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