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NINERALOQICXL CHXMISTRY.111.1-5768-264 .s513'031 '048-53125IT. v.------1 *53 1.5665.86 63.354 -84 4 *8311.45 12.491 '22 1 -31, 8.93 , 8.08m i n e r a1 og i c a 1 C h e m i s t ry.1 -4663-695 +0313'121-797.53The Brown Coal of Istria and Dalmatia. By LODIN (Ding!.polyt. J., 253,534).-The author gives an account of the strata of Istriaand Dalmatia belonging t o the eocene period, and of the geology oft h e deposits of brown coal. The coal in the Carpano Valley has thefollowing composition :-I, from the lower beds ; 11, from the lowerbeds altered by exposure t o atmospheric influences ; 111 and IV, fromthe upper beds ; and V, an average sample.----1-7059.584 '6012.361-187 33Water ..............Carbon ............Hydrogen ...........Oxygen ............Nitrogen............As11 ................Total ...............Yield of coke ........SUlPll llr ............8.84 1 14.96 8 *29 ---- --101 *46 101 -71 101 *5755.07 58.10 52-85VOL. XLVIII.7 -68 9.94 .--_____101 *01 101 *5658.07 56-012G ABSTRACTS OF CIIEMICAL PAPERS.Analysis of Cassiterite from King Co., N. Carolina. Ry J .D. BRUCE (Chem. A'ews, 50, 209).-The sample examined is of lightbrown colour, transparent, and of resinous lustre. Its sp. gr. is 6.956.For analysis, the powdered mineral was gently heatpd in a glass tubein a current of hydrogen, the residue digested with hydrochloric acid,the tin precipitated as stannous sulphide, and the filtrate treated inthe usual manner. The following are the results of analysis :-Loss on InsolubleSnOs.Fe20,. CaO. MgO. ignition. residue. Total.95.176 1.455 0.977 0.020 0.218 2.841 99.987The insoluble residue is probably chiefly silica.Apatite from Amelia Go., Virginia. By G. H. ROWAX (Chem.News, 50, 208) .-This specimen of apatite occurs imbedded in felsparin a vein of coarse granite, from which large sheets of mica and manyrare minerals are obtained. The crxstals are white and translucent,w i t h a shade of violet, and are cracked in various directions, laminatedparallel to face i ii, of vitreous lustre, and quite fragile. When lieated,it phosphoresces with a yellow light. The analy-tical data give the following :-D. A. L.Its sp. gr is 3.161.TotalCaO. Al,O,.Fe90,. P,O,. F. C1. ignition. residue. 0 for F)53.94 0.19 0-81 41.06 3.30 trace 081 0.63 99.33The insolubleI). A. L.Loss on Insoluble (less 1.39This corresponds with the formula Ca3P,08 + +CaP,.residue is probably due to adhering mica.Fluor-apatites. By A. DITTE (Compt. reitd., 99, 732-794).-Ametallic phosphate, e.g., calcium phosphate, is heated to redness for fiveor six hours in a platinum crucible with three times its weight of normalpotassium fluoride and a large proportion of potassium chloride.The prodnct is allowed t o cool and the residue treated with wat,er,when crystals of fluor-apatite, 3Ca3P20s,CaF,, remain undissolved.These crystals are quite free from chlorine, a result which agrees withGuntz's observation, that the heat of formation of calcium fluoride ishigher than that of the chloride.The amount of potassium fluoridepresent should not be more than 5 per cent. of the amount of potas-sium chloride, for if the alkaline fluoride is in excess the calciumphosphate is converted ivto fluoride. According to Guntz, the heatsof formation of barium and strontium flumides a t the ordinarytemperature are somewhat lower than the heats of formation of thecorresponding chlorides. It would appear, however, that a t hightemperaturcs this is not the case, for if barium or strontium phosphateis substituted for calcium phosphate in the foregoing reaction, thecorresponding fluor-apatite is obtained perfectly free from chlorine.Aiiother ruethod of preparation is as follows :-Calcium fluorideand phosphoric anhydride in suitable proportions are heated forseveral hours with a large proportion of potassium chloritle, and theproduct is extmcted with water af'ter cooling.In t h i s case thereaction can be ~epresei~led by one of the followu~g equations : IlIXERALOGICdL CHEMISTRY. 1276P,05 f 10CaF2 = 3Ca3P,0,,CaF2 + GPOF,24P,05 + 50CaF2 = 5(3Ca3P,08,CaF2) + 18PF,.The alkaline chloride simply plays the part of a solvent, from whichthe apatite crystallises. The phosphoric anhydride may be replacedby ammonium phosphate, care being taken t o avoid excess of thelatter. The corresponding barium, st'rontiurn, and magnesium com-pounds are obtained in A similar way.Calcium fluor-phosphate obtained in this way sometimes forms longprisms, the faces of which are striated parallel with the lateral edges,sometimes short prisms terminated by hexagonnl pyramids.Theya r e not altered by heat, but dissolve slowly in dilute acids in the cold,inore rapidly when heated. The barium, strontium, and magnesiumcompounds have t'he same form and properties. Iron fluor-phosphateforms transparent green needles wliich are difficiilt to separate fromthe fused tLmorphous matter which accompanies them.C. H. B.Origin and Formation of Masses of Calcium Phosphate inSedimentary Rocks. Their Relation to the Iran Ores andClays of the Siderolithic Horizon. By DIEULAFAIT (Compt. rend.,99, 813-816).-This paper is mainly a rbssumB of conclusions alreadypublished (Abstr., 1b84, 1272) respecting the origin of the phos-phorites found in limestone caverm.Comparative examinations of many specimens of iron orew and claysfrom the siderolithic horizon, and of the limestones with which theyare in contact,, leads to the conclusion that the origin of the foi-mer isintimately connected with the latter, and that tho iron ores and clayshave been formed by the destruction of the calcareous rocks, and arereally the residues left when the limestones were dissolved by perco-lating water from lakes and lagoons.The iron ores derive theirphosphorus from the original limestones, and are more highly chargedwith phosphorus the higher the proportion in which this elementexisted in the limestones and the peicolating water. c. H. B.Phosphatic Deposits of the South-ezst of France.By P.DE GASPARTN (Compt. rend., 99, 839--841).--The large proportion ofphosphoric acid in the fossils of the gault in the south-east of Francehas in all probability been derived from water containing phosphoricacid or phosphates i n solution. This water has percolated throughthe sandy matter composing the grits in which the fossils are enclosed,and the phosphoric acid has been retained by the calcium previouslyexistirig in the shells in the form of carbonate. This supposition issupported by the fact that in many localit'ies in the south-east ofFrance there are large phosphatic, chalky, and ferrnginous masses ofrock, the formation of which can readily be explained in tlie sameway.The solut<ion of phosphoric acid or phosphates may possibly havebppn derived from volcanic rocks by the action of the acid water alsoevolved clurjug volcaiiic disturhazices.c. €1. R.7,. 128 ABSTRACTS OF CHENICAL PAPERS.Investigation of a Saltpetre-earth from Turkestan. By y.LJUMTIN (Jour. Russ. Chern. fhc., 16, 617--638).-A sample of thlxearth was sent to the author from Fort Nukus, Province Arnu-Dari.Colonel Albanof found that the natives of the oasis Amu-DnIia preparenitre by boiling this earth with water and evaporating the solutionuntil it crjstallises on cooling; they use it for the mannfacture ofgunpowder withoutl any further purification. They regard thisimpure nitre as a poison. This earth covers an area of 7 squarekilos. on the frontier of China, over the ruins of the old city ofKunia-Ugrentch, in a country with very little rain.The earth, which is of a pale cinnamon colour, is dry, and can bereadily pnlverised between the fingers.It has a feebly alkalinereaction.The author gives a detailed account of the method used for thequantitative determination of t3he different constituents of the earth ;lie finds that when calcium oxalate is precipitated from a solution con-taining alkalis, appreciable quantities of the latter are carricd downwith the oxalate.In the following table, the results of the analysis are given in per-centages of the earth, dried a t loo", 96.21 parts of which are equalto 100 parts of air-dried earth :-Portion Soluble in Water.NzO,. c1. SO,. K,O. Na,O.* Si02,Fe20,,A120,.6-28 7.82 2.35 2.57 8.32 0.02CaO.MgO. Soluble humus.1-34! 0.80 0.15 = 29.65Subtracted oxxgen equivalent to 7-82 of C1 1-7627-89JE. Containing Li,O.Portion Soluble in Hyds.ochloric Acid.SO,. Si02. P205. &Ox. Pe203. A12C),. Ca0.t MgO. Mn,O,.0.38 0.018 0.314 0.58 2.91 2.75 7-58 2.50 0.11 = 17.142t Containing SrO. JE. Containing Na,O and Li,O.Porticn Insoluble in Water and Hydrochloric Acid,Organic substancesand water. SiO,. A1,03.* CaO. MgO. K,O. Na20.1.84 37-59 5.60 0.51 025 1.46 1.37 = 48.42Q Containing traces of Fe,03 and P,O,.Total nitrogen . . . . . . . . . . . . . . . . . . . . . , . .Organic nitrogen in this . . . . . . . . . . . . . . . . 1-750.1 MINERALOGICAL CHEMISTRY. 129Substances soluble in water. ............. 27-89Carbonic anhydride ....................5-73Substances insoluble in water and in acids. 48.42Total ............ 99.189 , 9 , hydrochloric acid. ... 17.14- __To this sum should be added the quantity of water of cryotallisationcontained in the salts at 100".The constituents of the portion of earth soluble in water may begrouped as follows :-....... 5.52 all nitrates, Potassium nitrate.Magnesium nitrate . . . . . 1.04Sodium chloride ........ 12.90Calcium sulphate ........ 3.25Magnesium sulphate ..... 0.66Sodium nitrate.. ........ 4-05>The total of calcium sulphate, including the portion soluble inhydrochloric acid, is 3-93 per cent., and from this CaSO, + HzO =4.97. This gypsum, according to Puchard, plays an important partin khe formation of nitre under the influence of a ferment.The analpsed earth may be regarded as comparatiTely very rich innitre, for in other countries earths containing only 0.26 per cent.areworked up wihh success.On comparing the composition of the portion of earth insoluble inwater, A, with the analysis of mud suspended in the water of Amu-Dari (Schmidt and Dorandt), B, the author finds a striking similaritybetween the two :-so,. .......SiO, ......P,O, ......co, ........K20 ........Sa2O ......Fe&, ......A1203 ......CnO ......MgO ......l ~ l ~ 3 0 4 . .....Humus ....Tvittel'. .....,4.0.5352.470.468.042-871.924.1 911.5711.353.860.150.961.63B.0.0049-620.228.172.151.654 7317.43Il-162.6 10.15 } 2.11---100~00 100.00 B.B.Blue Quartz fro= Nelson Co., Virginia. By R. ROBERTSON(Clrem. News, 50, 207).-This quartz is found associated with felsparin varying quantities ; it has a cbaracteristic waxy lustre, varies incolour from pale to deep blue, and is penetrated by numerous thi130 ABSTRACTS OF CHEMICAL PAPERS.brown films. A thin section under the microscope shows a networkof thin, acicular, brown crystals throughout the mass, so that, whenmagnified 400 times, it presents an appearance similar to that ofsagenite when seen by the naked eye. Some of the crystals arctwinned, forming geniculations common with rntile, The section isyellow by transmitted, and blue by reflected light.A fragment fused before the hot-blast blowpipe retains its bluecolour.Analysis yields the appended results per cent. :-Fe203, 0.539 ;TiOz, 0.069 ; SiO, (by difference), 9 9 3 . 2 . Itutile is frequently foundin the granulitic rocks of the district, and the magnetic iron ores ofthe locality contain large amounts of titanium oxide. D. A. L.Analysis of Pinite from Madkon Co., N. Carolina. ByC. L. REESE (Chem. News, 50, 209).-This miiieral is fouud inamorphous irregular masses. It is white, with a tinge of green, has awaxy lustre, it rough fracture, and is greasy to the touch. Itshardness is nearly 3 ; its sp. gr. = 2.822. The average of twoanalyses by the author gave the results under A, whilst under B arethe results obtained from the analysis of this mineral made by C.H.Slaytor in Bunsen's laboratory at Heidelberg.Si02. Al,O,. CaO. MgO. K20. Na2O. Water. Total.A . . .. 47.28 36.47 0.28 trace 11.40 0.74 4.39 = 100.5613.. .. 47-51 38.11 - - 13.37 - 1.05 = 99.84D. A. L.Amazon Stone from Amelia Co., Virginia. By C. @. PAGE:(Chew. News, 50, 208).-!L'his variety of amazon stone, in moderatesized crystals, is of uniform light green, or bluish-green colour ;whilst in large crystals the colour shades oE to white. Its cleavagelustre is vitreous, or pearly; its sp. gr. = 2.564. A thin sectionseen under the microscope shows the characteristic grated structureof microcline, along with a slight admixture of plagioclase. Analysisyields the following figures :-S O 2 . Al,O,. Fe203. CaO. MgO. K20. Na,O. Total.64.12 16.84 2.28 0.32 0% 13.34 1.88 = 99.04D.A. L.Albite frcm Amelia Go., Virginia. By R. ROBERTSON (Chew.News, 50, 2U8).-1'hk variety of a1 bite is occasionally found withinmasses of albite. It is bluish-grey, and slightly opalescent. Cleavageon 0 pearlr, arid regularly striated on i i pearlj. Its sp. gr. is 2 618.Analysis gave :-Si02. Al,O,. CaO. MgO. Na,O. K,O.67-06 21.i2 1.59 0.U3 10.~1 0.39 = 10O.Bcorresponding approximately with 6 mols. albite and 1 mol. anorthite.D. A. L.Analysis of Chrysocolla from Gila Co., Arizona. By R.ROBERTSON (Chem. News, 50, 209--210).-TLie mineral consibts ofcoal-black particles united by a much smaller quantity of brigh3iISERhLOGIUAL CHEMISTRY. 131bluish-green chrysocolla. The dark portion is purple-black, opaque,with sub-metallic to dull lustre, fracture rough, with tendency toconchoidal, and streak grey. Its hardness is 3 ; its sp.gs. = 2.04.Analysis gave the following figures :-SiO,. CuO. A120,. Fe2O3. OH,. Mn,O,. Total.31.58 30.28 6-27 0.84 28.71 2.62 = 99-90Neglecting the manganese and iron, which are probably uncom-bined, these number4 agree with the formula for asperolite, CuSiO, +;jH,O, wherein one-third of the copper is replaced by alumina. Thedark colour is due to the iron and manganese. D. A. L.The Pegmatite on the Borders of Vizhy, near Montbrison.By F. GoxNArtD (Cornapt. rend., 99, 881--883).-1n addition to theminerals already described (this vol., p. 3$), the pegmatite nearMontbrison conhins small, green, hexagonal prisms, truncated a tboth ends; these, however, are not emeralds, but crystals of greenapatite, similar to those found a t Iriyny and other localities.Not-withstanding the stahemelits of Passiiiges and Bournon that thispegmatite contains emeralds and ;tndalusite, the author has not beenable to find either of these minerals in it. C. H. B.Diamond-bearing Rocks of South Africa. By H. E. ROSCOE(C‘hem. News, 50, 243-244).-The diamonds are reached s t theKimberley Mine by shafts sunk through 3 feet of red sand and5 to 15 feet of tufaceous limestone to R soft, yellqw, earthy diamondrock 30 feet thick, succeeded by a soft, blue, diamond rock, proved toa depth of 282 feet. The diamonds are found in the yellow and blue‘( stuff ,” along with garnets, mica, bronzite, ilrnenite, pyrites, &c.The following specimens of rocks were examined:-I.A compactgreenish-grey rock, labelled “ The Hard Rock.” 11. A compact rockof dull rusty brown colour, “Layer of Ironstone.” 111. A friableearthy rock of greenish-blue colour, in which the dinmouds occur.I V . A mixture of’ several minerals, in pieces about the size of a pea,‘* Coarse, heavy deposit, Kimberley blue ground.” V. A similarmixture, in much finer grains, labelled “Pine heavy deposit, Kim-berley blue ground.” Sections of the tirst three specimens were cutnud sent to Professor Uonuey. An abstract, of his yeport upon themis as follows :-I. This rock is an actinolite-diabnse, and couid iiot bedistinguished from specimens obtaiuecl from various British localities,where rocks of palzozoic or greater age occur.11. This is ratlier adecomposed basalt belonging t o the sttine group as I, but probablyfrom a different mass, and altered in a ditf‘rrent way. These twosyecinieiis gave the following results 011 aualjsis :132 ABSTRACTS OF CHENICAL PAPERS.SiO, .........Fe,OB ........FeO.. ........Mn 0 ........CaO ..........Loss on ignitionA1203 ........MgO .........I. 11.5g.03 48-4715.53 16.33 - 9.859.64 1.654.54 0.486-99 8.434.55 7-38IIT.46.1 610.006.710.343.8416.63I5.55 at 120" } 15-43 { 93; 7*44 { 1.89 ,, red heat -Limonite.SiO, ............ 6.93A1203 ............ 6.85FezOs ............ 71.40FeO -Mn 0 -CaO ............. 0.71MgO ............0.86H,O ............. 12-53.........................Bronzite.55.172.95-5 * i 6-3.6432.83These have a very similar composition, the second differing fromthe first in containing a considerahle percentage of water, and in thefact that its iron is almost entirely in the peroxidised state. 111. Oft h i s specimen, Professor Bonney reports mainly as follows :-No. IT1is evidently a breccia composed of a compact serpentinons rock ofdark colour, the fragments and the paste apparently being similar incharacter, One or two scales of bronzite and a black mica arescattered in the matrix, with some small grains of a black mineralof irregular fracture, and one of a brown mineral. Microscopicexamination shows the ground-mass to consist of n ver-y minuteaggregation of doubly refracting crgstallites of no very definite butmther fibrous shape, and specks of ferrite.Here and there t,hecolouring mineral is cjpacite. Frequent cracks appeax to traverse theslide, occupied by a clearer mineral similar to that disseminatedthrough the slide. There is a small crystal resembling a hydrousbronzite. Be has a very strong suspicion that the fragments havebeen a basalt-glass, or an olivine-glass, more probably the latter,converted by hydration into a kind of serpentine. An analysis ofthe earth gave the numbers under 111 above. It was noticed thata peculiar smell, somewhat like that of camphor, was evolved ontreating the soft, blue, diamond earth with hot water. A quantityof the earth treated with ether gave a small quantity of a crystalline,strongly aromatic body, which was very volatile, burned easily witha smoky flame, and melted at about 50". The presence of thiscarbonaceous substance is most interefiting, and tends to confirmProfessor Cohen and Mr. Dunn's hypothesis that the carboniferousshales that are penetrated by the diamond-bearing " pipes " have beenthe source of the carbon which is now found as diamond. IV and VORGASIC CHENISTRT. 133which are samples of the deposit obtained by washing the “stuff,”show the minerals which accompany the diamonds. 100 grains ofNo. V contained :-Garnet 10.76, bronzite 3.64, ilmenite 54.80,pyrites 0-14, mica 0.20, limonite 16.12, pieces of the rock which haveescaped disintegration, with some limonite, 10.84, coarse sand, amixture of all the above, 3.46, The composition of the limonite andbronzite are given above. J. T

