) A reserve substance of proteid nature accu-mulates during digestive acts in the basal part of the vacuolated c ~ l l s ,and eventually takes the form of’ spheres ; the excretory pigmeritprobably takes its rise i u some re%idue from this ill)sol-l)ed proteid ; itIS also possible that fat is similarly formed. ( 5 . ) The medium illwhich digestive activity goes on is probaldy not acid.These observations relate to H y d m fuscu. In H. vyridis, whichcoiitains chlorophyll (the chloroplastids of Rap Lsnkester) the modeof nutrition seems to be different; gland cells do not form a con-spicuous feature in its endoderm, and apparently digestive secretionis less active.W. D. H.Influence of the Consumption of Water on the Alimentationof Animals. By W. HENNEBERG ( B i e d . C‘entr., 1888, 813--Sl8).-‘I’he author controverts the statements of Maircker and others wh288 ABSTHAGTS OF GHEJIIJAL PAPERS.1 .. ..2.. .. ..3 . . .. ..4 . . ..5 . . .. ..6 . . . . . .7 . . .. ..stttte that about 40 per cent. of the water consumed by animals re-appears in the form of vapour. Makinq use of the statistics of seveialexperiments, it is shown that the water which appears as urine and ttsdung forms, in sheep 61 t o 92 per cent. of the whole water consumed,and in oxen, 83 to 93 per cent.; consequentlyMarcker’s figure formporised water, namely, 40 per cent., is much too high ; it should befor sheep on the average 25.8, for cattle 12.6.E. W. P.- - ~ - -C.C.17461317124617208x0987 I 1080Coagulation of the Blood. By L. C. WOOLDRIDGE (PTOC. ROY.Soc., 44, 282--284).-An answer to criticisms by Halliburton (Abstr.,1888, 974).3.3993.2553.3113’3683.4943-3233.458Influence of Ethyl-alcohol on Metabolism in Man. By H.KELLER (Zeit. physiol. Cheni., 13, 128--134).-The experimeut wascarried out cn the author’s person, and lasted a week; the dailynourishment consisted of 500 grams of meat, 500 grams of bread,100 grams of butter, 1500 C.C. of spring water, and 2 grams ofcommon salt.On the 4th day, 150 C.C. of pure 96 per cent. ethyl-alcohol was mixed with the water.The urine was carefully collected, and in it the chlorides, sulphates,phosphates, and total nitrogen mere estimated. The following tablegives the results obtained :-20.922.022‘220’823-323.123.1I I I I n the Urine. I nay. Volume BodJ- I of urine. I weight. 1 c1.gram.628006225062250614006185061905----3.9191-848I ‘4591.9301.4161.2001.4412.9563’2803.2883 *3482 8912 *6963.112 -Remarks.SO3. 1 N. I150 C.C. alcohol.From this the following conclusions are drawn :-1. Alcohol acts as a diuretic. This is what previous authors haveobserved (K. B. Lehmann, Munch.ner med. Wochensch., 1886, No. 51,1887, No.23).2. There is a slight lessening of the nitrogenous oiitput on the dayon which alcohol was taken. This is perhaps explicable from thedestructive action of alcohol on digestive and absorption processes.T’hc following days showed a slight increase of the total nitrogen i nthe urine.3. The increase of phosphoric acid is too slight, and the length ofthe experiment too short to draw any certain conclusions concerningit.4. The increase of chlorine is also very slight, and perhaps dependsonly on the diuretic action of the alcohol. W. D. HPHYSIOLOGICAL CHEMISTRY. 289Metabolism of Acetanilide in the Human Body. By K. A.H. M~RNER (Zeit. physiol. Chem., 13, 12--25).-The urine of patientstaking this drug (antifebrin) was, as Muller first observed (Deutsch.mpd.Wochemch., 13.27), red, from excess of urobilin. The amount ofethereal hydrogen sulphates in the urine is increased, and the urinereduces alkaline solutions of cupric oxide and is strongly lsevorota-tory. The urine was evaporated to a syrup, extracted with 90-93per cent. alcohol ; to the extract, half its volume of ether was added,and then a warm concentrated alcoholic solution of oxalic acid, Thepotassium ethyl oxalate and the ethereal hydrogen sulphate form acompound which can be crystallised and purified by recrjstallisation.Three preparations were made and analysed, and the numbers ob-tained correspond with the formula NHAc-CGH1.SO4K,C2O4KEt.On taking antifebrin, then, a part of it is oxidised to form parac-et.nmidopbenol, and is excreted as an ethereal sulphate ; whether othersimilar acids are formed it, is not a t present possible to say.The strongly laevorotatory reducing substance is probably a deriva-tire of glycuronic acid.W. D. H.Metabolism of Furfuraldehyde in Fowls. By M. JAFFB andR. COHN (Ber., 21, 3461-3465).