ISSN:0368-1769    

DOI:10.1039/CA8854800125

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

ORGASIC CHENISTRT. 133Organic Chemistry.Some Reactions of Silver Cyanide. By C. L. BLOXAM (Chem.ATeu7s, 50, 155) .-€Iydrocyanic acid is evolved on treating pre-cipitated silver cyanide with concentrated nitric acid ; on boiling, thecyanide is entirely dissolved and silver nitrate crystallises from thecooled solution. If, however, the solution is decanted when onlya portion of the precipitate is dissolved, it deposits minute needlesRS it cools; these crystals, wbich mat together in a remarkablemanner when the solution is stirred, are silver nitrocyanide,AgCN,2AgN03 (Abstr., 1884, 168). The residue left by the nitricacid consists of unattacked cyanide mixed with some of these crystals.This change also takes place slowly in the cold with concentratednitric acid; a boiling mixture of nitric acid, sp.gr. 1.400, with anequal volume of water, appears to be the most suitable for dissolvingsilver cyanide as nitrocyanide.When precipitated silver cyanide is treated with a strong solutinnof sodium carbonate, i t becomes granular, and the granules areobserved to be fringed with minute needles. BJ- boiling the pre-cipitated cyanide with strong solutions of potassium or of sodiumcarbonate, it, dissolves practically without dec?mposition, but isconverted into small prismatic crystals, which are sparingly soluble inthe hot solution of the alkaline carbonate, and are completelydeposited from this solution as it cools.Action of Primary Alcoholic Iodides on Silver Fulminate.By G. CALMELS (Compt. rend., 99, 794-797).-25 grams of driedsilver fulminate were heated with 25 grams of methyl iodide and 40grams of ether in a sealed tube at 50" for 24 hours.The productsare silver iodide, methylcarby lamine, and 6-nitroethylene. Ethyliodide and the higher primary iodoparaffins react in a preciselysimilar CNAg : CAgNO, + 2MeI = 2AgI + CNMe +CH2 CH.NO,. I n this reaction silver fulminate is split u p intotwo parts. I n order if possible to obtain the intermediate com-pounds-100 grams of methyl iodide mixed with 50 grams of ether wereallowed to act on 50 grams of the dried fulminate a t the ordinaryD. A. L.mamner:CNMe : CMe.N02 ; CNEt : CEt.N02131 ABSTRACTS O F CI-IENICAL PAPERS.temperature for four or five days, but the only products obtainedwere a-nitroethylene and rrieth;ylcnrbylamine.EthJl iodide and itshigher homolopes behave in the same way.The nitro-derivatives of the ethylene series are chamcterised bytheir power of existing in two modifications, the &-derivatives formingcolourless liquids soluble in ether and cliloroform, whilst the f!-deriva-tives are yellow resirlous solids insoluble in the same solvents.Fiwm their cl\emical behaviour, it would seem that the former are thetrue nitro-derivatives, whilst the lattcr are oximido-~erivatives.From these results, it follows that silver fulminate contains twodissymmetric:tl groups, each of which contains one atom of silver.One of these groups is silrer cyanide, CNAg, whilst the othercontains the sub-group N/ 1 and the second atom of silver, thelatter being united with the second atom of carbon, which is indirect union with the nitrogen in the first group (this nitrogenacting as a pentad) and thus links the two groups together:-0'0C=N ,Silver fulminate. Mercuric fulminate.It is evident from this formula that the two metallic atoms in thesilver fulminate have diiyerent functions, arid this explains the non-existence of mixed fulminates of the alkali metals.The forniula alsoexplains generally the observed action of the halogens on thefulminates.The fulminates are isocyanides or metallic carbylamines united bynitrogen t o a bivalent residue of a metallic derivative of nitro-methane, the metal attached to the nitro-group being any metal what-ever.This function, which is peculiar to the carbylamines and doesnot appertain to the metallic nitriles (cyanides), may be termed thecnrbazilic function. The relation of the carbazylic type to the alliedtypes is showii by the following formulae :-C i N CH,.CH C : N.Me C : N.HNitrile. Metanitrile. Carbjllamine. Carbazjlic.C . H. B.Gallisin. By C. SCHMITT and J. ROSENHEK (Bey., 17, 2456-2167).--This paper forms a continuation of C. Schmitt and A.Cobenzl's communication on this subject (Abstr., 1884, Wl).Actioii of SuLphzwic Molrochlo~c'de on Gallisin.-When pure dry galli-sin is gradually added to sulphuric: monochloride, SO,Cl.OH, it isdissolved, hydrochloric acid being a t the same time copiously evolved.All lieating must be carefully avoided, as decomposition sets in a tabout 60-70"."'he syrup produced cuuld not be obtaiued in a crysORGANIC CHJ$,RIISTK.T. 135talline state, and as it is decomposed even a t ordinary temperatures itwas poured on to broken ice, and the aqueous solution thus obtainedneutralised with barium carbonate. The barium salt was obtained asa white flocculent precipitate by pouring its solution iuto alcohol ;wheu dried, it forms a white hygroscopic powder which is slowlydecomposed on exposure to the air, quickly a t XO-100'. The corn-position of this substance is C6H,OI8S,Ba2 + 5H20, aud it appears tobe idelltical with Claesson's barium destrosotetrasulphate (Abstr.,1879, 1033). The authors found the rotation of this bariuin salt inaqueous solution to be 52", Claesson obtaining 51" for his compound.If this is really identical with Claesson's compound, the non-crystal-lising of the chloride first formed is probably due to the presence ofimpurities.Action of Bromiize on GaZlisin.-30 grains of gallisin were dissolvedin 1$ litres of water, and heated for about six hours in a well-corkedchampagne bottle in the water-bath, bromine being added at intervals.Altogether i 5 grams of bromine were used.The pressure generatedwas considerable, and the odour of bromoform was perceptible eachtime the bottle was heated. The authors were unable to isolate theunstable brominated compound which is fortlied, andsthe product wastherefore treated with silver oxide. The silver compound was alsovery unstable and was a t once decomposed with sulphuretted hydrogen.The free acid could not be obtained in a c~jstalline or pnre form.Itis dextrorotary, but unlike other acids obtained in a similar manner, itgives a precipitate with lead salts. I f added to a solution of ferricchloride (even in small quantities), it prevents the precipitation offerric hydroxide by arnmouia. It reduces Fehling's and Knapp'ssolutions. When neutralised with calcium, barium, or cadmiumcarbonates, it yields uncrystallisable salts which are precipitated byalcohol. None of the compounds could be obtained in a pure ordefinite state.Dry Distillation of Gallisin with Liti,e.-The distillate separatedinto two layers. The aqueous layer contained acetic acid andacetone; the oily layer boiled a t 82-86" and is probably Fremy'smetacetone.Action ?/' Pancreatic Juice o n Gallisijz.-If gallisin is treated withpancreatic juice and the whole allowed t o rernmn for a considerabletime in a wartn room, the former is converted into a substance caphble9f undergoing alcoholic fermentation with yeast : the quantityconverted is dependent on the length of time during which thepancreatic juice 1s allowed to act, but the authors have not yet beenable to convert the whole of the gallisin into such ferineritablcsubstance .The Specific Rotary Pozvpr oj' Pure Gullisiu, in aqueous solution,increases approximately in proportion to the iucrease in quantity ofthe solvent.Analzjsis of Commercial GI ucose air d Qua,ntitntive Zsstiwzation ofGallisiri therein.-Neubauer states that gallisin does not reduceE'ehling's solution, and this statement has beer1 generally accepted ascorrect. The authors find that gallisin does reduce Fehling's solution,1.01178 grams gullisin requiring 100 C.C.of solution. The author136 ABSTRACTS OF CHEMICAL PAPERS.suggest the following as the best method of estimating pure gallisinand pnre glucose in the commercial article. A solution is made con-taining less than 1 per cent., and is titrated with Fehling's solution.Another solution is made, fermented with yeast, and then titrated.The latter titration gives t,he quantity of gallisin present, and thedifference besween the two, the quantity of pure glucose.L. T. T.Thiovaleraldehyde. By G. A. BARBAGLIA (Ber., 17,2654-2655) .-I n a previous paper (Abstr., 1881,34), the author showed that sulphurreacted with valeraldehyde at about 250" according to the equation4C5HI0O + S, = 2C,Hl0S + 2C5H&.He finds that secondary re-actions also take place which give rise to the formation of : 1, hydrpgensulphide, the quantity of which increases as the temperature is raised ;2, a heavy red-coloured liquid, distilling between 200" and 300°,and having an offensive odour recalling that of onions and putrid eggs,tlie quantity of this substance being greater the larger the amountof sulphur employed ; 3, trithiuvnZeraZdehyde, CH,.CH.CH.CH.CHS,crystallising in bright yellow silky prisms melting at 94.5"; it isiusoluble in water, very readily soluble in ether and alcohol.\s/ yA.K. H.Aldehyde and Ethylidene Derivatives. Value of the Car-bony1 Affinities of Carbon. By R. RUBENCAMP ( A ? l ? d e ? z , 225,267-290) .-The liquid boiling about 15", which Wurtz (Jahresberichf,1856, 597) and Bachmann (Anrzalen, 218, 42) considere'd to bemethyl ethyl acetal, is in reality a, mixture of dimethyl acetal anddiethyl acetal. The author regards the existence of the mixed acetalsas very doubtful.Ethijlidene diacetnte is formed by the action of silver acetate onethylidene acetochlorhydrin diluted with absolute ether ; the pro-perties of this body have been previously described by Franchimont.By a similar reaction, ethylidene dipopionnte, C,H,(C3H,02)2, andother analogous compounds can be prepared. The physical propertiesof these bodies are shown in the followiiig table :-Xp.gr. Index of refractionB. p. (corr.). at 15". at 28-2.Ethylidene diacetate . . . . . . . . 168.4 1.073 1.399,, acetopropionate. . . 178.6 1.044 1.402,, dipropionate. . . . . . 192.2 1.020 1.407,, acetobutyrate . . . . 192% 1.014 1.4065,, dibutyrate.. . . . . . . 215.5 0-9855 1.411, , ace t oval erat e . . . . . 194.1 99 0.99 1 1.408,, divalernte .. .. . . .. 225 0.947 1.414,, propiochlorhydrin . 135 (uncor.) 1.071 -9 7 butyrochlorhydrin . 149 ,, 1.038,, valerochlorhydrin . 162 0-997 --As the cornpound produced by the action of silver propionate onethylidene acetochlorhydrin is identical with the compound obtaineby the action of silver acetate on ethylidene propiochlorhydrin,and in like manner, as the body produced from silver acetate andetbylidene butyrochlorhydrin is identical with that obtained fromsilver butyrate and cthylidene acetochlorhydrin, the author concludesthat both the " carbonyl affinities " are of equal value.w. c. w.Some Reactions of Carbon Bisulphide, and its Solubilityin Water. By G. CHANCEL and F. P A R x E m I E R (Compt. rend., 99,892--894).-When baryta-water is mixed with an aqueous solutionof carbon bisulphide, or with a mixture of carbon bisulphide andwater, very little action takes place a t the ordinary temperature, butif the mixture is heated an abundant precipitate of barium carbonateis formed, and the supernatant liquid becomes yellow. If the mixtureis heated in sealed tnbes a t 100" for some time, the liquid graduallybecomes colourless, and the amount of barium carbonate formed isgreater than that calculated from the equation given by Eerzelius,Experiments made by heating known weights of carbon bisulphidemit8h an excess of a somewhat dilute solution of barium hydroxide at loo", in sealed tubes previously filled with nitrogen, show that underthese conditions the reaction is accIirately represented by the equa-tion CS, + 2BaH20, = BaCOs + BaS2H2 + H,O.If the mixtureis heated in contact with air, the same proportion of barium carbonateis formed, but, it is mixed with a certain quantity of barium sulphateforriied by the oxidation of the hgdrosulphide.The authors have employed this reaction to determine the amountof carbon bisulphide dissolved by water a t different temperatures,with the following results :-Temperature .. . . . . . . . . 34" 15.8" 30.1" 41.0"CS, in grams per litre . . . 2.00 1.81 1.53 1'053CSZ + 6MOH = MzCO3 -t 2M?CS, + 3HzO.The solubility diminishes rapidly above 30", and becomes nil a t theboiling point of the bisulphide. The solution of carbon bisulphidebehaves under changes of temperature in the same way as the solutionof a gas. C. H. B.Normal a-Hydroxyvaleric Acid. By W. JUSLIN (Bey., 17, 2504-2506) .-Hitherto Pinner and Bischoff's trichlororalerolactic acid wasthe only known derivative of tbe above acid. The author has now pre-pared the unsubstituted acid by the action of alkalis on moriobromo-valeric acid, and also by the action of hydrocyanic acid m d hydro-chloric acid on butaldehyde.The valeric acid employed was obtainedby heating propjlmalonic acid. Ethyl a-brontoualerate is a colourlessliquid of pleasant odour. It boils a t 190-192", and has a sp. gr. of1.226 a t 18" compared with water a t 4". This ether was thendigested on the water-bath with a solution of sodium hjdroxide, theproduct evaporated to dryness, treated with sulphuric acid, andextracted with ether. On evaporation, the ether left a- hydyowpulwicacid as a syrup which, in a vacuum, solidified to large tabukir crystals.It is yery deliquescent and melts a t 28-29". The barium salt form135 ABYl11_?CTS O F CHEJIICXL PLIPERS.glistening scaly crystals soluble in water ; the bluish-pcn C>ppey saltis sparingly soluble in water.€Iutaldeh!/de was prepared by the dry distilhtioa of a mixture ofcalcium butyrate and formate, and was converted into its hydrogen.sodium sulpkite coinpou~rl. This substance forms long silky crptnlseasily soluble in water, spnriiigly so in alcohol and insoluble in ether ;it was distilled with a concentrated solution of sodillm hydroxide,and the butaldehyde thus obtained heated with hydrocyanic acidin closed tubes a t 70".Ths nitrile was then boiled with fuming hydro-chloric acid, the excess of the latter acid evaporated off, and theresidue extracted with ether. On evaporating the ethereal solution,an insoluble oil was left, which proved to be the anhydride of thehydroxy-acid. This was reconverted into the acid by boiling withpotash, &c., and the acid thus obtained was found to be identical withthat prepared with a-bromoraleric acid.When kept in a desiccator,the hydroxy-arid is gradually converted into the anhydride.Acetonedicarboxylic Acid. By H. v. PECHMANN (Bey., 17, 2542-2545).-Citric acid is heated with sulphuric acid on the water-bathuntil the carbonic oxide evolved is accompanied by carbonic anhy-dride, and the whole then cooled and water added. Acetoizedica@oxyZicacid, CO( CH2.COOH),, crystallibes out in colourless needles. Thissubstance forms a compound with phenylhydrazine. When heatedalone, it is decomposed into carbonic arihydride and acetone. Themelting point is about 138". The same decomposition takes placewhen the acid is heated with acids or alkalis, or its aqueous solutionis boiled.The elhers of this acid are liquid, and the author is nowinvestigating their substitution products.Amides of Citric Acid and their- Conversion into Pyridine-derivatives. By A.. BEHRMAKX and A. LV. HOFMANN (Bey., 17, 2681-2699) .-Oitramide, C6H504(NHJ3, is readily obtained by the actionof very strong aqueous ammonia on trimethyl citrate a t the ordinarytemperature. If alcoholic ammonia is employed, the action is muchslower and the yield much smaller. It is sparingly soluble in cold,readily in hot water, and insoluble in alcohol and ether ; when heatedabove goo", it begins to turn brown, and at 210-215" it melts to ablack liquid. It yields no acetic derivative when treated either withatcetic chloride or acetic anhydride.If the mother-liquor from tbecitramide is evaporated to a syrup, acidulated with nitric acid, andalcohol and ether then added, citrodiamic acid, C,H,O,(NH,),.OH, sepa-yates; this crystallises in white scales melting a t 158", is readilysoluble in water and almost insoluble in alcohol and ether. Thesilver salt, C,H5O4(NH,),.OAg, forms a crystalline powder sparinglysoluble in water; the lead and other salts are soluble. If thesyrupy mother-liquor from the citramide is treated with ammoniaand silver nitrate, cwgevtic citramorimiate, C6H,0s(NH2) (OAg)?, isprecipitated as a yellowish-white powder. The free acid is extremelysoluble in water, less so in alcohol, and is insoluble in ether and lightpetroleum ; it melts a t 138".A better yield of the citramic acids isobtained by treating citramide with weaker ammonia.L. T. T.L. T. T0% ASIC CHEJJISTRT. 139Citi*azim'c ncid, C,H,NO, : citrnmide is treated with 4-,5 parts o€sulphuric acid (70-i5 per cent.), the mixture heated at about 130",and the solution poni-ed, after cooling, into '2 to 3 vols. water;the acid then separates as a yellowisli powder. It may also be:obtained by the action of sulphuric acid on the citvarnic acids.Citrazinic acid is very sparingly soluble even in boiling water andirisoluble in other neutral liquids ; boiling concentrated hydrochloricacid dissolves it sparingly, but it is soluble in warm concentratedsulphnric acid, and very readily in alkalis and alkaline carbonates.The solutions of the citrazinates assume a greenish-blue colorationon exposure to the air, the amrnoniacal solution becoming deep bluelike an nmmoniacal copper solution ; the addition of an acid destroysthe colour immediately.When citirtzinic acid is added to a hotneutral solution of potassium or sodium nitrite, a deep blue colora-tion is immediately produced. Citrazinic acid is very stable, andmay be heated to 275" without devomposition; i t carhonises above300" without melting. It may be boiled for hours with thestrongest alkalis without yieldinz a trace of ammonia, but is decom-posed by fusion with alkalis with formation of potassium cyanidp.The alkali salts are very soluble, the barium and calcium saltssparingly so ; the lead salt forms a yellowish, the copper salt a brown,and the silver salt a yellow precipitate.The n / P t h / Z saZt, C6H4&feN0,,forms lustrous scales, which are sparingly soluble in water, alcohol,and ether; the ethyl scrlt, CGH4MeN01, has similar properties. Adiacetyl-deriuatice, CJHS&2NOi, may he obtained by dissolving theacid in boiling acetic anhydride ; it is readily decomposcd by water oralcohol. When cit,razinic acid is boiled with tin aud hydrochloricacid, tricarbnllylic: acid is produced:-C6H5N01 + 2H,O + H, =C6H,06 + NH2. The authors think it very probable t h t citrazinicacid is a dihydroxy-pyridinecarboxylic acid, C,H,( OH),N.COOH.When it is heated with phosphorous pentachloride and oxychlorideat 2.50°, and the product treated witJh boiling water, a dichloro-prridinecarboxylic acid, C,H,Cl2N.C0OH, is obtained, melting a t210" ; this is sparingly soluble in water, moderately in cold, readilyin boiling alcolicll, and extremely soluble in ether ; it is insoluble inhydrochloric acid, but dissolves in warm concentrated sulphuric acid,and readily in all alkaline liquids.The silver salt, CjH,CIIN.COOAg,crystallises from 1)oilin-g water in magriificent; colourless needles. Bythe action of hydriodic acid on the chlorinated acid, a, p?/q*idiw,e-carbolrylic acid is obtained, which melts a t 306", and is identical withSkraup's ypyridinevarboxylic acid (Ber., 12, 233.2) and Weidel'sisonicotinic acid. I t is sparingly soluble in cold, more readily in hotwater, sparingly also in alcohol and ether; the alkali salts alescluble, the silver s a l t insoluble; the copper salt POITUS a bluish-green crystalline precipitate ; the platinochloride,(C,rr,N.C@OH)?.H,PtCl6 + ZHdO,crystallises in thick orange-yellow prisms. If, in the reduction ofrlichloropyridinecarhoxylic acid, as above, phosphorus be added, thecarbox? I-group is reduced to methyl, and pwiipicoZijie is obtained.A. .I(.If1.401 ABSTRACTS OF CHEMlCAL PAPERS.Action of Ethyl Chlorocarbonate on Nitrogenous OrganicCompounds. By E. v. MEYER ( J . pr. Chem., 30, 115-125).-Ethyl chlorocarbonate reacts with cyanethine, forming cyanethineIzydmhlo?-ide and ethyl cyanethiibe carboccylate, thus :ZCgHJT2.NHz + ClCOOEt = CgHJTz(NH,),HCl +C,H13Nz.N€I. GO OE t.This latter compound can be separated from the hydrochloride bytreatment with benzene, which dissolves the ethyl cyanethinecarboxylate.It is an easily fusible solid, boils a t 247", its aqueoussolution has an intensely bitter taste and an alkaline reaction, and bycontinued boiling is resolved into carbonic anhydride, ethyl alcohol,and cyanethine. EthyZ cyanet hine-cai*boxylnte is easily dissolved byacids, and is reprecipitated from these solutions by bases ; its solutionsare precipitated by several metallic salts, such as mercuric chloride,gold chloride, and silver nitrate. This compound may also beregarded as a derivative of ethyl carbnmate, and is, in fact, ethylcyanoconyZ- cnrbanzate, (C,H,,N,)'HN.COOEt. With ammonia it formsc!/nnethiize-cal.bami~e, C,H,,N,.NH.CONH,, and with aniline cyan-Ptl~ine-cal.haniZide, (CgHl3N,)'.NH.CONHPh.This latter compoundcrystallises from alcohol in long, silky needles, melting a t 184", it is avery stable compound, and unaffected by acids or bases. Whenheated in a current of hydrochloric acid gas, it is resolved intocyanethine and phenyl cyanate, thus :-(CgH13N,)'.NH.CONHPh = (C9H13Nz)'NHz + PhNCO.Cy anethine-carba;?ziZiJe is formed also by the direct union of phenylcyanate and cyanethine, a formation analogous to that of methyl-phenylcarbarnide from methylamine and phenyl cyanate.The " ozybase," C9H,,NZ.OH, obtained from cyanethine, reacts withethyl chlorocarbonate, forming a compound similar to that obtainedfrom cyanethine ; it is a liquid which is decomposed by boiling withmineral acids into carbonic anhydride and salts of the " oxybase."Cyanethine heated with acetic oxide a t 170" is converted intoacetylcycrnethiize, ( CgH13N2) .NH%, a crystalline compound melting a t59", and but sparingly soluble in water.Acetnmide, benzarnide, and acetanilide yield no ethyl carboxy-lntes when treated with ethyl chlorocarbonate.Quinoline yields thehydrochloride of ethylquinoline. P. P. B.Cystine. By E. KCLZ ( Z e d . BioZ., 20, 1-lo).-The author found5.33 per cent. H, as the mean of several analyses of pure crystallisedcystine, and consequently assigns the formula C,H6NSO2, insbead ofthe C,H,NSO, give11 by Hoppe-Seyler and others.C,H,NSO, = 5.00HQ=,H,NSOz = 5.78 H.The rotatory power when dissolved in a<mmonia is [ a ] j = - 1 4 2 O ,using a Jellet-Cornu apparatus ; Mauthner found -205-SS" ; thisdifference is, however, accounted for by the fact that Manthnerdissolved his crystals in hydrochloric acid.J. P. LORQSNIC CHEMISTRT. I41Prelparation of Pure Thiophene. By V. MEYBR (Ber., 17, 2641-2643) .-If in extracting thiophene from its mixture with benzenethe proportion of sulphuric acid be diminished, thiophene alone istaken up, and may be recovered in a state of purity by distilling thesulphonic acid. 2000 kilos. coal-bar benzene were treated with100 kilos. sulphuric acid, the product converted into lead salt, andthis distilled with ammonium chloride. The amount of thiopheneobtained was 1944 grams. The acid layer obtained after shaking withsulphuric acid should be a t once diluted with water to prevent car-bonisation.To obtain 100 per cent. thiophene, 400 kilos. benzeneare agitated for two hours with 16 kilos. sulphuric acid, the productconverted into the lead salt, then into the ammonium salt, and t,hissubmitted to distillation. A. K. M.Nitration of Thiophene. By V. MEYER and 0. STADLER (Ber.,17, 2648-2650).-The nitration of thiophene may be effected bypassing air saturated with its vapour through fuming nitric acid,when after some hours the liquid separates into two layers. Onpouring the product into water, a heavy oil separates. The mono-and di-nitrothiophene obtained may be separated either by steam dis.tiilaCion or by fractional distillat'ion. 1Clouzonitrothio~heIze, CaHsS.NOz,more closely resembles paranitrotoluene than nitrobenzene ; it is of apale yellow colour, solidifies in large prisms after fusion, has an odmrlike that of bitter almond oil; it melts at 44", boils a t 224-285"(corr.), and becomes red on exposure to light. It is insoluble inalkalis, and is converted by nitric acid into dinitrothiophene. Nitro-thiophene gives no reaction wit,h isatin and sulphuric acid.Dinifro-thiophene, CdH,S (NO,)?, crystallises from alcohol in yellow scales,moderately soluble in hot water, and is decomposed by alkalis with redcoloration. It melts at 52", is somewhat volatile in steam, and boilsat about 290" without much decomposition. Bfetadinjtrobenzene boilsat 297" (corr.). An isomeric dinitrothiophene is also obtained whichmelts a t 75-76', crystallises in needles, and is somewhat more vola-tile in steam.A. I(. M.Acetothienone and some of its Derivatives. By A. PETER(Bey., 17, 2613-2647).-Acetothze~one, C4H3S.COMe, is best preparedby the action of aluminium chloride on a solution of 10 grams thio-phene (98 per cent. thiophene) and 9.1 gram3 acetic chloride in50 grams light petroleum. When the reaction is ended, the petro-leum is poured off, and the product warmed and poured into water.After purification, acetothiGnone is a colourless oil boiling a t 213.5"(corr.), and remaining liquid at -15"; it has an odour closelyresembling t,hat of acetophenone; its sp. gr. is 1.167 a t 24' When atrace of it is heated with isatin and sulphuric acid, it yields the indo-phenine-blue colour.Thit;nyZ?nethyZacetoziii~e, CaH3S.CMe : NOH,obtained from acetothiiinone and hydroxylamine, forms a whitecrystalline mass, melts a t about 110', and giyes no characteristic reac-tion with isatin and sulphuric acid. Acefotl~i~onepherzyZhlldraz.i~ze,CpH3S.CRfe N.NHPb, is prepared by heating an aqueous solution ofacetothiiinone, phenjlhydrazine hydrochloride, and sodic acetate, andVOL. XLYITI. 142 ABSTRACTS OF CHEMICAL PAPERS.crystalliaes from alcohol in clusters of bright yellow needles meltingat 96". On oxidising acetothihone with alkaline potassium perman-ganate solution, a thiopheuic acid, CdH3S.COOH, is obtained meltingat 124.5" ; it yields the indophenine colour-reaction with isatin andsulphnric acid.Its identity with a- or P-thiophenic acid is not yetestablished. By the nitration of acetothiihone at -go, two isomericmononitro-derivatives are obtained, one crystallising in long yellowfour-sided vitreous prisms melting a t 122*5", the other in smalllustrous scales melting at 86".Decomposition of Benzonitrile by Fuming Sulphuric Acid,By A. PINNER (J. yy. Chem., 30, 125--127).-A reply to Gumpert'sremarks (this vol., p. 52) on the preparation of cyanphenine. Theauthor shows that Gumpert emploved a method different from thatused by Klein and himself (Ber., 11, 764), and cites further experi-ments to show that cyanphenine is obtained on adding benzonitrile toa large excess of sulphuric acid.By W. STAEDEL (Anna7en, 225, 384-388).-The dinitrotoluene melting at 60" which the author obtained fromTiemann's dinitrotoluidine melting a t 168" (Annulen, 217, 205), isshown to have the constitution C6H,kLe(N0,), [Me : NO, : NO, =1 : 2 : 61 by the following facts. On reduction with ammonium sul-phide, the dinitrotoluene yields a nitrotoluidine melting a t 90".Phthalyl orthotoluide melting at.180" forms two isomeric nitro-pro-ducts, which are converted by the action of alcoholic ammonia intonitrotoluidines melting at 90" and 109" respectively. Nitrotohidine(melting at 90') from dinitrotoluene (melting a t 60"), or fromphthalylorthotoluide, can be converted into orthonitrotoluene, and thenitrotoluidine melting at log", from phthalyl orthotoluide, yieldsparanitrotoiuene. The constitution of the following bodies has nowbeen ascertained.A.R. M.P. P. B.Dinitrotoluene.M. p.Trinitrotoluene.. 81" C6H,MeN0,N0,N0, 1 : 2 : 4 : 6Dinitrotoluidine . 168 C,H,h!feNO,NH,NO, 1 : 2 : 4 : 6Dinitrotoluene. . . 60 C6H,MeNo2NO, 1 : 2 : 6Nitrotohidine . . . 90 C6H,&!eNH2No2 1 : 2 : 6>, . . . 109 C6H3MeNH,N02 1 : 2 : 4 w. c. w.Brorno-substitution Derivatives of Orthoxylene. By 0.JACOBSEN (Bey., 17, 2372-2379).-The only halogen derivatives oforthoxylene previously described are those in which substitutionoccurs in the side-chains ; the present paper describes bromine de-rivatives obtained by bromination in the cold in which substitutionoccurs in the benzene-ring.Monobl.omorthoxyZene, C6H3MeMeBr [l : 2 : 41 is obtained by theaction of bromine in presence of iodine cn commercial orthoxylenein the cold, but is contaminated with bromoparaxylerie and bromo-metaxylene.I t s purification is effected by conversion into the sul-phonic acids and crystallisation of the barium salts, when the ortho-derivative separates in large crystals, and is readily separatedmechanically f porn the meta- and para-salts. Monobromoxylene iORGANIC CHEXISTRT. 143regencrated from the barium sulphonate by converting it into thesodium salt and heating this with concentrated hydrochloric acid at200". It is liquid, but solidifies below 0" to a fibrous crystalline mass,melts at-0.2", boils a t 214.5 under 760 mm. pressure, and has a sp. gr. of15" 1.3693 at -0, Heated with ethyl chlorocarbonate and sodium amal-15gam, it is converted into paraxylic acid, showing that the bromine isi n the para-position.Bromorthoxy Zenesulpphonic acid,C6HzBrM'e2.SO:3H + xH20 [Me : Rr : Me : SO,H = 1 : 2 : 4 : 51,is obtained by dissolving bromorthoxylene in weak Nordhausen sul-phuric acid ; it forms a fibrous crystalline mass, very readily solublein water, very sparingly soluble in cold dilute sulphuric acid.Itsconstit,ution is shown by the action of sodium amalgam on the sodiumsalt, when it yields sodium orthoxylene sulphonate [l : 2 : 51, Thehccrium salt, ( CsH2BrMe2.S03)2Ba + 3&0, crystallises in long hardprisms, and is very sparingly soluble in cold water. The sodium salt,CeH8Br.S03Na + 1&H20, crystallises in very long, slender needles, spar-ingly soluble in cold, very readily soluble in hot water.The potassiwnsalf, CpHeBr.SO,K + H20, forms thin glassy prisms, moderatelysoluble in cold water. By fusion with potash, the sulphonic acid issplit up into a variety of products, of which the only one that could beisolated was p-metabromosalicylic acid, and this only in very minutequantity.Bromorthoxyleneszc~honamide, CRH8Rr.SO2NH2, crystallises in longhairlike needles, melts a t 213", is sparingly soluble in water and coldalcohol, moderately soluble in hot alcohol.Broniorthotoluic acid, C,H,MeBr.COOH [Me : COOH : Br = 1 : 2 : 41,is prepared hy boiling bromorthoxylene with dilute nitric acid (1 : 5)in a reflux apparatus. It crystallises in stellate groups of needles,melts a t 174-176", is sparingly soluble in cold, readily soluble in hotwater, soluble in alcohol.The calcium salt cr.ystallises with 2 mols.HzO in small hard prisms. When fused with potash, the acid yieldsparahomometahydroxybenzoic acid.Dibromortho~yZenes.-By the action of bromine on pure bromortho-xylene in presence of iodine, two dibromo-compounds are formed, andcan be separated by crydallisation from alcohol, one only being solidat ordinary temperatures.Solid dibron~orthoxylene, C6H2MeMeBrBr [ 1 : 2 : 4 : 51, is formed inby far the largest quantity ; it crystallises in large rhombic tables orlong needles, is sparingly soluble in cold, readily in hot alcohol andhot glacial acetic acid, melts at 88", sublimes slowly a t a little abovethe melting point in large thin plates, and boils a t 278".Heatedwith methyl iodide and sodium, it yields durene together with somepseudocumene and regenerated orthoxylene.Liquid dibromorthoxylene,C6H2Me2Br2 [Me : Me : Rr : Br=l : 2 : 3(?) : 41,solidifies on cooling to a hard crystalline mass, melts a t + 6-8", boilsat 277", and has a sp. gr. of 1.7842 a t E " The endeavour to deter- 1 5 '1 144 ABSTRACTS OF CHEMICAL PAPERS.mine its constitution by replacing bromine by methyl groups did notlead to satisfactory results ; the action could only be started by re-peated additions of ethyl acetate, but much orthoxylene was thenregenerated ; neither isodurene nor pseudocumene were formed. Itis probable that this compound corresponds with the still unknown[l : 2 : 3 : 41 tetramethylbenzene.All attempts to prepare a pure tribromorthoxylene were unsuccess-ful, although by the action of bromine on solid dibromorthoxylene inpresence of iodine and a little glacial acetic acid a very small quantityof a substance crystallising in needles and melting a t 50-60" wasobtained ; this appeared to he an impure tribromo-derivative.Theend-product of the action of bromine on orthoxylene in the cold istetrabromorthoxylene, C,Me2Br4. I t crystallises in long needles, meltsat 262", and distils unchanged a t a very high temperature, is sparinglysoluble even in boiling alcohol, but is readily soluble in hob benzene.Jlercury diorthoxylena, ~~e~~eC6H,.Hg.C6R*~feMe, is obtained asa bye-product in the action of sodium amalgam and ethyl chloro-Carbonate on bromorthoxy lene.It crystallises in long, slenderneedles, melts a t 150," can be in great part distilled unchanged bycareful heating, and is sparingly soluble in ether and alcohol, readilyin chloroform, carbon bisulphide, benzene, &c.Pure monobromoparaxylene does not solidify a t -15", and boils a t205.5" under 755 mm. pressure. This differs from the figures givenby Jannasch (this Journal, 1874, 465) of + loo f o r the melting point,and 199*5-200*5" for the boiling point, but is in agreement with theearlier statement of Fittig and Jannsscli ( A n o ~ a l e i ~ , 151, 283).1 2 4 1 2Bromopa raxy lenesu Zpho7~ic acid,C6HzMezBr.80,H [Me : Me : BP : S0,H = 1 : 4 : 2 : ?I,crystallises in nacreous plates or flat needles.The sodium salt,C8H,Br.S0,Na + H20, crystallises in long thin prisnis or in rhombicor hexagonal tables. The buriu:rz salt cr~stallises in thin hexagonalplates, or small prisms, and is sparingly soluble i n hot water.B r o ~ ~ o ~ ~ u r a x ~ l e n e s z i l ~ h o n a ~ z i ~ ~ e , C6H2~~e2Br.SOzKH2, crystallises inflat prisms, inelts a t 806", is sparingly soluble in cold, readily solublein hot water. A. J. G.Nitro- and Amido-derivatives of Metaxylene. By E.GREVINGK (Ber., 17, 2422-2431) .-Cousecutive nzetacli.1Lits.ometax~le?~e,C6&&fez(N02)2 [bxe : NOz : Me : NO, = 1 : 2 : 3 : 41, is obtainedtogether with the symmetrical dinitrometnxylene melting a t 93" pre-viously described by Fittig ( A n n a l e n , 147,17, and 148,5), by treatingmetaxylene with a mixture of sulphuric and nitric acids a t a tempe-rature of 3-6".It crystailises in plntes, melts a t 82", and is morereadily soluble in alcohol and glacial acetic acid than the other modifi-cation. On nitration, hoth the diuitro-compounds are converted intothe trinitrometaxylene [Me : NO, : Me : NOz : NO, = 1 : 2 : 3 : 4 : 61,melting a t 176", described by Fittig ( h e . cit.).Consc~ci~tive ~netanitroxylt'dinr, C,W,Me,(NH,) .NOZ, is obtained by thereduction of consecutive disitrometaxylene with hydrogen sulphidORGANIC CHEMISTRY. 145in alcoholic ammcmiacal solut'ion. It crystallises in golden-yellowneedles, melts at 78", and is soluble in water, alcohol, and lightpetroleum. The acetyl derivative crystallises in white needles andmelts a t 149".The acetyl derivative prepared from the nitroxylidineof melting point 123", derived freom symmetrical dinitrometaxylene,also crptallises in white needles, but melts at 159-160".Symmetrical metadiamidometaxylene,C6H,Me,(NH2), [Me : Me : NH, : NH2 = 1 : 3 : 4 : 61,is prepared by reduction of tLe corresponding nitroxylidine (meltinga t l23?) with stannous chloride and hydrochloric acid. Afterbeiiig purified by sublimation, it forms snow-white crystals, andmelts at 104". The hydrochloride yields Bismarck brown withsodium nitrate, and a chryso'idine with diazobenzene chloride, showingthe base to be a metadiamine.Consecutice metCLdiamidonaetaxy Zen e,C6H2Me2(NH,), [Me : NH, : Me : NH2 = 1 : 2 : 3 : 4:.The reduction of 1 : 2 : 3 : 4 nitroxglidine cannot be effected bystannous chloride, tin and hydrochloric acid have therefore to be used.The diamine forms fine white crystals, and gives the colour reactionsof a metadiamine.Triumidometaxylerte, C6HMe2(NH,)3 [Me : NH, : Me : NH, : NH, =1 : 2 : 3 : 4 : 61, prepared from the corresponding trinitro-compoundby reduction with stannous chloride and hydrochloric acid, crystallisesin white needles ; its melting point could not be determined ; it doesnot melt up to 140", and suffers complete decomposition between140" and 150".The hydrochloride gives a greenish-brown colorationwith sodium nitrite, and a reddish-black coloration with diazo-benzene chloride.By the nitration of 1 : 3 : 4 metaxylidire, the two nitrometaxyli-clines already mentioned, melting at 78" and 123" respectively,were obtained.By treatment with ethyl nitrite, &c., to eliminatethe amido-group, the nitrometaxylidine of melting point 123" wasconverted into the nitrometaxylene [Me : Me : NO, = 1 : 3 : 41,boiling at 245.5" under 744 mm. pressure, and of sp. gr. 1.135 a t 15",already described by Tawildaroff ( Z e i t . f. Chenz., 1870, 418), andHarmsen (Abstr., 1881, 49); this by reduction with iroc and aceticacid, gave the unsymmetrical metaxylidine described by Hofmann(this Journal, 187i, i, 92) and Schmitz (Abstr., 1879, 156). 1 : 3 : 4aceto-xylide €orms white crystals and melts a t 128".Consecutice nitrometnxylene, C~H&~,.NOZ [Me : NO, : Me = 1 : 2 : 31,is prepared by the action of ethyl nitrite, &c., on the nitroxylidinemelting a t r8".It boils a t 225" under 774 mm. pressure, and has as . gr. of 1.112 a t 15". Reduced with iron and acetic acid, it givest i e consecutive metaxylidine described by Schmitz. 1 : 3 : 2 aceto-xylide crystallises in white needles and melts at 174".Action of Chlorine, Bromine, and Iodine on Sodium Para-cresolate. By C. SCHALL and C. DRALLE (Bas., 17, 2528-2536).-I . Action of ChEorinc.-When chlorine is passed through anhydroussodium paracresolate suspended in carbon bisulphide, the principalA. J. G146 ABSTRACTS OF CHEMICAL PAPERS.product is monochloroparlncresoZ, C6H,MeCl.0H. This compoundyields no sulphonic acid, whilst paracresol yields an ortho-sulphonicacid, so that the chlorine atom is probably in the ortho-position to theOH group.This was proved by treating it with phosphoric chloride,when a dichlorotoluene melting at 200" was formed, which on oxida-tion yielded orthodichlorobenzoic acid. Its constitution is therefore[OH : C1 : Me = 1 : 2 : 41. When the sodium salt of ihis substanceis treated with methyl iodide, i t Fields monochloro~a.mcresZl1 methylether, a colourless, feebly refracting liquid which boils at 213-215",and has a sp. gr. of 1.1493 a t 2.425" compared with water a t the sametemperature. This aniso'il when carefully oxidised with chromic acidyields monochloranisic acid, OMe.C6H,C1.COOH, which crystallises inwhite silky scales melting at 214-215". The barium salt crystalliseswith 3 i mols. H,O : the silver salt forms sparingly soluble scales.11.Action qf Bronziize.-This is similar to that of cblorine. Nono-brornoparacresol is a colourless liquid boiling at 213-214" ; its sp. gr.is 1.5468 a t 24.5". This compound is isomeric with that obtained byVogt and Henninger (Abstr., 1882, 729) by the direct bromination ofparacres0.l. Il.;ronobro?noparacresyl methyl ether boils at 225-227", andhas a sp. gr. of 1.4182 a t 24.5". ikIo?zobronaanisic acid crystallises inneedles melting a t 21.3-214" ; its baliunz salt forms small needles con-taining 3-&H20 : the silver salt is a flocculent amorphous precipitate ;the copper salt crystallises in green plates with 2$ mols. H,O.A small quantity of dibromoparucresql was also formed during theaction of the bromine on sodium paracresolate.This substance formsprisms belonging to the asymmetric system, and isomorphous withthose of dichloroparacresol. Dibromoparacresyl benzoate crystallisesin snow-white needles melting at 91-91-5". The dibromide was alsocoiiverted into the anisoil, but all attempts to oxidise this provedfutile.111. Action of Iodine.-This was similar to that of chlorine andbromine. As the authors were not able to isolate the moniodo-paracresol i t was converted into the methyl ether. Moniodopara-cresyl inethyl ether boils at 237-238". ilfoniodoanisic acid is identicalwith that already described by Griess (Annalen, 117, 54) and byPetzer (AnnadeN, 146, 302), a i d melts a t 234-235'.DiidoparacresoZ forms white plates melting a t 61-61 *5".Diiodo-parawesyl acetate forms white plates melting at 62-62-5". Diiodo-pamcresyl benzoate melts at 129*5-130".Saponification of Halo'id Ethers of the Benzene Series byNeutral Substances. By A. COLSON (Compt. rend., 99, 801-804).-The dibrominated derivatives of the three xylene glycols wereheated with 2 mols. H23 in sealed tubes at loo", and the rate andlimit of saponification were determined by estimating the amount ofacid liberated. The maximum limit of saponification is reached morerapidly than in the case of the corresponding compounds in themethane series, and is the same for all three isomerides, and probablyalso for their homologues. The isomerides are, however, distinguishedby the velocity of saponification, which is highest for the para- andlowest for the meta- derivative.I n the case of the dibrominatedL. T. TORGANIC CHEMISTRY. 147derivatives, the amount of acid liberated is only about 9 per cent. ofthe total acid, but as soon as this proportion is exceeded, the com-pounds rapidly decompose.When the dibrominated derivatives are mixed with an equal weightof ordinary alcohol, and allowed to remain for several days at 30-32",it is found that they are more rapidly attacked by the alcohol thanthe corresponding primary compounds in the methane series. Therate of snponification is highest for the meta- and lowest for the para-derivative, and this also holds good a t 100".If the haloi'd derivatives are heated with 2 molecular proportions ofamyl alcohol in sealed tubes at, loo", it is found that the brominatedderivatives decompose more rapidly than the chlorinated derivatives,whilst in each series decomposition ceases when about the same quan-tity of acid (about 5 per cent.of the total amount) has beenliberated. The meta-derivative is almost completely decomposed,although only a small quantity of acid is set free. This result isexplained by the fornia-ion of (?) bromamyline, CH,Br.C6H+OC5Hll.I t is evident that sitice the haloyd ethers are sensibly attacked byalcohol in the cold, and rapidly a t loo", this solrent should beavoided when working with these compounds.The ethers of the methane series acting on these haloid derivativesof the benzene series yield only one series of compounds, as shown inthe equation-C5H4(CH2Br), + Et,O = C6H4(CH2.0Et), + 2CLH5Rr.C.H. B.Conversion of Phenols into Amines. By K. BUCH (Rer., 17,2634-2641) .-Phenylparatolylamine is formed from phenol and para-toluidine, and from paracresol and aniline, by heating them with anexcess of zinc chloride a t 260-300"; also in very small quantity byheating phenol and paratoluidine with calcium chloride a t 300". Abetter yield is obtained by the action of antimony trichloride on amixture of aniline and paracresol a t 260", diphenylamine being, how-ever, also produced. When paratoluidine and phenol are heated withphosphoric anhydride, ditolylamine is obtained, but no phenyltolyl-amine. Paratoluidirie is produced on heating paracresol with ammo-nio-zinc chloride at or above 300O; ditolyl oxide, (CiH7)20, is alsoformed.This is moderately soluble in alcohol, and crystallises fromit in silky scales, and fram light petroleum in needles; it melts at165" and volatilises a t 100". Ditolyl oxide is also formed whenparacresol or a mixture of paracresol and paratoluidine is heated withzinc chloride. Diphen ylanzine is obtained in small quantity by theaction of calcium chloride at 300" on aniline and phenol. It is alsoproduced by the action of antimony tricbloride on aniline, but a muchbetter yield is obtained when a mixture of aniline and phenol isemployed . A. K. 51.The Action of Cyanogen Chloride on Ortho- and Para.amidopheneto'il. By J. BERLINERBLAU ( J .pr. Chent., 30, 97-115).--By the action of cj-anogen chloride on aniline, cyananilide an148 ABSTRACTS OF CHENICAL PAPERS.diphenylgunnidine are produced (Hofmann) ; its action on ortho- andpara-amidophenetoyl in ethereal solution is now studied and shown tobe similar. Orthoethoxyphen,ylc~janamide, EtO.C,H,.NHCN, formscrystals melting a t 94", almost insoluble in water, and which do notpolymerise on keeping or heating. If heated with hydrochloric acidat 1 2'uo, it does not yield orthoxyphenylcyanamide, but orthnmido-phenol ; when treated in ethereal solution with dry hydrochloric acid,a syrup separates out unsuited for further examination. When treatedwith sodium nlcoholate, the crystalline and stable sodium salt,E t0.c6Hi.NNaCN, separates, which is reconverted into the originalcyanamide by the action of acids : no polymerisation occiurs.Withsilver nitrate, an aqueous solution of this salt gives a curdy pre-cipitate of the siZver salt, Et0.CsH4.NAgCN. The behaviour of thesesalts with ethyl iodide and also with iodine was partially studied.This and the following silver salt are readily decomposed by sul-phuretted hydrogen, but no polymerisation takes place as with silvercyanamide.ParaethoxyphestyIcyanamiae melts at 78" ; only its silver salt couldbe obtained. Once crystals melting a t 160" were obtained: con-taining 1 mol. H,O more ; they are paraethoxypher/ylca~ban~ide,Et0.C6H4.NH.CONH2. This substance can also be prepared bymixing solutions of the hydrochloride of para-amidophenetoil withpotassium cyanate; it is almost insoluble in water; i t is not con-verted into the cyanamide or in any way altered by phosphoric anhy-dride.Treated for a long time with nitrous acid in alcoholic solution,a red precipitate, C9HllN202.N02, separates; if the acid acts for a8hort time only, an intermediate substance is formed insoluble inwater, but decomposing very rapidly.These substituted cyanamides can also be obtained from the corre-sponding thiocarbamid es.Orthoethoxy~henylthiocarbamide.-Orth,zmidophenetoi'l ie evaporatedwith ammonium thiocyanate, and the residue washed with water. Itmelts at 110". Mixed with lead hydroxide and dilute caustic soda,the lead sulphide filtered off, and acetic acid added, the above-described orthoethoxyphenylcjanamide seperates.Paraethoayphenylthiocarbamide was likewise prepared and con-verted into the corresponding cyanamide.A Lakmo'id.By M. C. TRAUB and C. HOCK (Ber., 17, 2615-2617).-W hen a mixture of resorcinol (100 parts), sodium nitrite( 5 parts), and water (5 parts), is gradually heated to l l O o , a briskreaction sets in and the mass assumes a red colour; when ther*eaction becomes less vigorous the heat may be raised to 115-120" ;ammonia is then abundantly evolved whilst the melt becomes reddish-violet, bluish-violet, and finally blue. The product yields a blue solu-tion with water, and on the addition of hydrochloric acid a precipitateis obtained ; this, when dried, forms lustrous reddish-brown grainsinsoluble in chloroform and benzene, but readily soluble in alcohol,acetone, &c., less so in ether and pure water ; these solutions have ared colour which resembles that of many red wines or raspberry-juice,and is changed to blue by the addition of a trace of alkali. Thifi dyea.BORGANIC CHEMISTRY. 149also dissolve^ in boiling concentrated hydrochloric acid, yieldinga bluish-peen solution, and in concentrated sulphuric acid to a deep-blue solution. The absorption-spectrum of the alkaline solutionresembles that of litmus, but the absorption-band is not so strong. Italso resembles litmus in its behaviour on reduction, the alkaline solu-tion being rapidly decolorised by hydrogen sulphide, but the colouris restored on exposure to the air. The authors hope to prove theidentity of this artificial colouring matter with the chief constituent oflitmus.A. K. M.Substitution of the Amido-group in Aromatic Derivatives byChlorine, Bromine, and Cyanogen. By T. SANDMIEYER (Ber., 17,2650-26.53) .-This is it continnation of experiments recently de-scribed (Abstr., 1884, 1311). I n order t o convert mefanitranilineinto metachloronitrobenzene, 4 grams of the former together with7 grams concentrated hydrochloric acid (sp. gr. 1-17'), 100 gramswater, and 20 grams of a 10 per cent. solution of cuprous chloride, areheated nearly to boiling and then a solution of 2.5 grams sodium nitritein 20 grams water is added drop by drop. I n the same way, para-clilorotoluene has been obtained from paratoluidine, orthochlorotoluenefrom orthotoluidine, and orthochlorophenol from orthamidophenol,but in the case of the two ortho-derivatives the yield is small.Para-phenylenediamine and met'aphenylenediamine also yield the corre-sponding dic hlorobenzenes. To obtain bromobenzene from aniline,12.5 grams copper sulphate, 36 grams potassium bromide, 80 gramswater, 11 grams sulphuric acid (sp. gr. l*S), and 20 grams copperturnings are boiled together until the solution is nearly decolorised,9.3 grams aniline added, the whole again heated nearly to boiling, andthen a solution of 7 grams sodium nitrite in 40 grams water graduallydropped in. The product is distilled, washed with soda and water,extracted with ether, dried, and fractioned. The amido-group mayd s o be replaced by cyanogen: 28 grams of a 96 per cent. solution ofpotassium cyanide are added to a hot' solution of 25 grams coppersulphate in 150 grams water, the solution heated to about, go", and asolution of diazobenzene chloride gradually introduced.The whole isthen d i d l e d , the oil extracted with ether, washed with soda solutionand with dilute sulphuric acid, and then fractioned. The amount ofbenzonitrile boiling at 184" obtained is 63 per cent. of the theoreticalamount. A. K. 11.Action of Ethyl Chlorocarbonate on Paranitraniline. ByH. HAGER (Ber., 17, 26'Lri-'Ltj32).-Pal.anitroyhen?Jluretkane (phenyl-en~amnitrourethane), N O,.C,H,.NH.CI)OEt, is prepared by heatingparanitraniline (6 grams) with ethyl chlorocarbonate (6 grams) forabout three hours at 120-130".It is sparingly soluble in water,readily in alcohol, from which it crystallises in long, brown, silkyneedles melting at 129". The mother-liquors contain a very smallquantity of a crystalline compound of metallic lustre which impartsa blue colour to silk. Paramidophenqlurethane, obtained by reducingthe nitro-compound, is sparingly soluble in water, readily in benzene,from which it c~*ystallises in long, brown, transparent prisms meltinga t 71-72' ; with ferric chloride, it yields a green precipitate whic150 ABSTRACTS OF CHEMICAL PAPERS.at once turns black and is readily soluble in alcohol with violetcoloration. It does not yield a carbamide when heated. The hydro-chloride, C,H,,N20,,HC1, forms readily soluble colourless needles ; themercury compound, ( C,H,2N20~,HCl)4,HgC12, crystallises from a hydro-chloric acid solution in long violet needles ; the stannichloride,(C,H,2N202,HCl),,SnC&, forms colourless scales ; the platinochloride,(C,H,,,YZO,),,H,P~C~,, is a light brown precipitate, and is decomposedby boiling with water ; the sulphate, C,H,,N,O,,SO,H,, is readilysoluble and crystallises in concentrically grouped arborescent forms ;t b e oxalate, C9H1',N2O2,C2O4H2, crystallises in violet needles, verysparingly soluble in cold, readily i n hot water Parabeizxoylamido-phenylurethane (phenylenepara.miclobenxoylurethane),NH%.C6H4.NH.C00Et,is obtained on gradually adding a mixture of benzene and benzoicchloride to a cold solution of phenyleneparamidourethace in benzene.It is insoluble in water, sparingly soluble in alcohol, from which i tcrystallises in slender violet needles melting at 230" ; by the action ofnitric acid (sp.gr. 1*53@), a small quantity of a trinitro-derivative isobtained ; this melts at 210" and crystallises from alcohol in slenderyellow needles. When paramidophenylurethane hydrochloride andbenzoic chloride, in molecular proportions, are heated together at140-150°, a substance is obtained which appears to have the formulaN( C,H,.NHB<),.COOEt. It is insoluble in water, very sparinglysoluble in alcohol and glacial acetic acid, and crystallises in slendercolourless needles melting above 360". Orthoparar~initropheny2ure-thane, C,H,(NO,),.XH.COOEt, is obtained by the nitration of para-nitrophenylurethane in the cold.It melts at 110-lll", dissolvessparingly in hot water, more readily in alcohol, from which it crystal-lises in light brown needles. When its a,lcoholic solution is warmedwith potassium hydroxide, ammonia is given off and diorihoparadini-t~ophenylamine (tetranit,.od~henylamin~~, NH( C6HJNB04)2, is produced ;this melts at B O O , is sparingly soluble in alcohol, more readily in glacialacetic acid, crystallises from the former in reddish-brown scales, andfrom the latter in yellow needles and prisms; with caustic alkali,it yields a dark red solution, which gives off ammonia when heated.When orthoparadinitrophenylurethane is submitted to the action ofammonium sulphide, orthamido~ara?l,itrophenyluretl~ane,NH,. C6H3 (NOz) .NH.COOEt,is produced. This is very sparingly soluble in water, readily inalcohol, and crystallises in orange-red needles orl prisms melting at162" ; it is decomposed by dilute acids into alcohol and the carbamide-derivative, N02.C,H,< Na> CO. This is sparingly soluble in water,readily in alcohol, from which it crystauises in colourless needleswhich do not melt at 300" ; it is also readily soluble in cold alkali. Bythe action of tin and hJdrochioric acid on orthoparadinitrophenylure-thane, both nitro-groups are reduced, alcohol is eliminated, and the car-bamide-derivative, CeH3(NH,,IICI)<NH>C0,HCl, is obtained. ThisNHNORQANIC CHEMISTRY. 151is extremely soluble in water, less so in hydrochloric acid, from whichit crystallises in nodular groups of small violet needles.The zincdouble salt, C7H7N30, 2HC1, ZnC12, crystallises from hydrochloric acidin long, dense, graphite-like needles of metallic lustre. The platinicand mercuric: double salts decompose very readily. The picrate,C7H7N,0, C6H3N307, forms gweuish-yellow needles. A. K. M.Oxidation of Paratoluidine. By H. KLINGER and R. PITSCHKE(Ber., 17, 2439-2444) .-The oxidation of paratoluidine has beeninvestigated by Barsilowsky (Abstr., 1879, 237) who used an alkalinesolution of potassium ferricyanide, and by Perkin (Trans., 1880,546),using chromic acid. The same substance, of the empirical formulaC7H,N, was obtained by both observers, but was regarded by Barsi-lowsky as a polymerised azotoluene, whilst Perkin considered thatit was probably a triparatolylenetriamine, ( C7H,),N3H3 ; the authorshave tberefore re-examined the compound.The substance was pre-pared by oxidation of paratoluidine with an alkaline ferricyanidesolution, and its identity with that obtained by the other authorsdetermined hy crystallographic mea,surement. I t melts at 220-225"(216-220", Perkin ; 244---245", Barsilowsky). Its salts can be ob-tained by sha.king a solution of the base in benzene with diluteaqueous acids, as dark violet or iridescent crystalline precipitates ;they are partly decomposed by washing and drying. The hydrochlo-vide, C28H,8N,,:!HCl7 was obtained in a pure state, and then formslustrous, violet plates, readily soluble in water and alcohol with in-tense reddish-violet coloration ; on addition of alkalis, the base isliberated.By the action of stannous chloride followed by tin andhydrochloric acid on a solution of the base in alcohol and hydrochloricacid, it is converted into paratoluidine and a leuco-base, C21H33N3. Asparatoluidine is also formed by the action of hydrochloric acid on thebase, it appears most probable that the latter is an amido-aso-corn-pound of the formula c2,H,7(NHz).N2.C7H7.Parulewcotoluidine, CzIHz3N3, crystallises in thin, white plates, whichvery soon turn red; it melts at 150", is very readily soluble in coldalcohol or in hot water or hot aqueous soda. The hydrochloride,C21H23N3,3HC1 + H20, forms colourless prisms or slender needles.Parurosatoluidine is prepared by oxidation of the leuco-base by acurrent of air, or more conveniently from the hydrochloride by the actionof a strongly alkaline f erricy anide solution.It crystallises in reddish-brown plates having a green lustre, melts at 150", and is decomposedat higher temperatures with formation of ammonia and toluidine. Itis readily soluble in alcohol, ether, and benzene, and dissolves in con-centrat'ed sulphuric acid with purple-red colour. A. J. G.Two Isomeric Isobutylorthamidotoluenes. By J. EFFRONT(Ber., 17, 2317--2351).-The author has already shown trhat anisobutylorthamidotoluene is obtained by heating orthotoluidinehydrochloride with isobutyl alcohol at 300" differing from thatprepared by Erhardt (Inaug. Diss., Zurich, 1882) by heating isobutylalcohol and orthotoluidine with zinc chloride.This latter substanc152 ABSTRACTS Of! CHEMICAL PAPERS.has ths constitution [Me : BUS : NH, = 1 : 3 : 21, whilst the baseobtained by the author is expressed by [Me : Bus: NH, = 1 : 5 : 21.5 . 2 ISOBUTYLORTHAMIDOTOLUENE, CsH,MeBup.NH2 [ 1 : 5 : 21, obtainedas above mentioned, forms a nearly colourless liquid of agreeablearomatic odour, which turns yellow on exposure to light, does notsolidify in a mixture of ice and salt, boils a t 243", and readily distilswith steam. It is nearly insoluble in water, but mixes in every pro-portion with alcohol and ether, and forms well characterised salts.The hydrochZoride, CIlHl7N,HCI, crystallises in long, thin needles. Itis sparingly soluble in cold, readily soluble in hot water.By longboiling of its aqueous solution, the salt suffers dissociation. Thehydrobromide, CllHliNJHBr, crystallises in long needles. The sulphate,(C,,H,7N)2,H,SOa, crystallises in white needles, sparingly soluble incold water. The ozalnte, ( Cl,H17N)2,H2Cz04, crystallises in silveneedles readily soluble in hot water, alcohol, and ether. The acety?derivative, C6H,MeBup.NH&, crystallises in greyish-white plates,melts at 162", is sparingly soluble in hot water, readily soluble inalcohol. The benzoyl-deramtive, C6H3MeBu@.NHE, forms small whiteneedles, melts a t 168", and is sparingly soluble in hot water or coldalcohol.I~obut,ylorthocresol, C6H3NeBuP.0H [l : 5 : 21, prepared by means ofthe diazo reaction from the amine, is a thick, pale-ycllow liquid offaint aromatic odour, sparingly soluble in water, readily soluble inalcohol, ether, and dilute aqueous soda.I.cobuf?llorthiodotolue7le, C6H,hfeBupI [l : 5 : 21, prepared by the actionof hydriodic acid on the crude solution of the diazo-cliloride, formslong white needles, melts at 34-35', and boils at 264-265".Byoxidation with chromic acid, it is completely oxidised ; by heatingwith dilute nitric acid, it is oxidised to nitrotolylisobutyric acid, orby further action it is converted into nitrotolylpropionic acid.NitrotolylisoSutyric acid,C6H,Me(N0,).CH2.CHMe.COOH [Me : NO, : C4H70, = 1 : 2 : 51,cryst'allises in white needles, melts at 139O, can be sublimed, issparingly soluble in cold, readily soluble in boiling water, sparinglysoluble in light petroleum, readily soluble in alcohol and ether.Thesilver salt, C,H,,(N02) .COOAg, crystallises in coloiirless plates, andis readily soluble in hot water.Nit rototy lpropiouic acid, Cti H,Me (NO,). CH,. CH,. C OOH, crystal lisesin thick white needles, meIts between 130-136", and is less solublein boiling water than the preceding acid.Experiments to convert isobu tylorthamidotoluene into the hydro-carbon by the action of ethyl nitrite were not auccessful. It wastherefore converted into the azo-chloride, and this treated withstannous chloride, when a hydrocarbon was obtained agreeing in allparticulars with Kelbe's metaisobutyltoluene (Abstr., 1881, 809).ToZyZpropionic acid, C6H&fe.CH2.CH2.COOH (Me : C3H502 = 1 : 31,is obtained by heating metaisobutyltoluene with excess of nitric acid(sp.gr. 1-15) for five hours a t 180", it crystallises in white needles,melts at 125", and sublimes readily. It is scarcely soluble in cold,sparingly soluble in hot water, readily soluble in alcohol and etherORGANIC CHEXISTRY. 153The silvelr salt, C9H11.COOAg, is crystalline, sparingly soluble incold, readily soluble in hot water. On oxidation, the acid is convertedinto isopht'halic acid.Isobutylorthoformotohide, C,H,MeBup.NH.CHO [I : 5 : 21, is obtainedby heating isobutylorthamidotoluene with formic acid at 250" ; itcrystallises in coiourless tables, melts at 105-106", is sparinglysoluble in hot water, readily soluble in alcohol and ether.I f heatedwith excess of zinc-dust, it is converted into isobutzJlorthotolunit1.ile7C6H3MeBup.CN. This crystallises in long, white needles, melts a t59-60", boils a t 248--249", is readily soluble in alcohol and ether,sparingly soluble in light petroleum, and insoluble in water. IsobutyZ-orthotoluic acid, ~ , H 3 M e ~ u ~ . c o 0 H [l : 5 : 21, is obtained, althoughwith difficulty, by the actiori of alcoholic potash on the nitrile; i t crys-tallises in white needles, melts a t 140", is sparingly soluble in hot water,readily soluble in alcohol and ether. The silver salt forms colourlessplates of the formula C,,H,,.COOAg. By oxidation with dilute nitricacid at 240', it is converted into krimellitic acid, thus showing theparent isobutylorthamidotoluene to have the constitution[Me: Bus :NH2 = 1 : 5 : 21.Di-ortjllotoluisobuty Zthiocarbamide, C S (NH.C,H&f eBup)2, prepared byheating an alcoholic solution of isobutylorthamidotoluene with excessof carbon bisulphide, crystallises in long, thin, silky needles ; melts at184"; is sparingly soluble i n hot alcohol, readily soluble in ether.O~thotoluisobutyltliiocarbinzide, C,H,MeBuP.NCS, is obtained in smallquantity in the preparation of the thiocarbamide, but is best preparedby heating the thiocarbamide with syrupy phosphoric acid. It formslong needles, melts at 46", boils, with partial decomposition, a t275--280", and is sparingly soluble in light petroleum, readilysoluble in alcohol and ether. When heated with metallic copper, ityields isobutylorthotolunitrile.Dimeth~lorthotoluisobutylantine,CBH,MeBu@.NMe, [Me : Bus : NMe, = 1 : 5 : 21,prepared by heating isobutylorthamidotoluene with methyl iodideand decomposing the resulting ammonium iodide by digestion withsilver oxide, forms an oil of aromatic odour, boiling at 250-251".The hydrochloride is white and crystalline.The platinochloride,(N~~eaCl,H,,)z,HzPt~~6, forms a red crystalline mass.3 . 3 ISOBUTYLORTHAMIDOTOLUENE,C6H3&leBu@.NHz [Me : Bup : NH, = 1 : 3 : 21,was prepared according to Erhardt's method (Zoc. cit.) ; his descrip-tion of the properties and derivatives of the base is confirmed by theauthor. Couverted into the diazo-chloride, and treated with zincchloride, it also yields metaisobutyltoluene.As according to theoryonly two isobntylorthamidotoluenes can be derived from metaisobutyl-tolnene, and as the constitution 1 : 5 : 2 has been shown to belong tothe author's base, it follows that Erhardt's base must be the 1 : 3 : 2compound. The following derivatives were prepared by methods simi-lar to those employed for the corresponding derivatives of the 1 : 5 : 154 ABSTRACTS OF CHEMICAL PAPERS.base. Isobutylorthoformotoluide, C,H,MeBufl.NH:.CHO [ = 1 : 3 : 21,crystallises in white tables, melts a t 103-105", is nearly insoluble inwater, readily soluble in ether and alcohol. Issobuty Zorthotolunitrile,C6H,MeBug.CN [1 : 3 : 21, is a colourless oil, can be solidified in afreezing mixture, boils a t 242-244", and is readily soluble in alcoholand ether. IsobutyZorthotoluic acid, C6H,MeBufl.COOH [ 1 : 3 : 21,crystallises i n silvery plates, melts a t 132", is sparingly soluble inhot water, readily soluble in ether and alcohol.The silver salt,C1lH1,.COOAg, crystallises in colourless plates. 07:-o~fhotoluisobutyl-thiocarbamide, CS(NH.C6H3MeBuP),, crystallises in white needles,melts at 175", and is soluble in hot alcohol. Orthotolzcisobutylthio-carbimide, C6H,MeBu@NCS, forms a white crystalline mass, melts a t44", and boils a t 267". It was further converted into the correspond-ing nitrile and 1, 3, 2 isobutylorthotoluic acid. A. J. G.Derivatives of Benzoylpseudocumidine : Constitution ofPseudocumidine and Benzaniline. By E. FROEHLICH (Be?., 17,2673--2681).-1n a previous paper (Abstr., 1884, 1319), the authormentioned the formation of benz~,y~I~thalopseudocumidic acid,CGH,. COOH,as an intermediate product of the action of alcoholic potash on hen-zoylpb thalopseudocumide.J t is insoluble in water, and crystallisesfrom alcohol in colourless microscopic needles melting a t 195" withseparation of water; the substance, dried in a vacuum, contains1 mol. H,O.C,HMe,E.NHZ,is insoliible in water, sparingly soluble in alcohol, ether, and coldglacial acetic acid, and crystallises from the hot acid in large, colonr-less, lustrous needles, melting at 170". Attempts to prepare theisocyanide of benzoylcumiditie were unsuccessful, whilst the carbamideand thiocarbamide could not be obtRined in a crystalline form, butonly as resins.The urethane, C,HMe,Bz.NH.COOEt, crystallises fromdilute alcohol in slender, colourless, silky needles melting a t 105".Dimet hy Z benxo!j lpseud ocuni i d ine met hiodide, C6HMe3E .NMe,,MeI, crys-tallises in magnificent, broad, coloudess prisms which, when placed ina vacuum, lose water and fall to a powder; the substance then meltsa t 187" with decomposition. The author discusses the constitutionof pseudocnmidine, and shows that its formula isThe acetyl-derivative of benzoylpseudocumidine,C6H21fe3.NH, [Me : Me : Me : NH, = 1 : 3 : 4 : 61,the amido-group occupying the same position as the h ydroxyl-groupin pseudocumenol. It is evident from this formula that the benzoyl-group in benzoylpseudocumidine cannot occupy the para-posi tion tothe amido-group, and from the close relationship between benzoyl-pseudocumidine and benzoylaniline, it is also improbable that thislatter substance is a para-derivative, as assumed by Doebner (Awnaleti,210, 266).The author thinks that i t is more probably orthamido-benzophenone. Of the phtl al'c derivatives of the three toluidines,that from parntoluidine alone gives a crystalline benzoyl-compoundORGANIC CHEMISTRY. 155whilst the other two yield resinous products. Phthalorfhotoluide,C,H,MeN CBH40,, obtained by heating together orthotoluidine andpbthalic anhydride, is insoluble in water, sparingly soluble in alcoholand ether, readily in hot glacial acetic acid, from which i t crystallisesin colourless needles melting at 182"; i t is converted into phthnl-orthotoluidic acid when heated with alcoholic potash or ammonia.Phthalometatoluide i s insoluble in water, dissolves sparingly in alcoholand ether, readily in hot glacial acetic acid, and forms sniall colourlessneedles melting a t 153" ; it yields phthalometatoluidic acid whentreated with alcoholic potash o r ammonia.Pht7,aZo~aratoliiide meltsat 204" (according to Michael a t 200°, Ber., 10, 579), and is con-verted by alcoholic ammonia or potash into phthaloparatoluidic acid.When phthaloparatoluide (75 grams) and benzoic chloride (45 grams)are heated at 170--180" for 6 to 8 bours with a little zinc chloride,hydrochloric acid is evolved, and benzoylpTathaloparatoZuide,CsH,MeE.N : C8H1O2,is obtained, accompanied, however, by a second substance not Setisolated.Benzoylphthaloparatoluide melts at 202", is insoluble inwater, sparingly soluble in alcohol and. ether, and readily in hotglacial acetic acid, from which it separates in deiise, well-formed,tetragonal crystals. When heated with alcoholic potash, it is con-verted first into benzoylphthaloparatoluidic acid, and then into ayellow-coloured base. It also yields a yellow base (probably benzoyl-tolnidine) with concentrated sulphuric acid. The second substancementioned above appears to be an isomeric compound, C22H15N03, oflower melting point ; it also yields a yellow base when treated withconcentrated sulphuric acid.Derivatives of Parahydroxydiphenylarnine. By &I. PHILIPand A. CALM (Ber., 17, 2431-24=18).