-When furfuraldehyde is given todogs and rabbits, a glycocine compound of furfurscrylic acid isexcreted in small quantity in the urine (Abstr., 1887, 1032). It ispossible, however, that this compound is the chief transformation-product, of furfuraldehyde, and that the greater part is furtheroxidised in the organism, a small proportion only escaping oxidationand appearing in the urine, since experiment shows that rabI)its fedwith furfuracrylic acid in quantities amounting to 6 grams, excretebarely 0.5 gram of the glycocine compound of the acid, and about2 grams of pyrompkuric acid, no less than 60-70 per cent.of thefurfuracrylic acid undergoing decomposition in the organisrn.Furfuraldehyde in aqueous solution was given to fowls, partiallyby the mouth and partially by subcutaneous injection, in quantitiesof 0-5-1 gram per day. The action was very marked, and resultedin death in the majority of cases after a few days. Pyromucic acidand pyromucornithuric acid were present in the excreta, but no traceof furfuracrylic acid or its derivatives could be detected.Pyrornucornithuric acid, C15H16NZ06, crjst allises in very small,colourless needles or shmt, thin prisms, melts a t 186", carbonises whenstrongly heated with the evolution of a pungent odour resembling thatof acraldehyde, and is sparingly soluble in ether, but readily soluble inalcohol, acetic acid and hot water.When heated with baryta-water,i t hydrolyses quantitatively into pyromucic acid and ornithine (A'ustr.,By N.JUVALTA (Zeit. physiol. Chenz., 13, 26--31).-A dog was fed on meatmixed with a known weight, of neutral sodium phthalate ; before andafter the experimerit it was fed on bone, so that the feces during thetime of experiment could easily be distinguished from those beforeand after.1878, 584). w. P. w.Is the Benzene-nucleus destroyed in' the Body?The urine and the feces were examined290 A RSTRACTS OF CHEMICAL PAPERS.The fseces contained 29.55 per cent., and the urine 12.95 of the saltgiven; 57.5 per cent.was therefore unaccounted f o r ; in a secondexperiment 68.76 per cent. was lost. There was no increase inethereal hydrogen sulphates in the urine, and gl~-curonic acid com-pounds were also absent. Hence, not being able to account for theloss, the author concludes that the substance had been destroyed,and therefore that the benzene-nucleus can be destroyed by the animalboay. W. D. H.By bl.~rARINd-zUCO (Gazzetta, 18, 199-207).-1n 188;3, Foa and Pallacaninroved the poisonous nature of the extract of the suprarenal capsules,but did not succeed in isolating the compound which gave thisproperty to the extract. The author commenced his researches byconfirn:ing this statement as to the poisonous nature of the extract,and found that a few C.C. of it waq sufficient to cause death in alarge rabbit when injected hypodermically. If, however, the solutionwas rendered slightly acid or alkaline, it no longer had any toxicpower.After various fruitless attempts to isolate the poisonous substance,the following method was adopted : Some 500 suprnrena1 capsules ofthe ox were ground u p with about five times their bulk of watfer, andthe mixture heated on the water-bath for some four to five hours.When cold, the liquid portion was expressed, and the residue againtreated four times successively in the same manner.The extracts wereunited, and their proteid matters precipitated by adding to the liquidits own volume of alcohol and half its volume of ether.After sepa-rating the precipitate, the alco!iol aud ether were removed by distilla-tion, and acetate of lead added to the filtered solution. The abundantbrown precipitate thus formed was removed, and the clear solutioiicarefully precipitated with basic acetate of lead, which then threwdown a dirty white precipitate consisting of lead ohlo~-icie and organiclcild salfs. The clear solution, after treatment with magnesia or,better, with argentic