-A continnation of Calm'sresearches on this subject (Abst,r., 1884, 592).Para7z~droaydi~hen?/Z-amine hydrobronzide, CI2HlINO,HBr, prepared by the action of hyd1.o-bromic acid on a solution of the base in anhydrous benzene, crystallisesin pale rose-colonred needles, and is very unstable.~~tros~arahydrozyphenylanzine, OH.C6H4.NPh.N0, is prepared byadding sodium nitrite to a well-cooled solution of the base in hydro-chloric acid. It forms yellow crystalline plates, or needles, or redtables, melts at 95", and is readily soluble in benzene, alcohol, ether,glacial acetic acid, and light petroleum. It behaves as a nitrosamine,giving Liebermann's reaction.M e t h y l ~ n r a m e t h ~ y d ~ ~ ~ i e ~ ~ 7 a ~ ~ n e , OMe.C6H4.NMePh, is preparedby heating parahydroxydiphenylamine (1 mol.) with methyl iodide(2 mols.), potash (2 mols.), and a little methyl alcohol for two hours at120-130". It forms a pale yellow oil of violet-like odour, and boils a t313".It behaves like atertiary amine, and yields a green colouring matter when heated withzinc chloride and benzotrichloride.Eth y lparaet hox,ydiphen ylamine, OEt. C&Tu'PhEt, resembles themethyl- compound, and boils a t 31 8-320".Paraisobutox?/cl~lLenyZamiil.e, 0Bup.COHJTHPh. Although preparedA. K. M.It rapidly turns brown on exposure to air136 ABSTRACTS OE' CHENICAL PAPERS.in a manner similar to the compounds just described, only thehydroxylic hydrogen is replaced by isobutyl in this compound. Itforms pale yellow quadratic plateg, melts a t 68", and is readily solublein benzene, alcohol, ether, and light petroleum.For my 1 par ah y dr oxy d ipheyzy lamin e, 0 H.C6H4. N P h. CO 33, prepared byheating the base with sodium formate and excess of formic acid,cryatallises in white needles, melts a t 1 7 8 O , is soluble in ether, hotbenzene, and glacial acetic acid, readily soluble in hot alcohol.Diacetylparaoxydiphenylamine, OZ.CsH,.NPhAZ, prepared in asimilar manner to the formyl-compound, forms large colourless prismsterminated by pyramids, apparently of the rhornbic system, melts a tl20", and is readily soluble in hot benzene, alcohol, ether, and glacialacetic acid.L)ibensoy~paraoxydiphenytamine, oE.c6&.NPhE, prepared byheating the base with benzoic chloride, forms pale yellow, compact,prismatic crystals, melts a t 175", is sparingly soluble in cold, solublein hot alcohol, more readily soluble in glacial acetic acid, benzene,and ether.On nitration, it is converted into a didro-compound,C,,H,,N0,(K02)2, forming a pale yellow, crystalline mass, whichmelts a t 194-195", is readily soluble in hot glacial acetic acid,moderately soluble in ether and hot benzene, very sparingly solublein alcohol. It gives a red coloration with concentrated aqueous soda orpotash ; addition of hydrochloric acid to the alkaline solution causesthe formation of a reddish-brown flocculent precipitate.A. J. G.Action of Carbon Bisulphide on Metaphenylenediarnine.By P. Guccr (Ber., 17, 2656--2658).-When an alcoholic solution ofmetaphenylenediamine is heated with carbon bisulphide, the solutionbecomes red, and hydrogen sulphide is abundantly evolved ; thiscontinues for about eight hours, and as it ceases thin, red prismaticcrystals make their appearance.These are insoluble in water, alcohol,ether, carbon bisulphide and benzene, hut dissolve very readily inammonia, witli orange-yellow coloration, and separate out again onheating tlie solution t o 50-60". From the results obtained on analysis,this substance appears to be a thiocarbol.~ylpIienyle~ze~~aminethiocar-tonate, c,H4<,,>sc.s2c. When the mother-liquor from thesecrystals is warmed, hydrogen sulphide is again evolved, and ayellow amorphous substance gradually separates, which is insolublein water, alcohol, et'her, carbon bisulphide, benzene, and coldammonia.Its formula appears to be CZ0HmN6S2, so that it may bederived either From 1 mol. C,H4(N: CS), and 2 mols. phenylene-diamine, or from 3 mols. phenylenediamine and 2 mols. carbonbisulphide, in which latter case it wouid be a dithioccnrbo?ayZtr~ph(~n~Z-enedianz ine, NH,. C,H,.NH. S C. NH. C6&. NH. S C. NEE. C6&. NH2. Onpouring the mother-liquor from this into water, a third substance,CI2H1 3N,S,, is obtained as an abundant orange-yellow amorphousprecipitate, extremely soluble in alcohol.NHA. K. 141ORGANIC CHEMISTRY. 157Mixed Azo-compounds. By E. BAMBERGER (Ber., 17, 2415-2422>.-Ethyl orthonitrophenylazoacetoacetate,C6H4 ( NOz). Nz . C H E . C 0 OE t ,is prepared by dissolving 3 grams orthonitraniline in hydrochloricacid, cooling with a mixture of ice and salt, and adding a diluteaqueous solution of 1.5 grams of sodium nitrite ; after remaining for1 2 hours, the mixture is largely diluted with water, neutralisedwith soda, and a dilute solution of, ethyl acetoacetate (2.9 grams) andpotash (1.3 grams) added drop by drop.After adding a few dropsof soda, the mixture is allowed to remain for a day in a warmplace, when the new praduot separates as a hard crystalline crust. Itis obtained on recrystallisation in lustrous golden-yellow plates, meltsa t 92-93", is readily soluble in alcohol, ether, glacial acetic acid, andchloroform, and also soluble in hot water.0 r f h o nit ropheny Zazoacetoacetic acid, C,H,( NO,) .Nz.CH hc. C 0 OH, isprepared by heat;ing the ethyl salt on the water-bath with potash for1-2 minutes, the potash salt which separates then being decomposedby hydrochloric acid.' It crystallises in lustrous golden-brown platesresembling mosaic g d d ; when heated, it blackens a t 183" and meltsat 185" with evolution SF carbonic anhydride ; it is readily soluble inglacial acetic acid,.glycerol, and hot alcohol, sparingly soluble in etherand cold alcohol. The ammonium salt forms golden-yelluw needles,the lead salt ayellow .pwder, the copper salt is obtained in greenflocks,and the bm-ium salt crystallises in tufts of yellow needles.Orthonitropl~snyZnzouct:to~~e, C,H4( N02).N, CH,.COMe, is obtainedby heating the acid (best mixed with glycerol), by heating either thefree acid or the ethyl salt with potash or, best, as follows : an alcoholicsolution of orthonitraniline is treated with the nitrogen oxidesevolved by the action of nitric acid on arsenious anhydde, the pro-duct of the reaction is poured into water, filtered, and the filtratemixed with ethyl acetoacetate and potash, and tbe whole digested for15 minutes a t 40" The mixture of nitrophenylazoacetone and a littleethylic nitrophenylazoacetoacetate which is then precipitated, isheated for a few minutes with alcoholic potash and poured into a largevolume of water, when the ketone separates in voluminous yellowflocks and can be purified by crystallisation.It crjstallises in long,silky, sulphur-yellow needles, melts a t 123-124", and is soluble inall the ordinary solvents? but is insoluble in alkalis.Orthoarnidoazoacetic acid, C6H4(NH,).N,.CHG.COOH, obtained bythe reduction of the nitro-acid with ferrous siilphate and ammonia,crystallises in satiny orange-red tables, melts with decomposition atl57", is very readily soluble in gtacial acetic acid and chloroform,moderately soluble in ether, somewhat soluble in water. It is veryunstable.The corresponding members of the toluidine series were prepared bysimilar methods from metanitroparatoluidine.Metanitroto Z~Ziual.aaznaeetoacetic acid, C6H.3e( NO,). N?. C H Z . C 0 0 €3,crystallises in long yellow needles, melts a t licj", is readily soluble inglacial acetic acid, alcohol, and glycerol. It is converted into thocorresponding ketone by the action of heat or of alkalis.VOL.XLVI1:. 158 ABSTRACTS OF CHEMICAL PAPERS.MetanitrotoZy Ilparaazoacetone, C6H,Me(N0.L).N,.CH,,COMe, crystal-Metamidoparaazoacetoacefic acid, C,H3Me (NH,) .N2. CHZ. C 0 OH,lises in lustrous orange-red prisms and melts a t 134-1 34.5".forms brick-red needles and melts at 162". A. J. G.Action of Acetic Anhydride on Benzamidine. By A. PINNER(BcT., 17, 2511-2516).-The author has reinvestigated the bodyC,,H,,N,, described by himself and Klein (Abstr., 1878,491; 1883,1099;and 1884, 1324) in order to determine whether this or C9H,N, is its trueformula. If its composition were C9H8N2, it must have the constitu-tion C61-f,.C<N>cMe, and should then yield a carboxylic acid onoxidation : but neither permangsnate nor chromic acid has any actionon it.When bromine is added to a solution of the substance inchloroform, deep yellow needles are deposited which appear to be abromine additive product. This compound is, however, very unstable,and the analytical results obtained agree as well for C,H,N,Br, asfor C,,H,,N,Br,. When dissolved i n fuming nitric acid, the oiiginalsubstance yields a compound which gives numbers correspondingfairly well with the formula C,dH,(N02)aN,. The most conclusiveproof of the correctness of the formula C1,H1,N3, however, is theformation of a mmosdphonic acid, CIdH,,N3. SO,H, by dissolving theoriginal substance in fuming sulphuric acid. This acid crystallises innodules with $H,O, and loses its water of crystallisation a t 140", butis then partially decomposed. It forms a crystalline sodiu,m saZZRolulde in water ; the barium saZt crystallises with 1OH,O in glisteningscales, very spwingly soluble in water.When fused with potash, theacid yields parahydroxybenzoic acid. When heated a t 100" withconcentrated hydrochloric acid, the original substance deposits a com-pound in shining scales, which is decomposed on the addition ofwater into the previously described hydrochloride. When heatedwith twenty times its weight of hydrochloric acid in closed tubes atlOO", the original substance is decomposed into benzoic acid andammonium chloride.From these results, there can be no doubt that, the substancc isdibsnzimidine, NH : CPh.N CPh.NH,.The author also attempted to determine the molecular weight ofcganphenine by preparing its sulphonic acid.The acid obtained con-tained one S03H-group t o every seven carbon-atoms, and thus gaveno clue to the molecular weight.NL. T. T.Action of Ethyl Acetoacetate on the Amidines. By A.PIKNER (Ber., 17, 2519--2520).-Ethyl acetoacetate reacts extremelyreadily with the amidines, water and alcohol being eliminated.X . C < ~ ~ , + Me.CO.CH,.COOEt = R.C<E>C4H60 + H,O+ EtOH.The compounds formed have basic properties. and their constitution iORCIANIO 0HE;IIISTRY. 159N co- probably R.C<": CMe>CH2. By means of phosphoric chloride,&c., they may be converted into derivatives of the nucleus,Benzamidine and ethyl acetoacetate thus yield a compound,CllH,ON20,which crystallises in prisms melting a t 215.5-216", and is sparinglysoluble in ether.It dissolves easily in acids, and yields a sparinglysoluble pl atinochlorid el ( C,,H1oNZO) Z,H2Pt GI6 + H20. When heatedwith phosphoric chloride, the compound C11HlnN20 yields a substanceof the formula CllH9NZCl, melting a t 71". This body is soluble inether, insoluble in water, and crystallises in rhombic plates. Theconstitution of the chloride is probably CPheNi CMe> CH.Acetamidine when similarly treated yields a compound, C6H8N20,which forms long silky needles soluble in water, sparingly so in ether.The amidines also react easily with the cyanates and isothio-cyanates. The author is now investigating these reactions.N CCI-L. T.T.So-called Phthalylacetarnide. By W. ROSER (Ber., 17, 2623-2625)..-This compound is an acid, and therefore cannot have the con-stitution implied by the name which was given to it by Gabriel. Theauthor suggests t)he name plithalimidylacetic acid. The calcium saltcontains + mol. H20, and forms a white crystalline precipitate, almostinsoluble in water ; the barium salt is readily soluble in hot water andcrystallises in small prisms containing 2 mols. HzO ; the silver salt,C IoH603NAg, is insoluble and amorphous. When phthalimidylaceticacid is boiled with alkalis, ammonia is liberated and acetuphenone-carboxylic acid produced. Of the two formulz for phthalimidylaceticacid, GO< G$>C.CH2.COOH, and CO< kE4>C CH.COOH, thefirst is considered the more probable, for if the second formula werecorrect, the compound CO<&;>C : CH.COOH should be formedby the action of methylamine on phthalylacetic acid ; this, however,is not the case.Gabriel's phtbalylpropionamide is probably phthalimidylpropionicacid.By the action of sodium-amalgam on phthalimidylacetic acid inalkaline solution, a dark violet-coloured liquid is obtained whichyields an almost black precipitate on the addition of hydrochloric acid.By H.KOLBE (J. pr. Chem.,30, 124--125).--k former communication (this vol., p. 58) con-tains an account of the preparation of isatoic acid from isatin ; thisacid when boiled with concentrated hydrochloric acid is resolved intocarbonic anhydride and anthranilic acid.This decomposit'ion offers aconvenient method of preparing anthranilic acid.CH C HC HA. K. M.Preparation of Anthranilic Acid.P. P. B.'m160 ABSTRACTS OF OHEMICAL PAPERS.Betaines. By R. SILBERSTEIN (Rer., 17, 2660-2665) .-Whenphenxlbetalns hydrochloride is heated a t about lOO", it splits up intodimethylaniline, carbonic anhydride, and methyl chloride. Onheating ethylic phenylbetayne chloride, or a mixture of ethyl chlor-acetate and dimethylsniline at a temperature not exceeding 130°, thefollowing reactions take place :and NPhMe.CH,.COOEt + 2HC1= NPhMe.CH,.COOH,HCl + EtC1.The phenylmeth~Zg7ycocine h ydrochzoride, NPhMe.CH2.COOH,HC1, ob-tained, forms colourless prisms readily soluble in water, less so inalcohol, and very sparingly in cold concentrated hydrochloric acid.Itis decomposed by continued heating with water with evolution of car-bonic anhydride and formation of dimethyl aniline hydrochloride. Whena mixture of dimethylaniline (1 mol.) and chloracetamide (1 mol.)is digested in alcohol, and the solution, after concentration, precipi-tated with ether,.plier~?llbetnzneamide chloride, NPhMe,CI.CH2.CONH,,is obtained. This, heated to 110-120", yields methyl chloride andphenl~/~neth?~lgZycocineu~~~~~e, NPhMe.CH,.CONH,, which is sparinglyfioluble in cold, moderately in hot water and in alcohol, from which Itcryshliises in silky prisms or scales melting a t 163" ; it sublimeswhen carefully heated, but, on distillation, is decomposed into ammonia,dimethylaniline, and other products ; when boiled with alkalis, ityields pheny lmet h ylgl ycocine.Pheny lmet hy lgl y cocinearnide hy dyo-chloride forms colourless prisms, readily soluble in water, moresparingly in alcohol. Phenylmethylglycocineamide is also producedwhen methylaniline and chloracetamide are heated together, and thehot aqueous solution precipitated by ammonia.Whm dichloracetic acid is heated with dimethylaniline, it appa-rently breaks up into carbonic anhydride and dichloromethane, whilsttrichloracetic acid yields chloroform and carbonic anhydride. I n thelatter reaction, an intermediake product can be obtained (probablyNPhMe,Cl.CCl,. COOH).Diethylaniline and methyldiphenylamine when heated with chlor-acetamide yield neither ethylic nor methylic chloride.The abovereaction with trichloracetic acid, however, may be effected not onlyby means of dimethylaniline, but also by diethylaniline, methyldi-phenylamine, quinoline, and pyridine.NPhMe2C1.CH2.COOEt = NPhMe.CH,.COOEt -t MeCl,A. I(. M.Action of Benzaldehyde on Nitromethane and Nitro-ethane.Ry B. PRIEBS (A?/naZen, 225, 319-364).-The preparation of phenyl-witroethlylene, CHPh : CHNO,, by the action of nitromethane on benz-aldehyde in t'he presence of zinc chloride has been previouslydescribed by the author (Abstr., 1884, 313). The formation of thiscompound may serve as a reaction for the detection of nitromethane.For this purpose the dilute solution, supposed to contain nitro-methane, is mixed with sodium hydroxide, and well shaken with anexcess of benzaldehSde.The unaltered benzaldehyde is removed byextraction with ether, and a current of air is passed through thesolution to expel the last traces of ether. On adding dilute sulphuriORGANIC CHEMISTRY. 161acid, a crystalline precipitate of phenylnitroethylene indicates thepresence of nitromethane. Phenylnitroethylene is identical withSimon's nitrostyrene (AnnaZen, 31, 269). It may therefore be pre-pared by the action of nitric acid, or better, of nitrous anhydride on itcold ethereal solution of styrene. Phenylni troethane yields benzoicacid on oxidation. With nitrous acid, it exhibits the nitrolic acidreaction. At 85", sulphuric acid (diluted with one-third its volume ofwater) decomposes phenylnitroethane into hydroxylamine, benzalde-hyde, and carbonic oxide, and strong hydrochloric acid splits it upinto phenylchloracetic acid and hydroxylamine. On exposure to thelight, phenylnitroethylene undergoes a gradual transformation intoisophenylnitroethylene, which is deposited from alcohol in rhombicneedles or plates melting between 172" and 180".PhenyZrLitroethy Zenedibromide, CHBrPh.CHBr.N02, prepared by adding bromine to nsolution of pheuylnitroethylcne In carbon bisulphide, crystallisesin the monoclinic system, namely, in a combination of OP withcmP . cmP00 and Po0 ; ,B = 83" 54'; a : b : c = 1.2568 : 1 : 1.3960. Thecrjstals dissolve freely in chloroform, benzene, and carbon bisulphide,and are decomposed, by boiling with alcohol, into hydrobromic acidand phenylbromonitroethylene, CBrPh : CHNO,.'l'he latter com-pound is more easily prepared by the action of soda instea,d of alcohol.It crystallises in iridescent golden needles 01' plates which melta t 67".When chlorine is passed into a solution of phenylnitroethylenedissolved in chloroform, the dicldoride, CHClPh.CHC1 NO2, is ob-tained as a thick syrup, which crystallises with difficulty; thecrystals melt a t 30". Phen yZchZoronitroeth?yZene, CClPh : CHN02, isdeposited from light petroleum in golden piates or needles which melta t 48".On nitration, phenylnitroethylene yields two isomeric nitro-pro-ducts ; if the acid is cooled in a freezing mixture, the para-derivativeis mainly formed, but a t a temperature of 25" a considerable quantityof the ortho-derivative is prodnced.Parnnr'trophenyZ.r~itroet1~ y Zene, N02.C,H4.CH 1 CH.N02, has been pre-viously prepared by Priedlander and Miihly (Bsr., 16, 848), fromparanitrvcinnamic acid.It unites with bromine, forming a dibromidemelting a t 102"; this crjstallises in colourless plates, soluble inbenzene and in glacial acetic acid. The orthonitro-compound is muchmore soluble in alcohol and other solvents than the para-derivativeIt forms needle-shaped crystals melting a t 106", which turn brown onexposure to the light. The dibromide also crystallises in needlesmelting a t 9U", which dissolve freely in chloroform, beczene, and inhot acetic acid.CMe.N02, is prepared by the actionof zinc chloride on a mixture of benzaldehyde and nitroethane.Theyield is by no means so good as in the case of phenylnitroethylene, asbenzamide and resinous bye-products are also formed. Pheny initro-propylene resembles the ethylene compound in many of its prnperties.It readily crystallises in rhombic prisms which melt a t 64". It-yieldsbenzoic acid on oxidation, and is decomposed by boiling alkalis intobetzaldehjde and ni troet'hnne. The dibromide, CHBrPh.CBrMe.NOz,Phen yZnitrop*opyZene, CHP162 ABSTRACTS OF CHEMICAL PAPERS.forms transparent prisms which melt between 77" and 78.5". This com-pound is not decomposed by alkalis.YuI.aniti-~hen,~lnitro;uro~ylene forms yellow needle-shaped crystalswhich melt at 114". The orthonitro-product forms pale yellow plateswhich are much more soluble in alcohol than the para-compound.The crystals melt a t 76".w. c. w.Paracarvacrotic Aldehyde. By E. NORDMANN (Rer. 17, 2632-2634) .--This aldehyde is obtained from carvaurol together with somesecondary products, by means of the chloroform reaction. It crystal-lises in white, flat, silky scales, melts a t 96", is insoluble in cold,sparingly soluble in hot water, readily in alcohol, ether, benzene, andchloroform, also in dilute sulphuric acid with greenish-yellow colora-tion. It gives no characteristic colour with ferric chloride, and fromthis it is concluded that the group COH has taken up the para- andnot the: ortho-position in reference to the hydroxgl group. Theformula ofpuracarvncrotic aldehyde is thereforeC6H,MePr(OH).COH [Me : OH : Pr : COH = 1 : 2 : 4 : 51.Like parathymotic aldehyde (Abstr., 1884, 56), it does not combinewith the hydrogen alkaline sulphites, but yields crystalline compoundswith aniline and phenylhydrazine.Action of Bromacetophenone on Amides. By F.0. BL~MLEIN(Ber., 17, 2.578-2581) .-On heating bromacetophenone with amides,there are formed neither the amides of acetophenone, nor isoindolesderived from them by the abstraction of a molecule of water, but sub-stances which differ from the latter class in containing about 2 percent. less carbon than that required by theory.Thus, if bromacetophenone be heated with acetamide, there isformed a basic substance crystallising in long needles ; this melts a t45", boils a t 241--'242O, and is easily soluble in alcohol and ether.Its hydrochloride forms a white crystalline powder.The corresponding compound obtained with formamide forms a,crystalline mass, and the benzamide compound forms crystals whichmelt at 103" and boil a t 339".It is proposed to investigate moreclosely the constitution of these substances.(Dingl. polgt. J., 254,23l.)-Onheating diphenyl carbonate with sodium phenate, basic sodium silicyl-ate is produced, in addition to phenol and diphenyl ether. (ChemischeFubrik u.f' Actien, formerly E. Schering, Berlin.) To prepare sa,li-cylic acid, 50 kilos. of diphenyl carbonate is heated with 54 of sodiumphenate €or 6 hours a t 160-170", with constant agitation ; the salicylicacid being subsequently extracted from the saline product.Brominated Phthalic Acids. By F.0. BLi?JlLEIN (Bey., 17,A. K. M.V. H. V.Preparation of Salicylic Acid.D. B.2485-2497).-When a-naphthol is treated with excess of bromine, acompound is formed containing six bromine-atoms in the molecule.This is very unstable and is probably a dibromo-additive product oftetrabromonaphthol, C,oH3Br4.0H,Br2, or a tetrabromo-additive proORGANIC CHEMISTRY. 163duct of Biedermann's dibromo-a-naphthol (Ber., 6, 1119). Theauthor has not further investigated this compound, but has studiedthe bromination of a-naphthol in the presence of aluminium bromide.In this way, the-author obtained a pentabromo-z-naphthol, C10HBB~*5.0H,which melts a t 238-239", crystallises in pale straw-coloured needles,and is almost insoluble in alcohol and ether, and only sparingly solublein boiling benzene, xylene, or cumene.The yield was about 90 percent. of the theoretical. This compound dissolves in alkalis to formmetallic compounds : CloH,Br,.ONa crystallises i n long needles, solublein alcohol and water: C,,H,Br,.OK in small colourless needlessparingly soluble in water.When oxidised with dilute nitric mid (one part C,,H,Br,.OH to 10parts acid of sp. gr. 1-15) a t loo", pentabromo-or-naphthol yields tetra-brorno-a-napJu%quinone, CloH2Br4.a. This compound crystallises ingolden-yellow scales which melt a t 265" to a dark liquid. It can besublimed with care, and is soluble in glacial acetic acid and inbenzene, sparingly so in alcohol and ether. It is isomeric with the tetra-bromo-@-naphthaquinone obtained by Fleasa (Inaug.Bissert., Zurich,1884). If the oxidation of the pentabromonaphthol with dilute nitricacid is carried out at 150°, instead of a t loo", and the action con-tinued f o r about 18 hours, dibromopkthalic acid, C6H,Br,( COOH),,is formed ; under similar circumstances Flessa's pmtnbromo-6-naphthol yielded tribromophthalic acid. Dibromophthalic acidcrystallises in long aggregated needles which are easily soluble inalcohol, ether, and boiling water, sparingly in petroleum. It melts a t206", and is converted into the anhydride. Dibromophthalic anhydride,obtained by sublimation of the acid, crystdiscs in long colourlessneedles melting at 208". It is easily soluble in alcohol, spariugly soin ether and water.The salts of dibromophthalic acid, except thoseof the alkalis, are sparingly soluble, and contain no water of crystal-lisation. The calcium salt is deposited as an amorphous precipitate,which becomes crystalline on standing ; the barium salt is similar tothe calcium ; the s i h e r salt forms a flocculent precipitate soluble inmuch boiling water, and crystallises from this solution in smallcolourless plates. When the anhydride is fused with resorcinol, abrominated fluoresce'in appears to be formed. This compound issoluble in alkalis and in alcohol to a red solution with an intensegreen fluorescence.Action of Bromine on Ortkoxy lene in Presence of Alunainiurn.--Inthis way, a tetrabromo-xylene, C6BrlMe2, was obtained, in which thebromination took place entirely in the benzene nucleus. This com-pound crystallises in colourless silky needles, melts a t 2541-255", anddistils without decomposition a t 374-375O.It is easily soluble inbenzene and xylene, almost insoluble in alcohol and ether. Tetra-bromo-xylene is not acted on by dilute nitric acid (sp. gr. 1-15> belowabout 250-2SU0, and then the oxidation is only partial. Nitric acidof sp, gr. 1.20 effects the Oxidation at 180-200", but the productconsists of a mixture of tetrt~bronzophthalic and tribromomononitro-phthalic acids, the complete separation of which could not be effected.If 5 grams of tetra,bromo-xylene are heated a t 170" with 50 C.C. ofnitric acid of sp. gr. 1.15 and about 10 grams of bromine, tstrabromo164 ABSTRACTS OF CHEMICAL PAPERS.phthabic acid is alone produced. This crystallises in small needles, verysparinglg soluble in the usual solvents.At 266" it melts and is con-verted into the anhydride. Tetmbronzophthalic anh.ydride, obtained bysublimation of the acid, forms small glistening needles which melt a t258-259", and are almost insoluble in the usual solvents. Thealkaline tetrabromophfhaZates are easily soluble, the salts of the otlhermetals sparingly soluble or insoluble. The bariunz and calcium saZfsform white crystalline powders. When fused with resorcinol, tetra-bromophthalic acid yields a brominated fluorescejin isomeric witheosin. This compound is soluble in alkalis to a dark red solutionshowing intense green fluorescence.From the above results, it is clear that in the pentabromonaphtholformed by the action of bromine on a-naphthol in the presence ofaluminium bromide, the three hydrogen-atoms of the nucleus con-taining the hydroxyl have d l been replaced by bromine, but theposition of the remaining two bromine-atoms in the other nucleus isuncertain.In the tetrabromo-xylene all the bromine-atoms are in thebenzene-ring. L. T. T.Constitution of Phthalylacetic Acid, By S. GABRIEL (Ber., 17,2521-2527) .-When phthalylacetic acid is distilled in a vacuum,carbonic acid i s evolved, and the distillate comprises a yellowish-whitesemi-solid mass. If a current of steam is driven through this mass,the distillate deposits small shining rhombic prisms, which melt a t58-60', have an odour resembling that of phthalide, and are solublein water.On keeping, however, they gradually polymerise to a yellowvitreous and odourless mass. Some of this polymerised body is alwaysformed in the retort when the white substance is distilled with steam.It is partly reconverted into the original volatile compound by distil-lation in a vacuum. The frehhly prepared volatile compound has thecomposition C9H602, and its constitution must therefore be either-C=CHa(a) C6H,<Eg>cH2, or ( 6 ) c6H4' >o This compound can 'coalso be obtained from the resinous bye-products obtained duringthe preparation of. phthhlylacetic acid. When treated with bromine,this compound absorbs Br2, yielding a crystalline substance, C9H,Rr2O2,melting a t 98-99'.The original volatile substance must thereforebe methylenephth~alide, and have the formula ( b ) , and the bromoderiva-tive must be methybenepkthalide bromide, c6H /CBr.CH2Rr0 qco/When gently warmed with potash, methylenephthalide is convertedinto acetophenon ecarboaylic acid ; probably according to the equationsIf the dibromide is boiled with water, it gives up hydrobromic aciORGANIC CHEMISTRY. 165and yields a methylenephthalicle oxide, C9H603. This crystalline com-pound melts at 144-146", and is identical with that previouslyobtained from acetophenonecarboxylic acid ( Abstr. 1878, 734).P11 thalylbromacetic acid, when similarly treated, yields a com-pound which is identical with bromomethyZe?ze~hthaZyZ, previouslyobtained by bromination of aceto piienonecarboxylic acid (Zoc.cit.).The name of this comDound should therefore be changed to bromo->o. C:CkiBr methyZeneph,thaZide, and its formula would be C,H4<- co-The compouiid previously described as benzylidenephthalyl alsoforms a crystalline dibronzide melbing a t 146", and should therefore becalled benzylidenepht~ialide; its formula is C6H4<<-cO ->O. Thedibromide, when boiled with alcohol, is converted into the crystallinecompound CI5Hl0O2Br.OEt, which melts at 149".C'CHPhL. T. T.Phthalyl Derivatives ; Conversion of Ketonic Acids intoLactones. By W. ROSER (Bey., 17, 2t;19-2622).-When ethylene-benzoylorthocarboxylic acid is dissolved in about 15 parts of concen-trated sulphuric acid, and the solution allowed to remain for sometime in the cold, slender yellow needles of ethinediphtbalyl separate :C O OH.C6H4. C 0. C Hz. C H?. C 0. CsH4. C O O H - 2 HZO =CO<??>C CH.CH: C<?Z>CO.When a solution of benzoylacetorthoc,arlooxylic acid in concentratedsulphuric acid is precipitated with water, phthalylacetic acid isobtained, as observed by Gabriel (Bw., 17, 2526), but this acid meltsabove 260" according to the author, and a t about 276" decomposeswith evolution of gas. By similar treatment, acetophenoneortho-carboxylic acid Tields a compound melting a t 213-215", insoluble inwater and cold alkalis, sparingly soluble in alcohol, and readily inacetic acid, from which it crystallises in colourless scales. It isperhaps a polymeride of Gabriel's phthalidimethylene, C9H6O2.Itmay be concluded from these experiment,s that acids containing thegroup :CH.CO.C,H,.CoOH [l : 21 are converted into lactones byconcentrated sulphuric acid. When et hylenebenzoylort hocarboxylicacid is heated with 10 parts concentrated hydrochloric acid in a sealedtube, the product washed with water and extracted with boilingalcohol, a residue of ethinediphthalyl remains, whilst the alcoholicsolution contains the anhydride CpH4<&~c~H~~Co>0. This is in-soluble i n water and cold alcohol, but crystallises from hot alcohol inslender silky needles melting at, 230-231'. It agrees in its pro-perties with the compcund obtained by Gabriel by heating the di-ketonic acid. A. I(. M.C O C H COReduction of Phthalimide and Phthalide. By C.GRAEBE (Bey.,17, 2598-2600) .-By the action of tin and hydrochloric acid,phthalimide is converted into a base of the composit'ion C,H,NO, whic166 ABSTRACTS OF CHEMICAL PAPERS.crystallises in needles melting a t 150", and boiling at, 337"; it issoluble in alcohol and ether, sparingly solixble in water. From itsready formation, and its reconversion into phihalide, one of *hefollowing forrriula can be assigned to it :the former of which the author considers the more probable, andassigns to it the name yhthuIzdhe. With sodium nitrite, i t forms itnitroso-derivative, C,H,<C(:;~Y?>O, which crystalliscs in goldenneedles melting a t 1X0, sparingly soluble in water, readily soluble inhot alcohol ; on heating it with soda, i t is converted into the mon-hy d roxy l-deri vative of meth y lbenzoic acid, OH.CH2. C,H,. C 0 0%.Phthalimide is converted into phthalide by treatment with tin andhydrochloric acid, and t'he addition of sodium nitrite to the product.The nitroso-derivative separates out, and phthalide is obtained on pre-cipitating its alkaline solution w,ith acid. Through the intermediateformation of this substance, phthalic acid may be converted intoorthoxy lene. V. H. V.Constitution of the Benzenetetracarboxylic Acids. By 0.JACOBSEN (Bey., 17, 2516--2518).--In order to determine the con-stitution of the three benzenetetracarboxylic acids, the author preparedtwo of them by the oxidation of durene, C,H,Me,. [l : 2 : 4 : 51, andisodurene [l : 2 : 3 : 51.Dureiie was first boiled with di1ut.e nitric acid,arid thus converted into a mixture of durylic and cumidic acids,and this mixture was then oxidised with permanganate. The tetra-basic acid thus obtained proved to be pyromellitic acid. By similartreatment', isodurene yielded mellophanic acid. The constitution ofthe three isomeric acids, therefore, must he :-Pyromellitic acid,C,H,(COOH), [I : 2 : 4 : 51 ; mellophanic acid, [1 : 2 : 3 : 51 ; andphrenitic acid, [l : 2 : 3 : 41. L. T. T.Action of Sulphuric Acid on AcetophenoneorthocarboxylicAcid. By S. GABRIEL (Ber., 17, 2665-26681.- When concentratedsulphuric acid (1 5 grams) is added to acetophenoneorthocarboq-licacid (1 gram), an amber-coloured solution is obtained; this is allowedt o remain for 24-48 hours arid then poured into water, when a brownresinous substance (A) separates.The filtrate yields a furtherseparation of a fine white powder (B) on standing. The substance Aforms (after purification) dense, yellow, pointed crystals melting a t215-216*5", sparingly soluble in alcohol, insoluble in alkali and inammonia. When it is heated a t 150-160"with hydroxylamine hydrochloride and alcohol, it yields an oximido-derivative, ClsH1203 : NOH.The second substance (B) is readily soluble in alcohol, glacialacetic acid, and in fixed and volatile alkali, from which it can be pre-cipitated by the addition of an acid; it melts at 132-135". Itsformula, C18H1,05, indicates that it is formed by the abstraction of oneIts formula is CleH1,04ORUANIC CHEMISTRY.167mol. H,O from 2 mols. acetophenoneorthocarboxylic acid. Thissubstance is a monolnasic acid (diacetophenor~ecarbozy Zic acid), asshown by the composition of the silver salt, C,8H,305Ag, and thebarium salt, (C18H,305)2Ea. When it is heated f o r some time aboveits melting point, it is converted into the compound ClsH,,Oi.A. K. M.Preparation of Isatin. (DingZ. polyt. .J., 254, 232.)