oxide and filtration, gave precipitates with allthe general reagcnts for alkaloids, such as auric chloride, potassiumniercuro-iodide, &c. The aurochloride WRS prepared and analysrd,when it was found to have the composition of neuriiie anrochloride,C,HI,ON,HAuCI4, with which it agreed in phjsical properties and inielding trimrthylamine when decomposed. The platinochloride,(C,H,,ON),,H,P tC1, was also prepared and analysed.The lead precipitate was next examined ; after beinq well washed,it was suspended in water, decomposed by hydrogen sulphide, filtered,and the filtrate treated with baryta-water, which threw down a pre-cipitate of barium phosphate. The excess of baryts was then removedfrom the solution by means of carbonic anhydride, and the clearliquid precipitated by basic acetate of lead, which t h e w down leadchloride mixed with lead salts of organic phosphatic acids. It wasfound to be impossible to separate these acids, but the presence of gly-cerophosphoric acid in the mixture was proved.Now, although the presence of neurine in the suprarenal capsuleswill not of itself account for the powerfnlly toxic action of theChemical Examination of the Suprarenal CapsulesPHYSlOLOOIChL CHEJIISTRY.291pT;ti*aCt, it was found tliat if the mixture of organic phosphatic acidsiiientioned above is saturated with neurine, a liquid is obtained which,even when very dilute, has all the poisonous properties of the extractitself. Experiments were also made with neurine orthophosphateand glycerophosphate prepared synthetically. It was found that thephosphate is far more poisonous than the hydrochloride ; whilst theglycerophosphate is intensely poisonous, 0.1 of a milligram beingsufficient to kill a frog.Tho poisonous principle being a compound of neurine with ailorganic phosphatic acid, i t is easy to understand how the action of‘acids or alkalis by destroying t h i s combination renders the extractinnocuous.C. E. G.Sugar and Allantoin in Accitic Fluid. By R. XOSCATELL~(Zeit. physiol. Chenz., 13, 20L-’204).-In a small number of cases ofcirrhosis of the liver, sugar occurs in the urine (Cobrat, L y o n . M,4d.,1875, No. 15: Lkpine, Gaz. m i d . de Paris, 1876, 126; Quincke,Berlin. klin. Tochensch., ”1876, No. 38).In the present case of liver cirrhosis, the urine was scanty, andgave no sugai’ reaction. The ascitic fluid, however, contained 0.15per cent. of sugar. Coii-firmatory test,s, including the fermentation test, were also successful.A crystalline substance was also separated in small quantities fromthe same pathological fluid, which chemically and crystallographicallywas identified as allantoin.W. D. H.This was estimated by Fehhig’s method.Antiseptic Action of Bile Acids. By P. LIMBOURG (Zeit. physiol.C‘hem,., 13, 196-201).-Bile and the bile acids have long been sup-posed to have an antiseptic action in the alimentary canal. Thepresent research is directed to determining more accurately whetherthis is the case, by means of qnnntitative ~ ~ n a l j s i s .Hirschler (Abstr., 1887, 310) has shown that phosphomol~bdicacid Iirec*ipitntes some of the products of digestion (peptone, propep-tone, $c.), while it does not precipitate certain others (amido-acids) ;these may be respectively termed Groups 1 and 2.Artiticial pancreatic juice was mixed with “ Witte’s peptone,” andinfected with bacteria from dog’s faeces.Digestion was then allowedto take place, a solution of sodium cholate being added to a certainnumber of the specimens.At the end of a certain interval, the following determinations weremade :-(1) Total nitrogen ; (2) nitrogen of substances belong togroup 2 ; and (3) ammonia. The following tables (p. 292) give theresults in percentages in two series of experiments.The quantity of amido-acids and of ammonia in the specimenswhere the bile salt was present is thus smaller than in those wherethe salt W;IS absent. I n other words, these experiments performedoutside the body fully confirm what one has been accustomed tobelieve occurs in the alimentary canal, namely, that bile prevents o r w.n. H. hiriders changes of a putrefactive nature thereTime.1 Nitrogen in Group 1. Nitrogen in GroupI IWith addition of 1 percent. sodiumcbolate.With sodiumWithout. cholate,1 per cent.Beginning of Expt. 1 . . . 