-The pre-paisation of this substance forms the subject of a patent taken out, bythe FarJ,enfabriken, late F. Bayer and Co. Instead of convertingthe products of the reaction of dichloracetic acid with aromaticamines directly into isatin, it is proposed to subject them to a processof oxidation, it having been found that during the reaction and thesubsequent process of purification oxidation by atmospheric oxygentakes place, and that the yield of imesatin, o r substituted imesntins,depends on the exteiit of this oxidation process. D.B.Methylated Indoles. By A. LTPP (Ber., 17, 2507-2511).-O~thomethylumidoclzlorosfyrene, CHCl : CH.C6H4.NHDle, was preparedby treating an alcoholic solution of amidochlorostyrene with the cal-culated quantity of methyl iodide. It is heavier than water, is easilysoluble in alcohol and ether, very sparingly so in water. I t is liquidat ordinary temperatures, may be distilled with steam, but not alone.It dissolves in hydrochloric acid to form a hydrochloride whichcrystallkes in small needles. When heated with sodium ethylate at1;3%--140", orthomethylamidochlorostyrene yields the same methyl-indole which Fischer and Hess obtained from methylphenyihydrazine-pyroracernic acid (Abstr., 1884, 1180).This reaction proves thecorrectness of the formula proposed for this body by Fischer andHew, as its formation must take place according to the equations-(I.) NHMe.C6H,.CH : CHC1 + NaOEt =NHMc.C6H4.CH CH.OEf; + NaCl.(11.) NHMe.C6H,.CH : CH.OEt = C6H4<~cH>CH 1 Me + Et.OH.Baeyer and Jackson's met,hylketole has the formulaso that skatole, the remaining methylindole containing the methylgroup in the side-chain, must be represented by the formulaL. T. T.Tolane Tetrachloride. By L. GATTERMANN (Ber., 17, 2601).-Schupphaus recently referred to a compound obtained by the action ofchlorine on boiling toluene (Abstr., 1884, 52), and it wits thoughtprobable that this might be a new dichlortolnene.The author finds,however, that the substance in question is tolane tetrachloride,CPhCI,.C2i1PC2, which was obtained in the same way by Liebermannand Homeyer (Abstr., 1880, 259). A. I(. M168 ABSTRBOTS OF CHEMICAL PAPERS.A New Method of Preparing Secondary Arnidoazo-deriva-tives. By R. HENRIQUES (Bey., 17, 2668--2673).--EthyI-lu-na~ht~c?ll-anline may be prepared from P-naphthylamine, and forms ZL thick oilwhich boils without decomposition, and does not solidify in a freezingmixture ; its hjydroc?dol-ide, C,,H,,N,HCl, is sparingly soluble in cold,moderately in hot water, crystallises in scales, melts a t 235", anddistils with but slight separation of hydrochloric acid.It forms anitrosamine, CI,H,,N,O, which melts at 49", and yields a yellowcoloration with concentrated sulphuric acid, When nitrosoethyl-naphthylamine and aniline are heated together in solution in glacialacetic acid, a violent reaction sets in, and a deep red liquid is obtainedwhich is kept boiling for some time; this deposits benzazoethyl-P-.nuphthyZamine, PhN2.C,,H6.NHEt, on cooling. The same compoundis also obtained from diazobenaene and ethylnaphthylamine. It formsred needles melting at 102-103°, is insoluble in water, but yieldsorange-red solutions with alcohol and other solvents. With concen-trated acids, it gives bluish-violet salts which are decomposed bywater. It yields a nitrosamine which forms rubj-coloured crystalsmelting a t 97"; when this is treated with aniline in glacial aceticacid, the nitroso-group is removed and the amidoazo-compound re-produced.Nitrosoethylnaphthylamiiie reacts with ortho- and para- toluidinein the same way as with aniline, the compounds obtained meltingrespectively a t 1'32" and 112-113".With amidoazobenzene, it formsazoZ,enze.rreazoethyl-~-naphtkylamine, PhNZ.C6H4.N,.C,,H6.NHEt, which,for comparison, has also been prepared from diazoazobeneene andethylnaphthylamine. It forms small cherry-red crystals, melts at141-142", and gives a deep blue colour with sulphuric acid. Thereaction with diamines is apparently less simple ; metaphenylene-diamine and toliiylenediamine give brownish-red dye-stuffs with thenitrosamine, whilst paraphenylenediamine gives no colour reaction.Methy lamine and phenylhydrazine do not react with nitrosoethyl-naphthylamine.Experiments in which the nitrosamine was treatedwith aminesulphonic acids yielded negative results ; no combinationoccurs i n glacial acetic acid solution, but if hydrochloric acid isadded colouring matters are formed.Streiff '8 nitrosophenyl-6-naphthylamine (AnnnZen, 209,157), whensubmitted to the above reaction with aniline, yields benzeneazophenyl-P-nnphthylamine, C'L2H17N3, corresponding with the ethyl-compound.It forms compact dark-red needles of metallic lustre, melting a t128-129" ; the mother-liquor contains phenylnaphthplamine, thisreformation of the amine constituting the chief reaction in the caseof the other nitrosamines which the author has examined.Nitroso-ethyl-a-naphthylamine and aniline yield, for instance, amidoazoben-zene, ethylnaphthylamine, and a little benzene~znethyZ-oc-na~l~t??yla~~n~,C,,H,,N, ; this is a stronger base than the @-compound, forms large,bright-red, transparent crystals, melting a t 58-59") and yields saltscr-jstallising readily in violet needles ; it gives a bluish-violet colourwith salphuric acid, Nit,rosodiphenjlamine and aniline (see alsoBer., 10, 1309) yield diphenylamine as the chief product, also amido-azobenze-ue and a small quantity of phenylamidoazobenzene, SimilaORGANIC CHEMlSTRY. 169results are obtained from nitrosomethylaniline and aniline. I n theaction of aniline on the nitrosamines of more complex substances,such as carbazole and tetrahydroquinoline, the NO group is eliminatedand the amine is reproduced.Nitrosonaphthol and its Derivatives.By 31, ILINSKI (Ber., 17,2581-2593).-a-Nitroso-/3-naphthol is best' prepared from /3-naphtholby the process suggested by Stenhouse and Groves (comp. Trans., 1884,294) ; in addition to its properties described by former workers, theanttior finds that it is volatile in a current of steam when pure, but ifimpure it forms resinous matters.Its potassium-derivative, C,oH,NO,K, crptallises in metallic, glisten-ing leaflets, soluble in water. Its n~nmo?az'u~n salt, crystallising in thesame form, is stable only in an atmosphere of ammonia ; on boilinga solution of the ammonium salt, t,he corresponding amido-deriva-tive, is formed.I t s silvw salt forms a red-brown powder, insolublein water and alcohol ; the siZwr-nnimonium salt crystallises in deli-cate green needles, and the hydrogen-siZver salt forms a microscopiccrystalline preciptiate. By the action of methyl iodide on the normalsilver salt, there is obtained the methyl ether of a-nitroso-P-naphthol,C,,H,NO2Me, which crystallises in long prismatic needles melting a t75", dissolving in concentrated sulphuric acid with formation of a redcolour.a-Kitroso-a-72.ap7LthoZ is best prepared from a-naphthol, together withits isomeride p-nitroso-a-naphthol, by the process of Sterihouse andGroves mentioned above : the two compounds are then separated bytlie difference of their solubility in dilute soda solution. The resultanta-nitroso-a-naphthol melts with decomposition a t 190".Its salts arecomparatirely unstable, and even on agitation with ether are recon-verted into the original substance. The potassium, sodium, calcium,barium, and magnesium salts are readily soluble in water. On tjheaddition of silver nitrate to a solution of the last-named salt there isprecipitated a red- brown resin, which on purification and subsequenttreatment with methyl iodide can be converted into tbs methyl etherof a-nitroso-2-naphthol, which crys tallises in needles, melting probablyat about 100". It is readily soluble in alcohol, ether, and benzene,but insoluble in water. ~~-Nitroso-P-naphthol and lJ-nitroso-a-naphtholdiffer in their reaction with cobalt chloride ; the formela yields a cobalt-derivative, containing no chlorine and unaltered by acids, alkalis,oxidising and reducing reagents, whilst the latter yields no such com-pound.By the action of ammonia on a-nitroso-P-naphthol a substance ofthe formula C,,H,N,O is formed ; this was ccnsidered to be a nitroso-amidonaphthalene, CloH6N0.NH2, but is more probably a quinon-oximine.V. H. V.A. K. M.a- and p-Hydrojuglone. By F. MYLIUS (Bey., 17, 2411-2414).-The earlier writers on the subject all regard juglone as occurring readyformed in the p e e n shell of the walnut, the author, however, findsthat this view is incorrect, and that it is formed by the oxidation oftwo isomeric crystalline bodies, a- and P-hydrojuglone, standing i170 ABSTRACTS OF CHEXICAL PAPERS.the same relation to it as that of the dihydroxybenzenes to quinone.Those substances occur i n all the green parts of the walnut tree, butthe shells of the ripe nuts do not contain even a trace of hydrqjuglones.No account of the method of preparation is given.a-HydrojugZone, CloH,03, forms colourless plates, melts a t 168 -1 70",is soluble in about 203 parts of water a t 25", is readily soluble inalcohol and ether, insoluble in chloroform; i t is readily soluble inalkalis with yellow colour, turning quickly to red on exposure to air.Ferric chloride or bromine-water oxidises it to juglone.On reducingjuglone, a-hydrojuglone is alone formed.Acett!l-a-hyd?.o~ziglorze, CloH,03Ac3 formed by digestion of a-hydro-juglone with acetic anhydride, melts a t 124".A solution of a-hydro-juglone or of juglone in organic bases yields nitrogenous componndsof juglone by oxidation in air. Of these compounds that with di-methglaniline, C,oHS03,NMe2Ph, is very readily prepared ; it crystal-lises in lustrous red tlables, and by treatment with hydrochloric acidis converted into a hydroxyjuglone of the formula C,H,O,.OH, havingthe charactem of a strong acid.p- HydrojugZorze crystallises in colourless plates, melts a t 97", issoluble in about 900 parts of water at 25", is sparingly soluble inalcohol and ether, readily soluble in chloroform ; it is readily solublein alkalis with yellow colour, which changes to red on exposure toair. It @ves a blood-red coloration with ferric chloride, and isconverted into a brominated product by bromine-water.It occurs inmuch smaller quantity tban its isomeride.On fusion with potash, both hydrojuglones yield phenol, salicylicacid, and metahydroxybenzoic acid.The author had independently arrived a t the same conclusion asBernthsen (Abstr., 1884, 1365) as to juglone having the formulaC,,,H60,. He further confirms Bernthsen's view that juglone is a hydr-oxynaphthaquinine, by showing that a-hydrojuglone also yields naph-thalene when distilled with zinc-dust. A. J. G.A Sulphoxide of Naphthalene. By A. G. EESTRAND (Ber., 17,2601-2694). Whilst preparing naphthonitrile by disbilling a mix-ture of potassium a- and P-naph thalene sulphonates with potassiumferrocyanide, the author observed the formation of secondary sub-stances which crptallise from the highest fraction of the crude nitrile.Two compounds may be separated by crystallisation from alcohol, oneof which is obtained in very small quantity and forms scales melt-ing a t 148" ; the other crystallises in long needles, melts a t 1 Ll", a,nddissolves very readily in carbon bisulphide, ether, benzene, warmglacial acetic acid, and alcohol.Its formula appears to be C,,H,SO.It is insoluble in acids and alkalis, and is not acted on by acetic anhy-dride ; it readily yields a bromine-derivative, and this crystallises incolourless needles melting a t 182", is rery readily soluble in carbonbisulphide, and very sparingly in alcohol and glacial acetic acid.Thecompound C,oH20S0 is probably napkthylenedinuphthy lsulphoxide,When its solution in glacial acetic acid is heated with potassium di-CioH6 : SO(CioH,),ORGANIC CHEMISTRY. 171chromate, dinup h t h y 7szclp h oxide, SO ( C is produced, and crystal-lises in prisms melting a t 162'. By the action of nitric acid (sp. gr.1.21) on naphthylenedinaphthylsulphoxide a t 130--140", a diviitro-naphthyl sulphide, S(C,H,.NO,),, is obtained, crystallising in smallgolden yellow prisms melting a t 230-231'. It is insoluble in alkalis,almost insoluble in alcohol and carbon bisulphide, and very sparinglysoluble in glacial acetic acid.Derivatives of the Isomeric Dinaphthols. By E. OSTERMATERand J. ROSENHEK (Rer., 17, 2453--2455).-The authors descrikeseveral derivatives of Dianin's a- and P-dinaphthols.a-DinuphthyZ diethy2 ether, EtO.CIoH6.CloH6.OEt, was prepared byacting on a-dinaphthol with alcoholic potash and ethyl iodide.Itcrystallises in white pearly scales melting a t 211", and is easily solublein hot benzene, sparingly so in ether or alcohol, insoluble in water.a-Dinaphthyl dimethyl ether, ( C,oH,.0Me)2, crystalhes in glisteningplates melting a t 251".@-Dinaphthyl diethyl ether, (C,,H6.0Et),.ci~ystallises in needles whichmelt a t go", and are soluble in alcohol and benzene. p-Dinaphthyldimethyl ether cryst'allises in double pyramids, soluble in benzeze,insoluble in alcohol ; it melts a t 190".The authors were unable to isolate the potassium or sodium com-pounds of a- or g-dinaphthol.These compounds are very nilstable,and in all attempts at purification were either partly or wholly recon-verted into the dinaphthol. Schaeffer's experiences wit,h a- and@naphthol were similar.A. K. M.L. T. T.Ethereal Oils. By 0. WALLACH (Annnlen, 225, 314--318).-Thechief constituent8 of oil of cajeput is identical with cyneol. The ter-penes contained in oil of bergamot and oil of eucalyptus are distinctfrom cynene. Oil of lemon yields a small precipitate with bromine,and a large quantity of the crystalline tetrabromide is obtained fromOZeum corticis aurantiorum. This compound closely resembles cynenetetrabi*omide, but differs from it in its melting point (104"). w. c. w.Oleum Cpe. By 0. WALLACR and W. BRASS (Annalen, 225,291-314) .-After referring to the researches of Volckel (Annalen,87,312), Kraut (Jalwesber., 1862, 460), and Faust and Homeyer (thisJournal, 1875,375)on this subject, the authors describe the experimentsby which they succeeded in isolating cpeoE, CIOH180, and cynene, CloH,6,from the crude oil.The separation depends on the fact that cpneolforms an unstable crystalline compound, ( C~oE180)2,HCl, when it istreated with the hydrochloric acid gas. This substance is decomposedby water into hydrochloric acid and cyneol. It is decomposed also whenheated in sealed tubes, yielding cynene, water, and hydrochloric acid.Pure cyneol boils at 176-177", and has no action on polarisedlight. It is oxidised to oxalic acid bynitric acid sp. gr. 1-15.Cyneol also forms an unstable crystallinecompound with hydrobromic acid, and with hydriodic acid it yieldsthe iodide C10H1812, which crystallises in transparent rhombic plates.The iodide is decomposed by heat into cpene and hydriodic acid.Its sp. gr. is 0.92297 at 16"172 ABSTRACTS OF CHEMICAL PAPERS.Ry slowly dropping bromine into a well-cooled mixture o i lightpetroleum and cyneol or rectified oZmm cynce, an additive product,C,oHIs0,Br2, is obtained, which crystallises in red prisms. If thecrystals are placed in a sealed tube and kept in a cool place, theyslowly decompose, forming a colourless liquid, which in the courseof time deposits a crystalline mass. By reciytallisation from chI(,ro-form, cynene tetrabromide, CloH16Br4, is obtained in rhombic cryat&melting at 125.5".Cyneol diiodide is formed when iodine acts on cyneol diluted withlight petroleum. It is deposited from its ethereal solution in longneedle-shaped crystals, which are more stable than those of thebromide.Cyneol is not acted on by metallic sodium, nor by sodium ethylateand ethyl iodide ; neither does it enter into reaction with hydroxyl-amine or phenylhpdrazine, nor yet with phosphorus pen tachlorideor benzoic chloride a t the ordinary temperature.These negative re-mits indicate that the oxygen in cyneol is not present in the form ofhydroxyl.Pure cynene is best prepared by warming a mixture of the iodide,C,,HlET2 (3 parts), with aniline (4 parts), amd distilling the product ina current of steam.The hydrocarbon boils at 181-182". Its sp. gr.is 0.85384 at 1~'. Pure cynene has a characteristic odour of lemons.When bromine is added to a well-cooled mixture of cynene and alco-hol or ether, crystals of the tetrabromide are deposited. Cynene isconverted into cymene by strong sulphuric acid or by phosphorusAction of the Halogen Acids;on Wormseed Oil. 11. ByC. HELL and A. RITTER (Ber., 17, cLG09-2614).-l'he action of hydro-chloric acid has been described (Abstr., 1884, 1363). When hydro-bromic acid acts on wormseed oil in the cold, a crystalline substanceis obtained, and is apparently the additive product CloH,,O,HBr,corresponding with the hydrochloric acid additive product previouslydescribed (Zoc. cit.). It is, however, much less stable than the lattercompound, and rapidly deliquesces and becomes brown on exposure tothe air.It melts between 33" and 35". A cynejie dihydrobrornide,C,,H,,Br,, may also be obtained, correspmding with the dihydro-chloride. This crystallises in white silky scales, melts at 64O, and isdecomposed by heat into cynene and hydrobromic acid, as also whenboiled with water or dilute alkalis. By the action of hydriodic acidon wormseed oil in the cold, crystals may likewise be obtained, butthe compound is so unstable that, it could not be isolated. Theflirther action of hydriodic acid yields cynene dihp?riodidR, C,,H,,I,,which crystallises in short white needles melting at 76-77', and iseven less stable than the dihydrobromide. It, can be kept for three orfour days only, even in the dark, and in a sealed tube.When heatedwith zinc-d ust aiid water, dihyclrocynene, C1OHIEr is obtained, boilinga t 166-167'. This is a colourless strorigly refracting oil, resemblingcynene in its odour. It may also be obtained from the dihydrochloride.On comparing the properties of the dihydrochlorides, bromides, andiodides of the terpenes with those of the uorrespmding cynene-pentasulphide. w. c. w0 RGANIC CHEMISTRY. 173derivatives, striking resemblances are observed. The dihydrochlo-rides of many of the terpenes melt, for instance, at nearly the sametemperature as cynene dihydrochloride. Further experiments are,however, necessary to decide whether these terpenes are identical orisomeric with cynene.By J. KACHLER and F.V.SPITZER (Ber., 17, 2400-2401).-The authors regard the compound,CIOHt602, recently described by Goldschmidt and Ziirrer (A bstr.,1884, 1364) under the name of campholenic acid, as identical with thesubstance termed by them hydroxycamphor, formed by the- action ofsodium amalgam on ,B-dibromocamphor. They consider the constitu-tion of this substance to be still unsettled, and will continue theirresearches on it. A. J. G.A. K. M.The so-called Campholenic Acid.Coal-tar Quinoline. By M. C. TRAUD and C. SCHARGES (Ber., 17,2618-2619).--In preparing qninophthalone from coal-tar quinoline, ared resinous substance is also produced which, however, is not formedwhen pure quinaldine or a mixture containing only quinoline andquinaldine is employed. When coal-tar quinoline (b.p. 2.35") isheated with a little phosphorus pentoxide, it assumes a more or lessintense reddish coloration, and on dissolving the product in water oralcohol, the solution obtained shows a splendid yellowish-greenfluorescence. Neither Skraup's quinoline nor pure quinaldine yield thisreaction. The fractions of coal-tar quinoline distilling below 200"behave like pure qninoline and quinaldine, whilst the portion distillingbelow 230" yields a feeble reaction.The above is a convenient method of recognising coal-tar quinoline.The reaction indicates the mesence of a third substance besidesquinoline and quinaldine, and this the authors are trying to isolate.A. K. M.x-Diquinoline from Azobenzene. By A. CLAUS and P.STEGELITZ (Her., 17, 2380--2383).-By heating a mixture of 20 gramsazobenzene, 80 grams glyceroI, 30 grams concentrated sulphuric acid,a.nd 20 grams Nordhausen sulphuric acid, for two days on the wuter-bath, there are obtained a-diquinoline (2 grams) and benzidinesulpbate (6 grams).By dissolving a-diquinoline in fuming nitric acid, heating on thewater- bath, and precipitating with water, nearly colourless, slenderneedles are obtained.These decompose without fmion a t 260", do notyield compounds with acids, and appear t o consist of a mixture ofnitration products. A. J. G.Synthesis of a-Diquinoline. By E. OSTERMAYER and W.HENRICHSEN (Ber., 17, 2444-2451).-This base was originally ob-tained by Weidel (Abstr., 1882, 69) by the action of sodium onquinoline at 192".The authors find that it can also be prepared frombenzidine by Skraup's reaction. For this purpose, benzidine sulphate(50 grams), nitrobenzene (25 grams), snlphnric acid (100 grams), andglycerol are slowly heated in a reflux apparatus, care being taken thatthe reaction does not become unmanageable. The yield of diquinolkeVOL. XLVIII. %174 ABSTRACTS OF CHEMICAL PAPERS.is very good (about 33 per cent. of the benzidine sulphate employed),but its purification is rendered difficult by tar-like products simul-taneously formed ; by substituting para- or ortho-nitrophenol forthe nitrobenzene, however, there is obtained not only a much largeryield (about 72 per cent. of the benzidine sulphate), but from theabsence of the tar-like products the purification is very easily effected.The aurochloride,C,,H12N2,HAuC14 + 2H20, crystallises i n very slender needles and isvery sparingly soluble.The sfannichloride, Cl8HI2N2,H2SnCl4, crys-tallises in colourless needles. The methiodide, C1BHT2N2(MeI)2, wasprepared by heating diquinoline with methyl iodide and methylalcohol in sealed tubes a t 120". Acompound with methyl chloride of like composition was also obtained.Weidel had described the methiodide as containing only 1 mol. ofmethyl iodide (Zoc. cit.).Diquinoline n i t r a t e is nearly insoluble in water.It crystallises in yellow needles.The compound with methyl s u b h a t e ,CI,H12J%(MeSOaH)2 + 2&0,prepared by heating diquinoline, methyl alcohol, and sulphuric acid insealed tubes at 180°, crystallises in colourless needles.Its diluteaqueous solution shows a bluish-violet fluorescence and gives a blood-red coloration with alkalis.Diquinoline unites directly with bromine to form two additive corn-pounds : an orange-yellow, apparently crystalline substance of theformula C,,H,,N,Rr,. and a pale yellow tetrabromide, C,,Hl2N2Br4.Both compounds are very unstable ; when boiled with water, they aredecomposed, diquinolirie being in part regenerated. By heating withhydrochloric acid a t 180-200 O , mono byom odiquiq? ol ine, C,,HllBrN2,IS formed amongst other products. It crystallises in tufts of needles,melts a t 150-155°, and is readily soluble in cold alcohol. Di-quinoliiLechli,riodide hydrochloride, C,sH12N2C121,,2HCl, is prepared byprecipitating an aqueous solution of diquinoline hydrochloride with asolution of iodine chloride.DiqiiinoZirLedisulp~~n~c acid, C,sHI2N2( S03H),, is prepared by theaction of nitrophenol, glycerol, and sulphuric acid on benzidinedisul-phonic acid ; it crystallists in colourless plates or needles, is sparinglysoluble in water, insoluble in alcohol, and has a very bitter taste. Thepotassium salt has the formula C18H12N,(S0,K), + H20.It isprobably identical with the disulphonic acid prepared directly fromdiquinoline by Weidel. A. J. G.Formation of Pyridine Derivatives. 11. CondensationProducts from Malic Acid. By H. v. PECHMANN and W. WELSH(Bar., 17, 2334-2395) .-In a previous eomrnunication, v. Pechmannhas shown that by the action of sulphuric acid on malic acid, formicacid and coumalinic acid are formed (Abstr., 1884,1124). The presentpaper deals with the derivatives of coumalinic acid.By the action of ammonia or ammonium carbonate on coumalinicacid 1 : 4 hgdroxynicotic acid is formed.The reaction proceeds morereadily if ethyl coumalinate is employed instead of the free acid. Thischange is most probably represented by the equationORQANIC CHEMISTRY. 175c(cOOH) ' CH>O + NH, = COOH.CH CH.C(COOH) CH.NH, <CH: CH-GO= H20 + COOH.C<cH:cH>C.OH. CH-NFor although the intermediate coumalamic acid could not be isolated,yet the analogous methyl coumalanilidate has been obtained. Thehydroxynicotic acid obtained is identical with Koniqs and Geigy'sh~droxypyritiineclarboxylic acid (Abstr., 1884, 1195) ; if heatedwlth phosphoric chloride it is converted into chloronicotic acid,C5H,NC1.COOH.This crystallises in shining plates, nielts withdecomposition a t 199', is readily soluble in water, ether, alcohol, andglacial acetic acid, sparingly soluble in chloroform and benzene. Theaqueous solution gives a pale-green precipitate with cupric acetate.By reduction with tin and hydrochloric acid, it is converted intonicotic acid. As the chlorine-atom in cb-loronico tic acid exhibitsproperties shown by Friedlander and Ostermaier to be characteristicfor the chlorine-atom occupying the position next to the nitrogen-atom, it follows that from its formation from hydroxyquinolinic acid,and from the known constitution of nicotic acid, that this hydroxy-nicotic acid must, have the constitut'ion [N : €30 : COOH = 1 : 2 : 51.Monomethy1 coumalairilidate, (C,H,NPh)(COOH>.COr>Me, is pre-pared by the action of aniline on methyl coumalinate.It erptallisesin citron-yellow needles, melts with decomposition at 140", is readilysoluble in hot alcohol, chloroform, and benzene, sparingly soluble inether, insoluble in water, and behaves as a free acid. It readilysuffers decomposition by the action of water, acids, or alkalis.Phenox?/nicotic a c i d , C,H,N(OPh).CfiOH [OPh : COOH = 1 : 4J7is prepared by boiling methyl coumalanilidate for a few minutes withsoda, &c. J t crystallises in lustrous white needles, melts a t 275-%0',can be sublimed by careful heating, is soluble in hot water, alcohol,and glacial acetic acid, nearly insoluble in ether, chloroform, andbenzene. By heating it with concentrated hydrochloric acid at 200°,a crystalline substance, probably p henoxypyridine, is obtained, whilstcarbonic anhydride is evolved.Metholrynicofic acid, C,H,N(OMe) .COOH + H,O, is obtained eitherby the direct methylation of hydroxynicotic acid or by condensationfrom coumalinic acid and methylamine.It crystallises in flat needlesof satiny lustre, melts a t 237-4238", is nearly insoluble in cold, butvery readily soluble in hot water, soluble in alcohol, ether, and glacialacetic acid, insoluble in chloroform and benzene. It has scarcely anybasic properties. A. J. G.Synthesis of Pyridine Derivatives.111. Coumalinic Acid.By H. v. PECHMANN (Ber., 17, 2396-2399) .-Bro?nocoi~n.raZi?zic crcid,C5H2BrO2.COOH, is prepared by heating a mixture of finely powderedcoumalinic acid (10 parts), glacial acetic acid (30 parts), and bromine(12 parts), with a little iodine, on the water-bath. It crjstallises i ncolourless, lustrous needles, melts a t 176", can be sublimed in smallportions, is readily soluble in alcohol, ether, glacial acetic acid, andchloroform, more sparingly soluble in benzene, insoluble in lightn 176 ABSTRAOTS UP CHEMICAL PAPERS.petroleum. It is nearly insoluble in cold, moderately soluble in hotwater, t'he solution soon decomposing, if boiled, with copious evolutionof carbonic anhydride and formation of a substance volatile in steam,and of very penetrating odour.Like coumalinic acid, it is convertedby alkalis into an acid yielding yellow salts. Ammonia gas passedinto an alcoholic or ethereal solution of the acid causes the pre-cipitation of a colourless crystalline salt. MethyZ bromocoumalinczte,C5H,Br02.COOMe, crystallises in prismatic needles, melts at 134", canbe distilled unaltered, is insoluble in water, sparingly soluble in ether,more readily soluble in alcohol and benzene.Bromhplrozynicofic acid, OH.C5H2NBr.COOH [OH : COOH = 1 : 41,is obtained as met'hyl salt by slowly adding finely powdered metliylbromocoumalinate t o two parts of concentrated ammonia, and sepamtesafter some time in crystals. The free acid is dimorphous, crystallisirigin long slender needles, or in strongly refractive rhombic tables.IGmelts a t 296", is sparingly soluble in boiling water, nearly insolubiein ether, alcohol, and glacial acetic acid. On boiling its aqueoussolution with cupric acetate, a green precipitate is formed. The methylsalt, OH.C5H,NBr.COOMe, cr.ystallises in colonrless, flexible, asbestos-like needles, melts a t 221-222", and is soluble in water, alcohol, andglacial acetic acid, only when heated.MrthyZ bron~ophe?iozynicotate, OPh.C5H2N Br.COOMe, is formed bythe action of aniline on an alcoholic solution of methyl broinoconmali-nate, there being no formation of the intermediate coumanalidate as inthe case of the non-brominated acid (preceding Abstract). T t crystallisesin lustrous white needles, melts at 183*5", can be distilled unaltered,is insoluble in water, soluble in alcohol, ether, and chloroform. Itsodour is peculiar, recalling that of rotten fruit. It is readily saponifiedb j heating i t with alcoholic soda.Oxidation of Piperidine. By C. SCHOTTEN (Ber., 17, 2544-2547) .-Benzoylpiperidine was suspended in water and oxidised withpotassium permanganate. Benzoylhomopiperidic acid, Ph.CO.C,H',,O,X,thus obtained crystallises in needles melting a t 94" to a clear liquid,and volatilises completely a t higher temperatures. It is moderatelysoluble in the usual reagents. It is easily soluble in ammonia oralkaline carbonates, and with these neutral solutions the heavy metalsgive insoluble precipitates. The acid decomposes slowly when boiledwith water, more rapidly with mineral acids. Heated in closed tubeswith concentrated hydrochloric acid at 100-110", it splits u p intobenzoic acid, and the hydrochloride of a nitrogenous acid. Honzopiperidicacid hydrochloride, C5H1102N,HC1, crrstallises in hygroscopic rhombicplates or prisms. These crystals are doubly refracting. The platino-chloride crystallises in easily soluble plates.By C. SCHOTTEN andJ. BAUX (Bey., 17, 2548--2551).-Benzoylconine was oxidised withperrnanganate in a similar way to that employed by Schotten withbenzoylpiperidine (przceding Abstract). Benzoylhomoconic acid,COPh.C8H,,02N, t h u s obtained, crystallises in prisms or needleswhich melt a t 142-143" to a clear liquid, and volatilises if moreA. J. G.L. T. T.A New Oxidation-product of ConineORGANIC CEEJIISTRY. 1'77strongly heated. It is very sparingly soluble in ether, easily inalcohol or ethyl acetat.e. When boiled with water, slight decomposi-tion takes place. It dissolTes readily in dilute ammonia or in alkalinecarbonates, and forms insoluble salts with most of the heavy metals :the silver salt is an amorphous powder. When heated with hydro-chloric acid in closed tubes a t lOO", this acid is decomposed intobenzoic acid and a nit,rogenous acid now under investdgation.Prom the stability of conine towards oxidising agents, the authorsare inclined to think that it contains the isopropyl group, and not thenormal one. L. T. T.Parabuxinidine, a Fourth Alkaloid from the Box Tree,Buxus Sempervirens. By G. A. BARBAGLIA (Ber., 17, 2655-2656).-The leaves and twigs of the box tree are extracted in the usualway, and the extract treated as previously described (Gazzetta, 1883,249). The product is dissolved in alcohol, nentralised with analcoholic solution of oxalic acid, the white precipitate boiled withwater, dissolved in dilute aqueons oxalic acid, sodium carbonate addedin slight excess, and the liquid extracted with ether. Parabuzinidinecrystallises from the ethereal solution in thin, colourless, transparent,microscopic prisms. It is insoluble in water, but very readily soluble inalcohol ; with oxalic acid, the alcoholic solution gives a heavy whiteprecipitate insoluble in water and alcohol. The dkaloi'd containsnitrogen, melts readily, has a rery bitter tastc, and burns with asmoky flame. A. K. M.Lupinidine from Lupinus Luteus. By G. BAUMERT (Anralm,225, 365--384).-1n order to separate lupinine from lupinidine, theauthor takes advantage of the fact that lupinine sulphate dissolvesfreely in absolute alcohol, but the acid sulphate of lupinidine is onlysparingly soluble in this solvent. The lupinine was further purifiedby Baeyer's process (Landw. Versuchs- Stat., 14, 161). Lupinidilzeplatinochloride is thrown down as an amorphous precipitate when analcoholic solution of lupinidine hydrochloride is added to an aqueoussolution of platinum chloride. This precipitate is somewhat suluble,but is redeposited from its solution i n a Tariety of different crystallineforms, all of which belong to the rhombic system. The crystals m every sliyhtly soluble in alcohol or hot water.Lirpinidine h ydrochlorida forms rhombic prisms which are veryhygroscopic. The aimchloride is unstable. The ucid suZphatP,C,HI5N,H,SO4, dissolves freely in water, but, is insoluble in absolutealcohol. The hydriodide, C8H,,N,HI, is precipitated on mixing con-centrated solutions of potassium iodide and the hydrochloride, Theprecipitate dissolves in alcohol ;md hot water, and the aqueous solu-tion deposits colourless plates containing h mol. H,O. The free baseis a thick oil, heavier than water, and has a bitter taste. It iseasily at'tacked by oxygen, especially in presence of acids, or potash,or soda. w. c. w.Albumin of the Splenic Fever Bacilla. By M. NENCKI (Be)..,17, 2605--2ti09$.-Nencki and Schaffer ( J . pr. Cliem., 20, 443178 ABSTRACTS OF CHEMlOAL PAPERS.showed that albumino'id substances formed the chief component (morethan 84 per cent.) of dried bacteria which had been generated in agelatin medium. Of these albuminoids, mycoprote'in formed morethan 90 per cent. The albumin obtained from the splenic fever.bacillus is found to contain only traces of mycoprote'in, whilst thechief component resembles in its chemical behaviour vegetable caseinand mucous substances. It is readily soluble in alkalis, but quiteinsoluble in water, acetic and dilute mineral acids. I n compositionsit, also appears to differ from mycoprote'in, but, like the latter, con-tains no sulphur. It is named by the author nnthra,zp-otezn.A. K. M

ISSN:0368-1769    

DOI:10.1039/CA8854800133

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年代:1885

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178 ABSTRACTS OF CHEMlOAL PAPERS.P h y s i o l o g i c a l C h e m i s t r y .Experiments on Digestion in the Horse. By ELLENBERGEB andHOFFMBISTER ( B i e d . Centr., 1884, 684--ti88) .--Previous experimentsof the authors were made on the digestive fnnctions of the mouth andstomach ; those now recorded refer to the intestines and their secre-tions; these secretions are difficult to obtain, the horse not having agall bladder, so that the authors were compelled to use extracts of thepancreas, liver, and mucous lining of the intestine. The reaction in thefore and true stomach was always found t o be decidedly acid; i t isalso acid in the fore part of the small intestine, but when the jejunumis reached the reaction becomes alkaline; the blind and large intes-tines are mostly alkaline.From experiments on three horses, it wasfound that it took 96 hours for the food to pass through the intestines.Only a portion undergoes a change in the stomach, the chief trans-formations taking place in the intestine. The co1itent.s of the stomachappear a relatively dry, crumbling mass, those of the small intestine arewatery, and almost fluid ; in the larger intestine, the contents take morethe fcrm of faeces, there is little starch present, but much indigestiblem a t h . I n the stomach, the activity of digestion is considerable ; thealbuminoids in the dry substance, when the animal is fed on oats,sink from 11.2 per cent. to 6 per cent.; the diffestion in the smallintestine is very active, only 23-52 per cent.undigested albumin and38-59 per cent. undigested carbohydrates being found therein, sub-stances which are unaffected by the secretions of the stomach beingrapidly digested here. The pancreatic ferments and gall enter a t theduodenum, and play a most important part in the digestion.J. F.Researches on the Fermentation of Cellulose, especiallywith reference to its Solution in the Alimentary Canal. ByH. TAPPEINER (Zeits. Bid, 20,52-134) .-The two chief propositionsare as follows : 1st. In which section of the alimentary canal does thesolution of celliilose take place ? 2nd. Is the solution produced by a8norganised or an unorganised ferment ? Weighed quantities from thPHP SIOLOGICAL CHENISTRP. 179contents of the different sections of the alimentary canal of oxen fedwith hay were placed i u suitable flasks arid divided into three equalportions.In the first both organised and unorganised ferments werealike destroyed by boiling the contents of the flask, this portion after-wards served for the determination of the cellulose in the sample ; the2nd part was maintained under conditions as near as possible likethose in the int'estine ; and the 3rd part was similarly treated, onlythe action of the organised ferment was inhibited by the addition ofantiseptics (thymol, &c.), which, at the same time, did not affect theunorganised ferment. Great difficulty was experienced in obtaining afair sample of the paunch contents. Scarcely any solution takesplace in the small intestine, about 6 per cent.in the large intestine,and a maximum of 36 per cent. in the paunch.In order to determine whether the intestinal gases were developedfrom the solid or liquid contents of the intestine, the clear liquid fromthe filtered paunch contents was digested with fibrin, egg-albumin,starch powder, and acetate of lime ; very little gas was evolved, andthat, moreover, consisted almost exclusively of carbonic anhydride.It is therefore evident that marsh-gas is formed from the solid con-stituents, although albuminous bodies, fat, and starch need notnecessarily be concerned in its production. For the artificial pro-duction of the marsh-gas fermentation of cellulose, a 1 per cent.neutralised meat-extract solution, and some cellulose (paper pulp),were sterilised and then infected with paunch contents.After 3-43days, a plentiful development of gas had occurred, which consistedalmost solely of carbonic anhydride and methane. The relationbetween the two gases a t the beginning was 7.2 to 1, a t the end of thefermentation 3.4 to 1. I n a quantitative determination, the authorfound 38 per cent. of the cellulose appeared as gas. The non-gaseous products were volatile fatty acids, acetic and butyric, with asmall quantihy of aldehyde.If these results be compared with the after-fermentation productsof the paunch contents, a strict analogy will be seen to exist betweenthe gases of these two fermentations :-From the From the From thepaunch contents paunch contents paper pulpof ox. of goat.fermentation. gg}.. .......... 75-47 75.29 76.98- - H ............... 0.07CH+. ............ 23.27 24.53 23-01N ................ 1.31 0.15 -The non-gaseous products of the paunch fermentation consists of asmall quantity of formic and propiouic acids and aldehyde, largequantities of acetic and normal butyric acids, and an acid having thecompofiition of butyric acid, but none of the characteristic propertiesof either the normal or iso-acid (formic, propionic, and normal butyricacids were not found in the artificial fermentation). As such largequantit,ies of fatty acids were formed, it was necessary to see to whatextent they existed preformed in the food (hayj : for this purpos180 ABSTRACTS OF CHEMICAL PAPERS.1 lb. of hay was digested with boiling water for one hour, but fromthis only 0.6 gram of fatty acids was obtained.The author con-cludes, therefore, that celliilose is the body which, for the most part,gives rise to carbonic anhydride, methane, and fatty acids through theaction of bacteria. The gaseous and non-gaseous fermentation pro-ducts of the caecum and colon of the horse agree with the marsh-gasfermentation products. This is true also for the big intestine of theruminants, only the amount of acid formed is not so large. More isformed after feeding with corn than after feeding with hay.Taking into consideration the fact that the putrefaction of albumi-nous bodies can proceed without any essential formation of methane,and the large quantity of this gas found in the case of ruminants, theauthor concludes that the marsh-gas fermentation of cellulose is theonly means by which cellulose is rendered soluble in the intestines ofruminants.With nourishiug media of certain composition, a fermentation andsolution of cellulose can occur without the formation of any methane,hydrogen and carbonic anhydride only being produced ; the otherproducts, however, remain unaltered The fermentation that takesplace in the horse's stomach is siniilar to this, and is considered b ythe author to be a hydrogen fermentation of cellulose.J.P. L.Odour and Poisonous Effects of the Products of the Fer-mentation produced by the Comma Bacillus. By W. NICATIand RIETSCH (Compt. rend., 99, 928--929).-Pure cultivations ofthe comma bacillus have a characteristic ethereal odour, quitedifferent from that of putrid substances.This is the odour of theintestinal matter of cholera patients in the early stages, especiallyif it is kept in a moist atmosphere a t 25-35" for 24 hours. If purecultivations of this bacillus in Koch's gelatin or in beef tea, after atleast eight days, are freed from bacilli by being passed through aPasteur's filter, and the clear liquid is injected into the circuIatorysystem of dogs, choleraic symptoms of varying degrees of violenceare produced. The same liquid when injected under the skin hasno effect. Recent cultivations are also absolutely inactive.C. H. B.Value of Disinfectants in Chicken-cholera. By COHN ( C o ~ z p t .rend., 99, 934-935) .-The intestinal matter and some very vasculartissues from poultry which had died from chicken-cholera were treatedwith copper sulphate, zinc chloride, chloride of lime, or borax, in dif-ferent proportions, and various animals were inoculated with t'he pro-ducts. Copper sulphate and zinc chloride are much more efficientthRn borax or chloride of lime, but their complete efficiency dependsentirely on their being mixed intimately in considerable quantity withthe infected matter, and left in contact m-ith it for some time.C. H. R