79 -825 *5 After 24 hoursAPter 48 hours, , . , . . . . 47 -833 -7 . . . . . . . .20.246 *755.6I IWith addition of0 *5 per cent. 0.25 per cent.sodium sodiunicholate. cholate.With addition ofWith-out. 0.5 per cent. 0.25 per cent.sodium sodiumcholate. cholate.Beginning of Expt. 2 . . .After 24 hours.. . . . . . . .59 *3 40.750.7 1 44-6 I,j 49.1 1 55.PHY SIOLOGICRL CHEMISTRY. 293Carbohydrates in Normal Urine. By N. WEDENSKI (Zeit.physioZ. Chenz., 13, 122-l27).--Brucke, Bence-Jones, Pavy, Huiziiiga,Abeles, and others have affirmed the constant presence of smallquantities of dextrose in normal urine ; while other<-See,aen, Kiilz,Moscatelli, &c., have denied it.The more recent work of UdrAiiszk-y(Abstr., 1888, 180, 863) shows that Carbohydrates are normallypresent i n small quantities, and Landwehr (Cecntr. Med. Wiss., 1885,369) prepared animal gum from normal human urine.I n the present research, the urine was shaken with excess of benzoicchloride ; insoluble benzoyl compounds of the carbohydrates are thusformed and crystallise out. Estimation of the carbon and hydrogen inthese gave a result intermediate between those obtained by controlexperiments with glycogen on the one hand and dextrose on theother.This led to the conclusion that probably a mixture of twocarbohydrates is present ; this was corifirmed by treatment withsodium hydroxide ; part went into solution and the remainder wasundissolved. The insoluble residue was soluble in alcohol and gavethe tests for gi-ape-sugav; the soluble part was found to consist of asubstance having the reactions of animal gum. W. D. H.Glycogen in Diabetic Urine. By W. LELTBF, (Chem. Centr., 1888,1278-1279, from V~TC~OW'S Archia, 113,392-393). -In the precipitateobtained by the addition of alcohol to the urine of healthy personsand of those suffering from diabetes insipidus, the author could notfind any carbohydrate or glycogen ; in the urine of persons sufferingfrom diabetes mellitus, however, a carbohydrate in varying quantitywas detecked which proved to be glycogen.J. W. L.Physiological Action of Paraxanthine. By G. SALOMON (Zeit.physiol. Chem., 13, 187--195).-Recent re+earches on the physiolo-gical action of caffe'ine and allied substances have suggested thenecessity of working out the action of paraxanthine which is anisomeride of theobromine.The experiments were made mostly on frogs ; the lethal dose forthese animals was found to be a weight equal to 0 15 to 0.2 per 1000of body-weight when administered subcutaneously. Given by themouth, larger doses are necessary to produce botli physiological effectsand death ; this is even more the case when paraxanthine is given inthe solid state-for the crystals are very insoluble. Like xantliine,ttieobromine, and caff'e'ine, this drug has an action both on the centraliiervous system and on the muscles ; the action on the muscles occurswhen the drug is applied locally t o them. Their excitability islessened, and ultimately disappears altogether. The muscles becomeJtaFd, but complete rigor of' the muscles during life is never seen.The action on the central nervous system is seen in abolition ofreflexes.The action of all these drugs is thus very similar ; all produce thesame creeping movements ; then the disappearance of all spontaneousmuscular activity and complete abolition of reflexes without a pre-liminary increase ; the heart remains intact. Respiration is similarly,affected by both theobromine and paraxanthine ; it is first hurried,VOL. LVI. 294 ABSTRACTS OF CHEMICAL PAPERS.then slowed, and after death the lungs are found to be fully dis-tended.Caffe’ine prodnces a rapid rigor of the muscles after death; this isnot markedly the case with paraxanthine.A few experiments on warm-blooded animals (mice) gave the fol-lowing results : paresis of the hinder extremities and increase ofreflex activity, producing tetanns ; peculiar creeping, dragging move-ments are thus produced. The dose of the poison must be twice tofour times as large as for frogs. W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8895600287

出版商:RSC    

年代:1889

数据来源: RSC