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DOI:10.1039/CA8854800178

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

VEOETdBLE PHYSIOLOGY AXD AGRICULTURE.Chemistry of Vegetable Physiology and Agriculture.181The Ammoniacal Ferment. By A. LADUREAU (Compf. rend.,99, 8'77-878) .-The ferment which converts carbamide into am-monium carbonate exists in considerable quantitty in the soil, in theair, in rain, and in many subterranean waters. It acts as readily in avacuum or under a pressure of 3 atmos. as under the normal pressure,and equally well in presence of air, oxygen, nitrogen, hydrogen, car-bonic anhydride, or nitrous oxide. Anaesthetics, with the exception ofchloroform, which retards fermentation, exert little or no action on it,and fermentation is only prevented by somewhat high proportions ofthe ordinary antiseptics.This ferment converts all the carbamide produced by the animalkingdom into ammoniacal salts, and thus places many millions of kilo-grams of these salts daily a t the disposal of plants.C. H. B.Peptonic Fermentation. By V. MARCANO (Compt. rend., 99,811--813).-1f a few drops of the sap of the American aloe areallowed to fail on some chopped meat covered with water, and thewhole is kept at 3 5 4 0 " , active fermentation immediately com-mences, with evolution of inodorous gases, and after about 36 hourathe fibrin completely disappears, and is converted into peptone, to-gether wit,h some pepsin and small quantities of ethyl alcohol andlactic acid. This fermentation is also produced by many other sapsand by the juices of many fruits. It is due to a rnucor, which canbe submitted to several successive cultivations withcut losing itsactivity.C. H. B.Germination of Linseed and Sweet Almonds. By A.JORISSEN (Ann. Agronomipues, 10, 468475) .-The author hasstudied the influence of germination and growth on the develop-ment of hydrocyanic acid in the flax and sweet almond. 20 gramsof crushed flax seed do not yield more than 2 mgrms. of hydrocyanicacid, but after some days of germination 14 mgrms. are obtained fromthe same quantity. The young plants, however, yield only traces onplunging them suddenly into boiling water and distilling the whole,so that probably a glucoside similar to ampgdalin or laurocerasin isformed during germiuation, and splits up under suitable conditionsinto hydrocyanic acid, glucose, and benzaldehyde.Sweet almonds contain mere traces of amygdalin, but when theyare kept moist and allowed to germinate in darkness for some weeks,a well-marked odour of benzal dehyde is produced, and hydrocyanicacid can be obtained in recognisnble quantity (2 mgrms.) from asingle seedling.The amygdalin is concentrated in the radicle andgemmule, the cotyledons containing very little. By suitable treat-ment, the three substances, benzaldehyde, glucose, and hydrocpnicacid, were isolated from 15 germinated almonds. The author believe182 ABSTRACTS OF CHEMICAL PAPERS.amygda,lin and similar glucosides to be decomposition-products of thealbumino'ids of the seeds. J. M. H. M.Chlorophyll in the Living Cell and Assimilation of Carbon.By J. REINKE ( B e d . C'entr., 1884, 692--69tj).-The reduction of car-bonic anhydride in plants is a function of light and of the chloro-phyll, but to properly understand the process it must be studied inthe living plant.The author did so, using the leaves of Pltanerogama,and observing their absorption-spectra, he found that of the ordinarychlorophyll solution different from that obtained from the living leaves,the latter agreeing amongst themselves. He believes that chloro-phyll experiences some chemical change when it is dissolved. The solu-tion of the fresh leaves shows no fluorescence, but the ordinarysolution shows a fine red fluorescence, due probably to the disaggre-gation of the substance, which the author believes to exist in a fixedstate. The speclroscopic examination of light reflected from theleaves is of interest, the extreme red to line B being very brilliant,the space beiween C and E moderately so, the dark blue and greenbeing weak. The author agrees with Lommel that the maximum ofcarbon reduction coincides with the maximum of absorption of thechlorophjll spectrum, that the molecules have a vibratory motion, andwhen they meet a ray of light in unison with them they assimilate itslife-giving force, and chemical changes result.The author founds Rtheory on 1% observations that the atomic group on which dependsthe reduction have an oscillation rate of 440-450 billions per second,arid are set in motion by r a p of light of similar rate, whilst they remainunaffected by rays of higher or lower refrangibility.J. 3'.Presence of Amylase in Leaves. By L. BRASSE ( C m p t . rend.,99, 878--879).-l'he author has found amylase in all leaves whichhe has examined, including those of the potato, dahlia, maize, beet-root, tobacco, castor-oil plant, &c. The amylase can be extracted byDubrunfaut's method. The leaves are bruised in a mortar, digestedwith cold water for 24 hours, squeezed, and the solution mixed withone and a half times its volume of alcohol of 90-93", and filtered.The filtrate is again mixed with the same proportion of alcohol, andthe precipitate collected on a filter and washed two o r three timeswith a small quantity of alcohol of 63". This precipitate contains theamylase.To detect the amylase, 0.5 gram of starch, 20 C.C. of water, and10 C.C.of an aqueous solution of amylase of such strength that 10 C.C.corresponds with 10 grams of fresh leaves, are placed in a small flaskand kept a t 63" in a water-bath for some time. Similar flasks con-taining a solut8ion of amylase alone are treated in the same way, andthe reducing sugar is estimated by difference. Each flask is closedwith a cork, and contains from 8 to 10 drops of chloroform. I nevery case, the starch is converted into reducing sugar and dextrin,but no microbes are developed.Chemical Composition of Hazel Pollen. By A. v. PLANTA(Lmzdw. Versuchs-Xtat., 31, 97-114) .-Hazel pollen separated f r o uC. H. BJ'EGETABLE PHYSIOLOGY AND AQRICULTURE. 183the dried catkins by means of a fine sieve is a very fine pale-yellowpowder, which keeps for any length of time when perfectly dry.Itconsists of very small uodules (from 0.026 to 0.0337 mm. in diameter),o€ triangular and oval shape, each nodule having three openings forthe pollen tubes, and being surrounded by two membranous coatsclosely united together. The contents of the nodules consist chiefly ofprotoplasm and oil with a lit,tle starch.Hazel pollen contains 9-19 per cent. of water, of which nearly half isgiven up on drying over sulphuric acid. The quantity of nitrogen wasfound to vary in two samples from 4-70 to 5.50 per cent., and the ashamounted to 3.81 per cent, By employing the usual factor for theconversion of nitrogen into proteilds, the nitrogen-free substances wereinferred to amount to about 64.3 per cent.of the dried pollen.The impossibility of mechanically breaking up the pollen nodules,and the difficulty of thorough extraction of their substance by liquidagents, rendered the estimation of the separate organic constituents noeaay task, and some of them couid only be determined qualitatively.Of nitrogenous bodies, globulins, peptones, hypoxanthine, and amido-compounds were definitely traced: the latter yielding about one-twelfthof the total nitrogen. Cane-sugar was found in Considerable quantity,amounting to about 14.7 per cent. of the dry pollen, and starch wasestimated at 5.26 per cent. A yellow colouring matter containing nonitrogen was found in quantity amounting to 2.06 per cent., and con-sisting probably of two distinct bodies.Cuticula was put down a t 3-02,and wax at 367 per cent., the latter consisting probably of myricylpalmitate. The presence ofcholesterin was also noted, and a resinous substance of bitter taste wasfound in quantity amounting to 8-4 per cent.By J. M. H. Mum0 (Clzem. News, 50,227).-Strawberries grown in a field in Kent contained-water 89.30per cent., organic matter 10.27, ash 0.43. The composition of the ashwas as follows :-Sand and insoluble matter 6.61 per cent., calcium phosphate 23.91,containing 11.70 per cent. of phosphoric anhydride ; magnesium phos-phate, trace ; potassium carbonate 60.77, containing 41.40 per cent. ofpotmzssium oxide ; magnesia 2-93, soda 1.29, sulphuric anhydride 3-88,uiidetermined 0.61.The figures seem to show that in the strawberry the whole of thepotash exists in combination with organic acid, and the whole of thephosphorus as calcium phosphate. Strawberry growers assert thatplants forced in pots with the aid of guano or very rich soil have manyblossoms, but they do not all set, or if they do the fruit is inferior i nsize and quality to the smaller quantity produced in poorer soil.Itseems probable that a special manure containing a fair proportion ofpotash would produce good results.Ensilage and Acidification of Green Fodder. By J. KONIGand others (Bied. C'entr., 1884, 677-680).-Green maize, previouslycut fine, was stored in a silo 5 metres deep, with cemented walls. Atthe time of storing, three casks were filled with the same fodder, andFatty acids amounted to 4.2 per cent.J.I(. C.Ash of Strawberries.J. T184 ABSTRACTS OF CHEXICAL PAPERS.they were compared a t intervals with samples drawn from the silo.Unfortunately one of the walls became damaged, and water leaked in,but the experiment was suficiently successful to convince the authorthat the loss of dry substance in green maize stored in silos whichare air and damp-proof does not exceed 10 per cent. E. Lecouteux re-cords experiments made to ascertain whether the maize should be cut(chopped) or stored whole. He recommends chopping, as by that meansthe portions lie closer together, and facilitate fermentation ; the fineand coarse portions of the fodder are more evenly mixed, so that cattJecannot pick out the choice morsels. Stutzer has tried the acidifica-tion of green clover.He found that the digestible alhumino'ids werediminished by one-half in the operation, the comparison being madehy artificial digestion. A feeding experiment was made with ensilage-grass by Insinger, in Holland. Out of a lot of 32 cows, 4 were fedon the ensilage; the others on hay. The period of lactation waslonger with the 4 cows ; the creamometer-indication lower ; butterpercentage higher, 54 litres of their milk producing 2.5 kilos. ofbutter, the same quantity of milk from the others giving 2 kilos. only.The colour of the butter was rather dark. J. F.Removal of the Bitter Principle from Lupines. By E. WILDT(Ried. Cerdr., 1884, 6i5-6T7) .-Experience has shown that exposureto the atmosphere sweetens lupines, and removes their poisonousqualities.As this cannot be done even by strong heat, the authorthought that the change was caused by a process of oxidation, and thatit, could be greatly accelerated. He placed the seeds in dilute hydro-chloric acid, and then treated them with a solution of calciumchloride ; they were then well washed with clean water. By this pro-cess t.he bitterness was quite removed, and probably also their poisonousqualities (but this has yet to be proved on a large scale) ; the loss ofnutritive matter was small. The author thinks that lupines preparedin this way will be found to be a,good and cheap fodder. Cattle,sheep, and swine eat thern with more or less readiness, but the reportsby cattle-feeders as to the results are not unanimous: some say theyare not H fattening food, and that draught oxen and horses grow leanon them, owing probably to the excess of nitrogenous constituents.J.F.Ensilage of Frozen Potatoes. By J. FITTBOGEK and 0. FOERSTER(RiedCentr., 1884, 681-683).-1n the autumn of 1881, a sudden andsevere frost damaged large quantities of potatoes throughout Ger-many. The quantity was so large that the distilleries were not ableto use them, and they had to be stored in silos. The authorsembraced the opportunity of examining them a t different times-attime of storage and after 50, 76, and 140 days. At the last examination,the loss of crude protei'n was 33.7, and of crude fat 83.3 per cent.Cattle and swine eat freely of them, but sheep did not, take them.The authors do not recommend the proceeding unless nothing elsecan be done with the tubers.J. F.Cultivation of Sugar Beet. By P. P. DEHBRAIN (Compt. rend.,99, 920-92Q-It has been observed in many cases that the use oVEGETABLE PHYSIOLOGY AND AGRICULTURE. 185a manure rich in nitrogen increases the proportion of this element inthe beet, but diminislies the proportion of sugar. The author finds,however, that by using .properly selected seed, e.g., the cultivatedvariety of Messrs. Vilmorin, the proportion of sugar is not diminishedby even a highly nitrogenous farmyard manure, whilst the totalyield of roots per hectare is considerably increased, especially if themanure is mixed with sodium nitrate.One of the causes which diminish the proportion of sugar in thebeet is the late sprouting of young leaves, the development of whichuses up the sugar previously formed in the root.If, however, thelast month of vegetation is dry, this growth of new leaves does nottake place, and the value of the roots is increased.Hop Culture in Peat Soils. By M. FLE~SCHER (Bied. C'entr.,1884, $-lQ.-The author gives analyses of the soil of a hop plantationin East Prussia, established in a boggy situation. The constituentsindicate great suitability for the culture in question, but owing to thelightness and porosity of the soil, the frost penetrates it easily inwinter, and injures the roots of the plants.C. H. B.J. F.On Rotations. By P. P. DEHSRATN (Ann. Agronomigues, 10, 433-457) .-The author reviews the leading systems of rotation practisedin the north of France and in Germany, and suggests a modificationof the prevailing Prench rotation, fonnded on the experiments whichhave been for some years carried on at the Agricultural Station ofGrignon (Paris).The increasing importance of stock-raising, and the development ofbeet sugar refineries and spirit distilleries, have brought about the sub-stitution of a crop of sugar beet for the bare fallow formerly customarythroughout large districts of France and Germany.This beet croptakes the place of the English turnip crop at the head of therotation, which runs thus:-beet, corn, seeds, corn. All the farm-yard manure intended for the rotation is given to the beet crop, andthis has the effect of producing a heavy crop of large roots poorin sugar.The French refiners pay for the roots according to the grossweight, and not on the percentage of sugar ; hence the farmers havegone on applying larger and larger dressings of dung, and supple-menting these by applications of nitrate of soda and sulphate ofammonia, with the view of getting heavier and heavier crops. Thenatural result has followed, that the French sugar industry is in alanguishing and critical state. In Germany, on the other hand,where the refiners pay for the roots according to their richness insugar, the industry has undergone an immense development. TheGerman farmers, in order to secure roots of good quality, commencethe rotation with a wheat crop manured with farmyard manure, aiidtake the sugar beet crop the year after.To do this successfully theyare obliged to grow a variety of wheat (Sheriff Square Head) arhichwill stand the heavy manuring without running t,oo much to Straw,and becoming laid. The Sheriff' Square Head wheat, however, pro-duces grain of inferior quality and low market value, and on thisground the author does not recommend the German system. Neithe186 ABSTRACTS OF CHEMICAL PAPERS.does he think well of putting potat'oes a t the head of the rotationinstead of sugar beet, because potatoes derive little or no benefit fromheavy dressings of farmyard manure, and it is a mistake to supposethat the subsequent crops of the rotation utilise anything like the fullvalne of the manure unused by the potato crop.From the results of' several years' experiments a t Grignon, it isinferred that maize cut green for fodder would do well to begin arotation over districts of similar soil and climate.During the earlyHtage of growtb, khe ground can easily be kept free from weeds, anddnring the later stages the growth is so luxuriant that weeds arestifled. Large applications of farmyard manure always produce avery heavy increase in the maize crop, and are more efficacious thanany othw manures which have been tried. The maize can be madeinto ensilage, which the author thinks the better plan, or can begrown in successive port'ions, and cut as reqnired for feeding. Veryheavy crops can be obtained (70,000-100,000 kilos.per hectare atGrignon, with 30,000 kilos. farmyard manure per hectare), and thesucceeding wheat crop is decidedly better t,han when i t followssugar beet. Moreover, the maize being cut in September, moretime is allowed for preparing the ground for the autumn sowing ofwheat than when beet is grown, which is pulled i n October. Thewheat, crop should receive 5,000--10,000 kilos. farmyard mannrc, and200 kilos. nitrate of soda. At Grignon, sulphate of ammonia cannotbe substituted for the nitrate of soda without injury, but on othersoils (Rothamsted, for example) it is found to answer well. Thesugar beet crop is to be taken after the wheat, and is to be manuredwith 20,000 kilos. farmyard manurk, 'LOO kilos. nitrate of soda, andalso superphosphate on soils where it is found to produce an increase,which is not the case at Grignon.In the fourth year, the groundcarries oats sown with seeds, and manured with 5,000-10,000 kilos.farmyard manure and 200 kilos. nitrate of soda; fifth year, clover ;sixth year, wheat or oats ; and seventh yeay, potatoes; all withoutmanure. If the oats in the fourth year are sown with sainfoininstead of clover, the ground may be left in sainfoin two or threeyears before taking the next wheat crop.Manuring Experiments. By G. DRECHSLER (Ried. Centr., 1884,664--670).-TThese experiments were made in Hanover in 1580, withvery careful precautions against error. Each manuring was repeatedat least three times, and each manured plot was surrounded by a tleast four unmanured.Those experiments alone were considered tobe quite successful in which the yields of the uiimanured plots werevery close to each other, and the results of the three trials of themanured plot were nearly concordant. Under such conditions, nnumber of landowners undertook to carry out experiments to ascer-tain how Chili saltpetre operates on potatoes as compared with thepotash salt, and to compare the action of kainite on potatoes, barley,and oats with a compound manure containing kainite, sulphate ofmagnesia. and common salt.The potash gave unexpectedly low results in all experiments, beinglower in heavy, well-tilled lands than on light soils ; the increase inJ. M. H. MVEGETABLE PHYSIOLOGY AND AGRICULTURE. 187almost all cases consisted in large tubers ; Chili saltpetre and phos-phat.es, with few exceptions, yielded very good results.In the trialswith the compound manure, some were unsuccessful, because of a dryseason, but in the completed experiments the results mere more infavour of potash than of kainite, whilst the compound manure cameout very badly. J. F.Notes on Manuring. By G. DRECHSCER, (Ried. Centr., 1884,658--664).-The author has made many experiments himself, and hasstudied the results of those made by others, witb a view of modifyin?the theories of Liebig, on which most of the modern pract'ices ofmanuring are founded, the rule being that manuring is to be regu-lated according to the requirements, or rather the constituents, of thecrop to follow, allowing for the disposable nutritious matters con-tained i n the soil ; and as the knowledge of this cannot generally beobtained in advance, experience on1 y must be relied on, namely, if theuse of a manure incrpases the yield, i t is concluded that there was adeficiency in the soil ; if the manure is inoperative, the soil is supposedto contain a surplus.From his experience, the author formulates new theories of manur-ing.(1.) The nutriment in the soil and that contained in manuresare of different natures, and by reason of the difference in their solu-bilities, combinations, &c., they operate differently on the plant.(2.) The power of different plants to assimilate nutriment frommanures varies, and differs sometimes in the same class of plants.(3.) He divides the process of manuring into two parts-the a1.t ofsupplying to the soil the matters deficient, which he calls fiel(1manuring; and that of supplying for the plant the nutriment it isknown to require; this he names plant manuring. These theoriesadmitted, the question of manuring becomes a consideration not ofthe soil, but of the plant, and the first t'hing to be learned is the re-quirements of the CI-op which must be supplied in the manure, whatmodification of such requirements is found on growing it in certainsoils, and what is the best and cheapest manner to supply the neces-sary matter in the manures.The author commends Wagner forcarrying out experiments in this direction so carefully by means of potculture, but recommends further field experiments. J.F.Manuring Experiments with Chili Saltpetre. By L. Roc11( R i e d . Cenfr., 2884, 673).-Experiments were made with plots ofwheat and rye 2s t o whether larger or smaller quantities of sodiumnitrate gave the best results. 1; kilos. to about one-fourth of a squaremetre pave a better crop t,han 24 kilos., but the summer was dry andhot, and the harvest time wet, so that the results of the experimentsare of little value. J. I?.Preservation of Ammonia in Stable Manure. By TROSCHKE(Ried. Centr., 1881, 670--672).--The addition of gypsum to stablemanure, particularly in warm stalls, is known to cause decompositionof the ammonia and evolution of sulphuretted hydrogen. The autho158 ABSTRACTS OF CHEMICAL PAPERS.tried kainite as a substitute, with the following result for three month+’contact in warm weather :-Loss.With kainite. Gypsum.In dry substance ........ 20 per cent. 31 per cent.Nitrogen 10 ,, 38 9 , ................He therefore thinks the employment of gypsum unadvisable. Fur-ther experiments were made as to the power of Stassfurt salts to formcombinations with ammonia. 100 grams of each salt were mixed withdifferent percentages of ammonia, and the number of grams combinedwith the salt after 24 hours is given.80 per cent.100 grams. 20 per cent. 50 per cent. mixture.Magnesium chloride ...... 6.2 11.5 12.6Magnesium sulphate ...... 5.5 6.9 7.0Gypsum ................ 5.0 17.8 19.8Kainite .................. 3.2 6-4 7-3Carnallite ................4.5 9.0 9.4Krugite .................. 3.0 7.8 10.5Kieserite ................ 4.5 10.5 11.1In order to learn the power of the salts to absorb ammonia in thegaseous form, portions of each were exposed in large flasks to thevapour of ammonium carbonate for one, two, and three days, withthe following results :-Combined with grams NH, in-100 grams of 1 day. 2 days. 3 days.Magnesium chloride . . 6.1 11.3 12.0Gypsum. ............ 5.0 9.9 12.8Krugite. ............. 1 *9 3.7 4.5Magnesium sulphate . . 5.1 6.4 6.9Kainitu. ............. 2.9 4.2 6.2Carnallite ............ 4.1 5.5 9.0Kieserite ............ 4.1 8.2 10.5The substances should be used in a very fine state of division.Experiments on the Nitrogen of Peat. By P. REDER (TJied.CerLtr., 1884, 652, 655).-The author wished to ascertain the eft’ectproduced on the nitrogen contained in peat by the addition of certainmatters thereto. The original sample contained a total of 3.225 percent.,of which 0*109 mas in the formof ammonia, 0.0.53of nitric acid, and 3-154in inorganic combination. One portion of the peat was left with freeaccess of air, another without air ; to neither of them was any additionmade. To other seven samples were added calcium carbonate, freshlyburnt lime, gypsum, magnesia, potassium carbonate, sulphuric acid,quartz sand. The samples were left for 12 months and then examined.All showed a loss of nitrogen, with the exception of that treated withsulpliuric acid, and the author attributes the increase of nitrogen inthat sample to absorption from the air of the laboratory. A featureJ. FASALYTICAL CHEMISTRY. 189common to all was an increase in the amount of nitrogen existing asnitric acid, and a diminution of its other combinations. J. I?.Effects of Fresh Stable Manure on Potatoes. By GAGNAIRE(Ried. Centr., 1884, 700).-It has been found by the author as well asby other observers that the application of fresh manure a t the time ofplanting caused a conRiderablg increased yield of potatoes, but thatthe plants were more liable to disease. A field so manured comparedwith another which had received the manure the previous autumnshowed an increase of one-eighth in the yield, but when the tuberswere stored a great part of them became bad in a few weeks.J. I?

ISSN:0368-1769    

DOI:10.1039/CA8854800181

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

ASALYTICAL CHEMISTRY.An a1 y t i c a 1 C h e m i s t r y.189Modification of Dumas’ Method for the Estimation ofNitrogen. By G. S. JOHNSON (Chem. News, 50, 191).-The modifi-cation suggested is as follows :-A long combustion tube is drawn outa t the front end, so as t o form a delivery-tube ; in the front, reducedmetallic copper is packed, and behind this copper oxide, whilst quiteat the back a platinum boat (4 to 5 inches long) is inserted. Thesubstance to be burnt is put in the front half of this boat, the backpart being filled with pure powdered potassium chlorate ; a cork witha piece of glass tube passing through closes the back end of the com-bustion tube. When in operation, a stfream of carbonic anhydride issent through the tube, and is continued steadily throughout the com-bustion.After 10 minutes, the whole front part of the tube is heated,and as soon as all free nitrogen is driven out of the tube, the trough,tube with caustic potash, &c., are adjusted for the reception of thenitrogen from the substance under examination, which is first heatedwithout fusing the potassinm chlorate. When the evolution of nitrogenceases from this destructive distillation, the heating is extended to thechlorate, and the operation is complete with the cessation of the pro-duction of nitrogen. The advantages claimed are that the air is drivenfrom the copper oxide more rapidly by a stream of carbonic anhydridea,t a red heat than iii is at the ordinary temperature. When platinum,gold, or silver salts are burnt, the metal remains in the boat with thepotassium chloride, and after washing may be weighed, whilst observ-ing the ratio that the nitrogen obtained in the first part of the com-bustion (the distillate) bears to that obtained from the cornhustion ofthe residue (after heating the chlorate) may be of use in determiningthe constitution of the nitrogenous compounds.D. A. L.Method of Testing for Iodine in Presence of Large Quan-tities of Bromine. By P. S. BRITO (Chein. News, 50, 21O).-Whenbromine and iodine are liberated by chlorine, and in the usualmanner carried down b j chloroform, the bromine masks the colourVOL. xLvrIr. 190 ABSTRACTS OE’ CHEMICAL PAPERS.of the iodine if it is in excess. The author finds that the addi-tion of a few crystals of ferrnns sulphate removes the brown brominecoloration, and renders visible the minutest trace of iodine dissolvedby the chloroform.By this means a trace of iodine was detected in“ pure ” potassium bromide.Rapid Estimation of Fixed Ammonia. By J. W. PRATT(Chem. News, 50, 19d).-The present method is well suited for test-ing “ gas-water ” and “ bone-liquor.” Free ammonia is determinedas usual by direct titration. For the fixed ammonia, about 25 C.C. ofthe liquid is evaporated to dryness with 25 C.C. decinormal sodiumcarbonate, ignited to get rid of any organic matter, redissolved i nwater, and titrated. The amount of fixed ammonia is easily calcu-lated from the quantity of sodium carbonate consumed. Allowancemust be made for, or the method must be modified, if the liquid hasa non-volatile alkalinity.D.A. L.D. A. 1;.Electrolytic Estimations. By A. CLASSEN (Rer., 17, 2351-2359).-1n a recent paper (Abstr., 1884, 1426) Wieland has criti-cised adversely the methods for the electrolytic estimation and separa-tion of iron, manganese, and aluminium described by the author(Abstr., 1881, 1081 ; 1882, 896). Numerous fresh results are nowgiven, confirming the accuracy of these methods, and it is pointedout that Wieland’s failure to obtain good results is entirely due to hisneglect of precautions stated to be necessary in the author’s earlierpapers. A. J. GQuantitative Analysis by Electrolysis. By A. CLASSEN (Ber.,17, 2467-2485) .-This is a continuation of the author’s previouscommunications (Abstr., 1881, 1081, and 1882, 896) on this subject.The author advises the use either of one of the ordinary batteries(Bunsen, Leclanchb, Daniel], &c.), or of a small Siemens dynamo-meter.By the help of an arrangement to regulate the rate ofrevolution, and the introduction of a rheostat into the circuit tofurther regulate the current, the author has obtained very satis-factory results with a Siemens machine. Thermoelectric batterieswere not found to work satisfactorily. Two Bunsen cells are sufficientfor most purposes, and are connected either in series, or as a pair,according as the metal in question is easily deposited or not. Theauthor estimates the strength of the current by the number of C.C. ofgas generated per minute by the decomposition of acidified water.Estimation of Copper and Cadmium .-These metals are rediicedfrom solutions of their ammonio-oxalates by a weak current (twoBunsens joined as a pair).If a stronger current is used, they aredeposited in a spongy coiidition. They may thus be separated fromother metals requiring a stronger current for their electrolysis, Toseparate copper from iron, excess of ammonium oxalate is added tothe mixed solution, and the copper then deposited in the cold by acurrent from two Bunsen cells arranged as a pair : in about 10 hoursall the copper is deposited. More ammonium oxaiate is then added,the Bunsen cells arranged in series, and the iron electrolysed. ThANALYTICAL CHEMISTRY. 191separation of copper from nickel, from cobalt, and from chromium, iseffected in a similar manner.The separation of copper from man-ganese can be effected in the same way, but the current must be keptas constant as possible, as otherwise traces of manganese may bedeposited on the positive pole or of mnnganic dioxide on the negative.In separating copper from zinc by the electrolysis of their ammonio-oxalates, the action must be stopped as soon as all the copper isdeposited. The separation is more easily effected if the solution tobe electrolysed is acidified with sulphuric acid. Copper cannot besepalmated from antimony, arsenic, mercury, bismuth, or cadmiumby the electrolysis of their arnmonio-oxalates. It may, however, beeasily separated from cadmiam if the solution is acidified with nitricacid and electrolysed. In these reactions, pot'assium ferrocyanide isthe best means of testing whether all the Copper has been deposited,as the ammonium test loses much of its delicacy in presence of oxalicacid.Estimation of Antintmy.-The method previously proposed for theestimation of antimony by electrolysis in the presence of excess ofammanium sulphide (Abstr., 1881, 1081) has several drawbacks.Thesmell produced is very unpleasant, and if the ammonium sulphidecontains polysulphides, or free ammonia, unsatisfactory results ai eobtained. Better results are obtained with sodium or potassium s u l -phide, but even here care must be taken that no polyaulphide ispresent, and that the sulphide employed is free from iron andalumina.The electrolysis must be conducted in the cold, and acurrent yielding 2 to 3 C.C. of electrolytic gas per hour employed.The quantity of antimony in solution must not exceed 0.2 gram.Estimation of %.--Tin is best deposited from solutions of itsammonio-sulphide. If dilute sodium or potassium sulphide is em-ployed, the precipitation is only partial, and the author believes thata complete separation of antimony from tin might be effected byusing concentrated sodium sulphide.Est irnatwn qf Platinum (Potassium, Ammonium) .--The depositionis effected by the current from a single Bunsen cell. The solutionemployed may be acidified either with hydrochloric or sulphuric acid,and ammonium or potassium oxalate added : the solution should beslightly warmed.The author contends that the estimation of potas-sium, ammonium, and nitrogen, by means of the electrolytic dcposi-tion of platinum from their platinochlorides, is more exact andexpeditious than the ordinary gravimetric method.Estimation of Irort.-In separating iron and cobalt, both metals aredeposited by electrolysis of the double oxalates, and the total weightfound. This deposit is then dissolved in dilute sulphuric acid, 2ndthe iron titrated with permanganate, or it may be dissolved in hydro-chloric acid, and the iron then oxidised with hydrogen peroxide-and titrated with stannous chloride. The cobalt is estimated by dif,ference. The same method may be employed for separating iron andnickel, but the reduced metals require strong hydrochloric acid fortheir solution.This method of estimation may also be employed wit11a mixture of iron and zinc, provided that the quantity of zinc present,is less than one-third that of the iron; if the zinc exceeds this pro-0 182 ABSTRACT8 OF CHEMICAL PAPERS.portion, the results are unsatisfactory. I n a solution containing iron.and uranium, the iron may be deposited by means of a current fromtwo Bunsen cells in series, whilst if a large excess of oxdate is used,the uranium is retained in solution.Est;matioiz qf Zim-Zinc is_ sepmated from chromium or fromuranium by electrolysing the oxalates by means of a current yielding10 C.C. electrolytic gas per minute; the zinc is dcposited and thechromium or uranium remains i n solution.In the electrolysis of the mixed oxalates of chromium and uraninm,the latter metal is deposited as hydroxide, whilst the former remainsin solution.Cobalt in the presence of chromium or manganese, isestimated in a manner similar to that described above for the estima-tion of zinc. L. T. T.Decomposition and Analysis of Slags. By M. W. ILSS (Chem.News, 50, 194--196).-The following methods are thoee which arein daily use, and are recommended bp the author for the analysis ofores and slags connected with the lead-silver industry. To sample andprepare for analysis: slag is allowed to run upon the end of R steelbar, or the bar is dipped into a pot of freshly drawn slag, then plungedinto cold water, and the slag dried, and finely powdered. This methodof rapid cooling does not materially affect the chemical composition ofthe slag, but rendera i t readily decomposable hy l~~di*ochloric acid.Theauthor finds that all slags containing from 30 to 42 per cent. of silicaare entirely decomposed in this manner, and, moreover, he believesthat the method would auswer equally well with iron slags. ThesiZica is determined much in the ordinary way, care being taken tothoroughly oxidise the iron before evaporation. &'or iron, about0.5 gram of prepared slag is decornposed with hydrochloric acid, diluted,reduced with zinc, diluted to 500 c.c., about 25 C.C. of concentrated sul-phuric acid added, and the iron titrated with - permanganate. Forwawganese, the finely powdered slag is decomposed with hydrochloricacid with the addition of a few drops of nitric acid, the solution isboiled, and sulphuric acid is added until all the hydrochloric andnitric acids are replaced by it.This solution is diluted to 150 c.c.,boiled, the iron pvecipitated by excess of zinc oxide emulsion, and isfiltered off along with the silica. The filtrate is made up to 500 c.c.,and thc manganese determined by titration with permanganate. ForcaZcium, the filtrate from the silica determination is heated, madealkaline with ammonia, and oxalic acid added 00 dissolve the iron;the calcium oxalate is collected, washed, dissolved in hydrochloricacid, filtered, diluted and decomposed by boiling wjth a large quantityof sulphuric acid ; the oxalic acid is then titrated with permanganate.When greater accuracy is desired, the iron and alumina are removedas basic acetates, the manganese by bromine-water, the zinc byhydrogen snlphide, and the filtrate is treated in the usual manner.For z i i ~ c a gram of substance is digested with a mixture of 10 C.C.hydrochloric, 5 grams nitric, aild 5 grams sulphuric acid (allconcentrated), until t8hick fumes of the last-named acid appear, themass when cool is diluted to 150 c.c., filtered and washed with hotN5ASXLTTlCXL CHEMISTRY.193water. The solution is treated with 2 C.C. hydrochloric acid, satnratedwith hydrogen sulphide, and the precipitate is filtered and washed.The liquid is boiled and oxidised with potassium chlorate, the ironand alumina are then precipitated with a large excess of ammonia,and filtered off, the filtrate is acidified with hydrochloric acid, madeup to half a litre, and the zinc titrated with standard ferrocyanide,using uraiiiuni acetate as indicator.Manganese, nickel, and cobnl tinterfere with this reaction, and must be removed before titra-tion, also when ammonium chloride is present, a correction must bemade. Lead is best determined in the dry way ; if, however, all thelead can be got into solution as nitrate, the following method isaccurate:-Add zinc oxide emulsion to the solution and titrate in thecold with decinormal permanganate to a slight rose tint, warm, and addpermanganate until the second tint is observed. Sulphur is estimatedby fusing the substance with caustic potash, and, after removal of theiron, oxidising with bromine-water, and finally precipitat,ing as abarium sulphate.E’or arseiaic, Pearce’s method is the best, whilstVolhard’s volunietric silver method, when it can be used, proves anexcellent one. Other substances are estimated by the ordinarymethods. D. A. L.Remarks on the Analysis of Soils. By W. RNOP (Landw.Versuchs-Stat., 31, 155--158).-To estimate the quantity of lime andmagnesia present as carbonates and in combination with hnmic acid,the author recommends mixing the soil with potassium chlorate andheating until oxygen begins to be evolved. If the soil is very rich inhumus, it must be first mixed with a sufficient quantity of pure quartzsand, in order to prevent the action from being too violent.Thismethod was tried with a very rich soil from Banat, and yielded per-fectly satisfactory results. The sample contained 27 per cent. water,23 per cent.. humus, and the remainder was composed almost entirelyof quartz and silicatetJ of alumina.By T. MOORE (Chem. News,50, 15l).-The author recommends the following process for the sepa-ration of zinc from nickel as effectual and easy. Expel the excess ofacid by evaporation from the solution containing the two metals, dis-solve the residue in 20-25 c . ~ . of water, and precipitate with excessof ammoniiim sulphide. Dissolve the precipitate by heating it withpotassium cyanide, make up the solution to 250 c.c., add a few C.C.of sodium acetate solution, acidify with acetic, acid, aiid heat to boil-ing.After a few hours wash the zinc sulphide with water containinga small quantity of sodium acetate and hydrogen sulphide, and finallyconvert i t into oxide in the usual manner. To estimate the nickel :-Evaporate the filtrate and washings to dryness with aqua regia, dis-solve the residue in water, and precipitate with potassium hydroxideand bromine. Redissolve the precipitate in dilute sulphuric acid,adding ammonia, and precipitate the metal by electrolysis.New Method for Separating Copper from Cadmium. By P.GUCCI (Bey., 17, 2659-2660).-After bismuth has been separated inJ. I(. CSeparation of Zinc from Nickel.D. A. L134 ABSTRACTS OF CHEMICAL PAPE t<S.the usual way by the addition of ammonia, hydrochloric, nitric, orsulphuric acid is added in sufficient quantity to redissoive thehydmnides of copper and cadmium, and then the copper is precipi-tated by a 10 per cent.solution of ammonium benzoate added inslight excess. The filtrate is tested for cadmium by the addition ofammonia and ammonium sulphide. This separation is very complete,and may be used with advaiitage in quantitative analysis.A. K. M.Determination of Iron and Chromium in Alloys. Hy H.YE’rERSON (Ghern. News, 50, 210).-The author’s method is based onthe fact that chromium sulphate in a sulphuric acid solntion is oxi-dised into chromic acid by boiling with permnnpnate. Half a gramof finely divided alloy is dissolved by boiling with 35 C.C. of dilnte sul-phuric acid ; if any hydrocarbons are dissolved they are oxidised withpermangnnate, and the ferric salt thus formed is redaced with zinc,the liquid diluted to 1 litre, and the iron titrated with permanganate.When the titration is complete, the liquid is boiled, while perrnangan-ate is dt-opped in until there is a plentiful precipitate of manganicoxide, which is filtered off and well washed with hot water.Whencool, the chromic acid is determined in t.he liquid by adding ferrousammonium sulphate in excess and titrating back. If the amount ofchrominm only is required, it is neither necessary to deskmy the hy-drocarbons nor to dilute to such an extent. D. A. L.Estimation of Ammonia in Potable Water. By G. GORE(Chem. News, 50, 182--186).-The author has investigated thissubject experimentally? and below is given an epitome of his experi-ments, results, and conclusions.The water employed in the experiments was an ordinary potablewater yielding, by Wanklyn and Chapman’s method, 0-026 per mil-lion “ free ” and 0.138 per million ‘‘ albuminoid ” ammonia.When 500 C.C.of this water were distilled without previous addi-tion of sodium carbonate, the first 50 C.C. of distillate contained onlya trace of ammonia ; when, however, a similar quantity of this waterwas mixed with various ammoniacal compounds before such distilla-tion, the first 25 C.C. always contained ammonia, as will be seen fromthe appended tbble :-Mgrms. of NH,added.0.j0.050-0280.040.025750.02368Mgms. NH, dis-tilled over in 25 c . ~ .In form ofammonia solution 0.117 9 77 0.019ammonium carbonate 0.019,? chloride 0-024,, sulphate 0.0125,, phosphate 0.0120From the resnlt of a special experiment, the anthor a.ttributes thisdistillation of ammonia to the dissociation of the salts by heat. Itdoes not take place in presence of aluminium salts, and therefore insuch cases sodium carbonate mast be added before distilling. It isevident from these results that the more correct way of determininANALYTICAL CE-IEJLISTRY. 195the presence of “fret: ” or “ saline ” ammonia in a water is by simpledistillation. The water in question evidently contained a mere traceof such ammonia, or none at all, as there were no aluminium com-pounds present. The 0.026 per mil. of “ free ” ammonia (see above)rtiust haye come from other compounds, and it is shown that thec:irbonate appears to act on the organic nitrogenous matter.Whenthe distillate from the ordinary carbonate method is returned to theretort and re-distilled, it gives a slightly larger amount of “free ”ammonia, and by mixing the alkaline carbonate with the sample ofwater 12 hours before distillation a still larger increase is obtained.Other experimeds show that distillation of a water with alkalinepermanganate alone gives as large a total quantity of ammonia aswhen a, previous distillation with sodium carbonate, or distillationwith a mixture of the two is resorted to ; also that the water whendistilled first with potash alone, khen with permanganate alone, yieldsmore ammonia than when a mixture of the two substances is em-ployed.Ordinary permanganate was found to contain ammonia.Caustic soda does as well as potash for rendering the permanganatealkaline. A very dilute solution of urea is not converted into ammoniaby distillation with sodium carbonate, only slightly if alkaline perman-gmate is employed, and ahout one-third of it is so converted when i tis distilled first with potash, then with permanganate. The residue leftIn the retort after completion of the ordinary ammonia estimation,evaporated to dryness and heated t o redness, yields a large additionalamount of ammonia. The sample of water used in these experimentshad a greenish colour when viewed in depths of about a metre ; thiswas shown to be due to vegetable matter which could be precipitatedby aluminium chloride ; after its removal, the water was found to con-tain less “ albumindid ” ammonia ; by this treatment, therefore, theamount of ammonia due t o such vegetable matter may be approxi-mately determined.The effect on the amount of ammonia of hcat-i n g the water nearly to boiling, or of exposing it to sunli6ht andwarmth, or of agitating it with atmospheric air previous to distillation,is seen in the following tables :-E f e c t of Heating.Free ammonia (bydistillation without Albuminoi‘Jsodium carbonate). ammonia.Not previously heated.. .. 0.010 0.1 30Heated for two hours. ... 0.026 0.160,, seven hours.. 0.025 0.160Not shaken ............ 0.005 0.140Shaken for five hours.... 0.005 0.1959 , ten ,, .... 0.010 0.185Unexposed. ............ 0.020 0.1 10Exposed .............. 0.030 0.130Efect of Agitation with Air.E f e c t of Exposure to Xunshine and WarmthTotal.0.1400.1860.1850.1450.2000.1950.1 390.16196 ABSTRACTS OF CHEMICAL PAPERS.In all these cases, although the water has become to a certainextent more wholesome, yet when test'ed by the permanganate methodit, appears more impure than before the change. In the last experi-ments, the exposure was continued until the regetable growth whichformed in the water apparently ceased to increase. The author de-scribes a special tube for the evaporation and subsequent heating toredness of residues as mentioned above; he likewise makes specialreference to the various innocuous sources of nitrogen in water.D.A. L.Detection of Cyanides in the Presence of Compound Cyan-ides. By W. J. TAYLOR (Cliem. News, 50, 227).-Cynnides, whenin the presence of compound cyanides, cannot well be detected by theordinary methods. It is necessary to find a substance which, whilstfreely decomposing the cyanide, will leave the ferrocyanide untouched.This condibiori is fulfilled by hydrogen sodium carbonate. I n thedetection of cyanides in the presence of compound cyanides, all thatis required in qualitative analysis is to distil with an adeqnate volumeof water and an exces8 of hydrogen sodium carbonate; if the pre-liminary exwminat'ion shows the presence of mercury, a few grams ofzinc must be added, as mercury cyanide is somewhat refractory, butis readily decomposed in presence of metallic zinc.J. T.Viscosity of Oils. Ry W. P. MASON (Chem. News, 50, 210).-Inorder to obtain uniform and comparable tests with regard to theviscosity of oils, the following apparatus and niethods are suggested :-A glass cylinder, 22 inches Jong and lainch in diameter, is fitted toa brass bottom, one-eighth of an inch tlrick, in the centre of which isa hole one thirty-second of an inch in diameter, the metal being bevelledawag from the outside surface of the metal a half-inch or more fromthe hole. Eighteen inches above the plate the cylinder is marked withR thick line (the standard head), and between the 16 and 21-inch pointsthere are graduations every one-eighth of an inch.I n using the in-strument all readings are compared with distilled water at 15.5". Todetermine the viscosity of an oil :-See that tlie temperature is normal,take sp. gr., and from it calculate what head will equal 18 inches ofwater (this will be inversely as the sp. gr.). Fill to and maintainthis head whilst timing the flow of lU0 C.C. of the oil, uhich whendivided by the standard time will give as quotient the viscosity of theoil undcr txamination. Such an instrument has been found to workvery well. D. A. L.Examinaticns of Butter. By H. LEFFMARN (Chem. News, 50,192).-As an example of the quality of the butter supplied in Phila-delpbia, 20 samples, sold under Tarious names at prices ranging from25 to 45 cents per pound, were examined by determining the amountof alkali required for the saponification of the fat, siipplemented byWxnklyn's alcoholic-soda test.The numerical results are quotedunder the name " acid-equivalent," which means the neutralisingeffect of 1 gram of fat expressed in equivalenbs of standard acid. 10of tho samples gave the odour of' ethyl butyrate, with acid-equivalenANALTTICAL CHEJIISTRY. 1975.5 or above ; these were " genuine ;" with tbe other samples theodour is indistinct or absent ; four of them are " doubtful " with acid-equivalent not below 5.0 ; the remainder with equivalent below thisnumber are classified as " bogus."By L. W.MCCAY (Chem. News, 50,15l).-With regard to this met,hod of butteranalysis, the author points out that the evaporation of the alcohol fromthe mixture of fat, caustic potash, and alcohol is essential, and isreadily and effectually accomplibhed by applying suction to the interiorof the flask whilst it is heated on the water-bath.AR soon R S themass when shaken shows no tendency to froth, i t may be dissolved inwater, decomposed with acid, and distilled. The author preventsbumping during t'his operation by using small spirals of platinumwire with small pieces of pumice threaded and twisted on each end ofthe coil, D. A. L.D. A. L.Notes on1Reichert's Method of Butter Analysis.Methods of Butter Analysis. By A. HANSSEN and C. E. SCHMITT(Bied. Centrr., 1884, 707-710).-Hanssen has made an exhaustiveexamination of the chief methods of butter analysis, and contributesthe following notes on the subject.Meltin,g point.-The addition of 15per cent. of pure tallow raises the mclting point from 33" to 36-37",and the addition of 20 per cent. raises it to 38.5", but the addition oftallow to the fatty acids obtained by Hehner's method causes no per-ceptible difference. Heat does not appear t o affect the yield of in-soluble fatty acids from either pure or mixed butter; after five hours'boiling, the author obtained 85.5 per cent. The loss of the acids in theprocess of saponitication by alcoholic potash is extremely small, andis lessened by using absolute instead of dilute alcohol. I n Hehner'smethod, the quantity of wat'er employed in washing the precipitatedfatty acids is important, if too little be used or insufficiently stirred,the volatile portions are not fully removed.The authors advise$he use of 2 to 2Q litres, and always a constant quantity; from thewash-water of this process he obtained caprylic, capric, and caproicacids by evaporation with soda, distillation, separation of barium salts,&c., &c.Reichwt o r Meissl's Method.-5 grams of the butter is saponifiedwith potash and absolute alcohol in a flask with a reflux condenser ;the alcohol is then distilled off, the last traces being removed byblowing air through ; the acids are distilled with sulphuric acid, andthe dist'illate titrated with decinormal soda ; pure tallow required only0.3 c.c., pure butter 29.6 c.c.; the number of C.C. found minus 0.4,multiplied by 3.42, gives the percentage of pure butter in the sample,v1z.:-Butter fat.15 per cent. added tallow (25.0 C.C. - 0.4) x 3.42 = 84 5 per cent.20 9 , 9 ) (23.3 C.C. - 0.4) x ,, = 78.5 ,,30 ,? f ? (20.3 C.C. - 0.4)~ ,, = 68.0 ,,Koettstorfer's method, in which the alkalinity of alcoholic potashsolution is diminished less by butter fat than other fat's, is then men198 ABSTRBCTS OF CHEMICAL PAPERS.tioned.the amount of potash neutralised in milligrams :-The author found the difference a s follows-the figures beiug20 per cent. 25 per cent. 30 per cent.Butter fat. tall0 w . tallow. t,allo w.228.4 222.7 221.0 218.3The authors think the Reichert method the hest for the detectionof tallow in butter, and next that of Koettstorffer.Sehmitt khinks that the Lechartier-Reichert system is the best ; itcoiisists in the distillation of vo1:dAe fatty acids from the saponifiedbutter and titration of the distillate with phosphoric acid of 1.45sp. gr. (10-12 c.c.) ; when the distillate amounts to 60 C . C . the con-denser is washed with boiling alcohol and titrated with one-tenthnormal soda ; this operator multiplies the C.C. used by 0.352 t o obtainthe amount of butyric acid.New Reaction for Albuminoi'ds. By W. MICHAILOFF (Chmn.News, 50, 246; from Joux. Rms. Chenz. Sot..).-The reaction alsoserves for the nitrogenous and sulphuretted derivatives of thedbumino'idu. The substance in qiiestion is added to a solution offerrous sulphate, treated with sulphuric acid (undiluted), and thencautiously mixed with a very small quantity of nitric acid. If nitrogenand sulphur are present there appear, along with the well-knownbrown rings, also rings of a blood-red colour, formed apparently at theexpense of the nascent ferric oxide and of the tbiocyanic acid formedsimultaneouslj from the albumino'ids by the action of the sulphuricacid, The appearance of a faint rose colour must be disregarded, asit is produced on merely mixing the reagents without any albuminoi'dbody. J. T.J. I?

ISSN:0368-1769    

DOI:10.1039/CA8854800189

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

198 ABSTRBCTS OF CHEMICAL PAPERS.T e c h n i c a1 C h e m i s t r y.Clarification of Turbid River Water. By LUEGER (BingZ.polyt. J., 254, 233--242).-The author discusses in detail the purifi-cation of water by filtration through sand. He states that the1)rohlem to be solved requires the settlement of the followingquestions :--(1) Is the existing sand adapted for the clarification ofturbid water? (2) At what pressure (head of water) is the com-plete clarification effected ? and (3) What is the magnitude of thetotal filtering surface for a certain quantity of wat8er t o be filtered ?An important element in the success of the filtration of water throughsand is the uniformity in the size of the grain of the sand. Sanddiffering in its degree of fineness admits of the filling up of thel~ollow spaces between the coarser grains by the finer particles, so thateventually the filtering surface is rendered impermeable by water.D.BTECHSZCA L CHE IIIST RT 199Preparation of Sulphuric Anhydride from Nitrosyl Sulphate.By 0. v. GRUBER (Dingl. potyt. J., 254, 139).-The author obtainssulphuric anhydride from the so-called chamber crystals, producedby interposing a series of small chambers between the Glover towerand the ordinary system of chambers. When the whole of the nitricacid is introduced into the system through the Glover tower at adensity not under 58" B., the chambers contain the mixed gases in theproportion necessary to form the compound 2SO3,N2O3,3H2O. FromGay-Lussac towers this compound is obtained in a purer form.Itmay be prepared in small chambers specially constructed €or thispurpose, the chambers being fed wit,h sulphurous anhydride andnitric anhydride. The resulting crJ-stals are freed from all nitro-genous constituents by heating them in acid-resisting retorts andpassing a current of dry air, or oxygen and sulphurous anhydride,through them. Thus liquid and, in some cases, solid sulphuricanhydride is produced, the percentage of anhydride depending on thedryness of t'he crystals attacked. The nitrogenous constituents arepassed into a system of chambers, or recovered in the Gay-Lussactower. D. B.Composition of the Gases produced in the Combustion ofPyrites. By SCHEURER-KESTNER (Campt. rend., 99,531 7-919) .-Theamount, of free oxygen pyesent in the gases from pyrites burners isalmost always somewhat less than that calculated from the composi-tion of the original air and the arn0,uiit of ferric oxide and sulphurousanhydride formed.I n 1875, the author showed that this deficiency isdue, in part a t least, to the formation of sulphuric anhydride. I nthese earlier experiments the determinations of different constituentswere made with different samples of the gases, and since the composi-tion of the gases from the burners is somewhat variable, this met>hodof procedure introduced sources of considerable error. He has there-fore made further experiments, in which all the constituents weredetermined in the same sample of gas. A large volume of t-he gasesfrom the burners was drawn through a standard solution of iodine untilthe latter was jost decolorised. The amount of the sulphurous anhy-dride was thus obtained, and the amount of the sulphuric anhydridewas estimated by determining the total sulphur in the iodine solution,and in a small wash-bottle containing water through which the gasespassed on their way to the aspirator.The proportion of oxygen wasascertained by analysing the gas collected in the aspirator.The results obtained show that the deficiency of oxygen in theburner gases is entirely accounted for by the proportion of sulphuricanhydride formed. In only two out of 15 experiments, and those ofshort duration, was sulphuric anhydride absent, whilst in theremaining 13 its proportioi varied fro;$ 0.1 t o 8.5 per cent.C. H.B.Recovery of Hydrochloric Acid as a Bye-product in theAmmonia-soda Process. By L. MOND (Dingl. polyt. J., 254, 220).-The liquors resulting from the separation of the bicarbonate areheated in a distillation apparatas to remove all volatile salts ofammonia. lnstead of treating the fixed salts of ammonia with lime200 ABSTRACTS OF CHEMICAL PAPERS.the liquors are concentrated by evaporation, and after the removal ofthe sodium chloride, the ammonium chloride is allowed t o crystalliseont. The latter is mixed with two equivalents of sulphuric acid, andheated in iron or leaden pans, the hydrochloric acid given off beingcondensed in the usual manner. The residue left in the pan, con-sisting of hydrogen ammonium sulphate, is converted into ammoniumsnlphate by treatment with gaseous ammonia obtained by distillinggas liquor. It may be used also for the manufacture of manures bymixing it with calcium phosphate in mch proportions that the excessof acid in the salt is sufficient to dissolve all the insoluble phosphatepresent, and form superphosphate.Consumption of Fuel in Blast Furnaces.(DingZ. pdyt. J.,254, 167--177).-Fehland (Eisen and Stahl, 1884, 331 and 497)gives some data as to the time expended in the passage of hhe chargesthrough the blast furnace, as this circumstance must be duly con-sidered i n calculating the capacity of blast furnaces.I n discussing the use of raw coal in blast furnaces, I. L. Bell statesthat some Pennsylvanian pits yield a variety of anthracite which,apart from what may be indicated by actual chemical composition, isody capable of performing a duty 10 per cent.below that of artifici-ally prepared coke, and requires a more highly compressed blast,owing to the fact that it crumbles away on exposure to heat. For thepurpose of illustration, a specimen of bituminous coal from theBrockwell seam in South Durham, gave by analysis-D. B.C. H. 0. N. S. H20. Aph.81-47 4.57 5.04 0.91 1.22 0.76 5-51The coke made from the same coal contained 92.44 per cent. ofcarbon obtained by calculation. By the aid of Dulong's formula, aheat,irig power of 7651 cal. was obtained for the coal, and 7395 cal.for the coke. To confirm the correctness of this calculation, Bellrefers to the observations made by Donne11 on the North EasternRailway, who found that the consumption per mile of coal and cokeby the same engine was practically the same.The volatile con-stituents of coal are, however, only partly oxidised in the blastfurnace, but might be useful as a means of reducing the ferric oxideto the metallic state. As a further illustration, a description of theworking of a blast furnace is given, using cannel coal from Lanark-shire, the furnace having a height of 22.5 metres, and being blownwith air at 427". The coal was analysed by Rocholl with the followingresults :-H,O given offat 100". C. H. 0. N. S. Ash.11.62 66-00 4.34 11.09 0.94 0.59 5-42Volatile .. . - 12.59 4.34 11.09 0.94 - -The following figures contain the results of the analysis of thegases taken from the blast furnace :TECHNICAL CHEMISTRY.201coz. CO. CH,. CZH,. H.Per cent. by vol.. ... 6.29 29.04 2.84 0.24 6.85,, by weight. 9-66 28.36 1.59 0.23 0.48N. NH,. HzO.Per cent. by vol.. ... 54.63 0.13 -,, by weight. 53.34 0.07 6.27The proportion of carbon as CO, to carbon as CO is as 1 is to 4.62,the escaping gases showed a temperature of 190", whilst, the blastaveraged 427". The charge consisted of the following mixture calcu-lated on 100 parts pig iron :-Coal. Ironstone. Limestone.212.0 187.5 54.7The carbon contained in the charge was as follows :-Fixed carbon in the coal used.. ...... 113.226.7Carbon in the limestone ............ 6.6146.53.56.9Carbon in the hydrocarbons .........-Deduct carbon absorbed by pig iron ..Deduct carbon in tar.. .............. --Carbon in escaping gases.. .......... 136.1The weight of the escaping gases per 100 parts pig iron is asfollows :-Carbon. Oxygen. Hydrogen. Nitrogen.CO, .... 81.3 22.1 59.2 - -CO .... 238.6 102.2 136.4CH,.. .. 13.4 10.1 - 3.3 -CZH, ... 1.9 1.7 - 0.2 -H . . . . . . 40 - - 4.0 IO . . . . . . 443.9 - - - --NH,.. .. 0.6 - - 0.1 448.9 .... 5.8 0.5 HsO 52.7841.4 136.1 242.5 13.4 449.4- -- --- -- - -The quantity of heat developed is ascertained by the following calcu-htion, whilst, for the purpose of comparison, the values of a furnaceusing 111% parts of coke are given, in which Cleveland calcinedironstone is smelted, the carbon in the coke employed being 108parts :202 ABSTRACTS OF CHENICAL PAPERS.Raw coal.Fixed carbon.................... 113.2Deduct carbon in limestone ...... 6.5Leaving carbon to develop heat.. .. 106.7Heat developed in burning carbon tocarbonic oxide ................ 256,080 cal.Heat developed in burning part ofthe carbon to carbonic anhydride 124,040 ,,Heat developed in burning the hy-drogen ...................... 93,500 ,,Heat contained in the blast. ....... 59,600 ,,Total heat developed ........ 533,220 ,,--Appropriation of Heat.Fusion of slag .................. 50,270 cal.Decomposition of water .......... 1.5,810 ,,Expnlsion and decomposition of thecarbonic anhydride in the minerals 41,180 ,,Expulsion of hydrocarbons ........ 122,8W ,,Evaporation of water............. 15,2 55 ,,Reduction of the ferric oxide ...... l63,5.50 ,,Carbon contained in the pig iron. .. 8,400 ,,Iteduciion of silicon, phosphorus, andTransmission through the walls ofsulphur ...................... 21,330 ,,the furnace.. .................. 27,435 ,,Fusion of the iron.. .............. 33,000 ,,Carried off in cooling water.. ...... 9,090 ,,Carried off in escaping gases ...... 44,765 ,,552,885 ,,Coke.102.08.293.8---225,120 cal.182,560 ,,-59,595 ,,467,275 ,,83,510 cal.13,600 ,,51,*;10 ,,1,560 7,7,200 9 7-165,540 ,,20,870 ,,18,290 ,,33,000 ,,9,090 ,,55,215 ,,459,385 ),It will be perceived that in the case of the furnace using raw coal amuch less oxidation of the carbon takes place, and in consequence amuch smaller development of hea,t. The heating power of the carbonis, however, largely supplemeiited by the combustion of the hydrogen,but all the heat developed by the combustion of this gas, and far more,is absorbed in the act of expelling the volatile portions of the coal.The reducing action of the blast furnace gases on spherosiderit,eceases when one-third of the carbonic oxide has been converted intocarbonic anhydride, so that, for example, on exposing Cleveland ore tothe gases escaping Prom a furnace 20 m.in height little or no reductionwas effected. I n the case of the furnace using raw coal, these limitsare fasr from being reached, for iu its escaping gases the proportionwas 4-62 parts of carbonic oxide to one of carbonic anhydride, orincluding the hydrogen and hydrocarbons, tJhe ratio was 6 22 parts taone of carbonic anhydride.Of the carbon introduced into the furnace,it may be assumed that none of that contained in the hydrocarbonTECHNICAL CHENISTRT'. 20 3reaches the neighbonrhood of the tuyeres. Hydrogen, however, theresult of the decomposition of atmospheric moisture, is always presentin the gases a t that place, whether the furnace is usicg coal or coke.In using coke or coal, it is estimated that the carbon which ought tobe found in the gases per 100 parts by weight of pig-iron is asfollows :-Coke. Coal.Due to reduction of ferric oxide. . 32.9 pts.From decomposition of limestone. 8.2 6.332.9 pts.Total ............Actually found ........Deficiency ........Carbon in the coke ............Deduct the carbon contained in thecarbonic anhydride being re-solved into carbonic oxide ....Solid carbon in hearth ......41.1 39.432-6 22.18.5 17-3102.0 113.2-- --8-5 17.3--93.5 pts.95.9 pts.It will thus be seen that there is no great difference in the twoexamples as to the quantity of carbon which actually reaches tlietuyeres for fusing the iron and slag. The advantage of working withlofty furnaces is the increased period of time during which the ore i sexposed to the reducing action of the carbonic oxide a t a temperatui-ebelow that which suffices to have carbonic anhydride decomposed bycarbon. l'his circumstance is said to be the cause of the disap-pearance of carbonic anhydride in the older furnaces used in Cleve-land.Whilst a furnace 24 m. in height yields about 32.6 pts.carbon as carbonic anhydride per 100 pts. of iron, a furnace 15 m. inheight yields only 27.4 pts. The disappc-arance of the carbonicanhydride in the Scotch furnaces is partly due to the presence of thehydrogen emitted by the coal. On passing hydrogen over limestoneplaced in a heated tube, Bell found that about one-haIf the carbonicanhydride was resolved into carbonic oxide, water being formed.The carbonic anhydride is reduced a t the tuyeres, but the aqueousvapours generated are decomposed by the coal. The gases a t thetuyeres of a Scotch furnace consisted of 1.43 per cent. carbonicanhydride, 32.96 carbonic oxide, 2.60 hydrogen, and 63.04 nitrogen.By adopting the nitrogen as the basis of the calculation, the carbonpresent works out t,o 1032 instead of 106.7, as 4413.9 parts of carbonare present for 100 pts.of pig-iron. In the case of the Scotch canrielcoal, it may be assumed that the heat produced by the combustion of thegases contained therein will suftice for their own expulsion. 100 pts.coal should give 58.83 coke, consisting of 91.63 per cent. carboii,0.50 water, and 7-87 ash. The quantity of heat required to smelt100 kilos. pig-iron in the Scotch furnace, using the coal as coke, insteadof raw coal, is estimated at 417,815 cal. The heat developed byburning one part of carbon to carbonic anhydride and 2.28 to carbonicoxide with a blast heated to 427", amounts to 4587 cal. per kilo204 ABSTRACTS OF CHEMICAL PAPERS.of carbon.This is equal to 91.1 kilos. carbon per 100 kilos. pig-iron, andby adding 3.5 per cent. carbon found in the pig-iron, 94.6 kilos. areobtained, corresponding with 103.25 kilos. coke containing 91.63 percent. of carbon. But the coal actually used in the furnace contained113.2 kilos. of fixedcarbon, equal to 123.5 kilos. of coke, so that there isa waste of 18.6 kilos. carbon per 100 kilos. pig-iron when raw coal iswed. The 18.6 kilos. of carbon, or, say 20 kilos. cannel coal, are notworth in the market above 15 pfennigs, which is less than the cost ofconverting this cod into coke.In employing raw coal in blast furnaces, it must be borne in mindthat for the condensation of the tar and ammonia, given off by thecoal, about thirteen times the quantity of gases has to be dealt with, ascompared with tlio space occupied by the volatile constituents of thecoal in the process of coking.It is said, however? that there is nomore ammonia and tar obtained from a ton of coal distilled by Peaseand Co., in the Carvbs’ oven, than is obtained by Baird and Co. fromthe coal used in the blast furnace, yiz., about 9 kilos. ammoniumsulphate, valne 2.3s. and about 1.8s. worth tar ; recently 13% kilos.sulphate and 102 kilos. tar have been obtained. D. B.Extraction of Nickel and Cobalt from its Ores. By P.MANHBS (DingZ. polyt. J., 254, 271).-It is proposed to separate thegangue accompanying sulphuretted and arsenical cobalt and nickelores by fusion, and subject the product to a current of air in aBessemer converter until almost the whole of the iron has disappeared.The residue contains from 15 to 20 per cent. of metalloids, and 1 to ‘Lper cent.of illon, the remainder being nickel, cobalt, aEd copper, whichare separated in the usual manner (compare Abstr., 1884,515).D. B.Japanese Bronzes. By G. MARQUARD ( D i ~ g l . polyt. J., 254,138).The Bavarian Technological Museum a t Niirnberg contains 18 platesof Japanese bronzes from Kioto, which have been recently examinedby the author. He found that these plates were composed of f i v edifferent alloys, which are recognised by a uniform mark on the faceof each plate. The following anal-pes give the composition of thealloys arranged in accordance with the transition of colour from brassto pure copper :-Cu.Sn. Pb. Zn. Fe. As.1. Brass . . . . .. .. .. 73-28 - 0.79 25.71 traces traces2. 0 mark of .. 72.60 4.0 11.74 ‘11.48 0.21 ,,3. OO{ the ,,4. C alloy . . 82.17 3.96 13.34 0.28 0.24 ,,5. Copper (containing traces of lead and iron).The high percentage of lead in the alloys was used probably tofacilitate the mechanical treatment of the castings and the colouringby the aid of chemical agents.. . 75-43 3.18 15.07 5.64 0.45D. B.Nitrogenous Contents of American Beers. (Bid. Cen tr.,1884, 717).--Fifteen samples of beer were examined in the officiallaboratory a t New Pork, the percentages of nitrogenous substancTECHNICAL CHENISTRF. 205in the extract ranged from a minimum of 7.5, to 14.5 wihh an averageof 9.8, the variations are therefore within very wide limits.Cultivated Wine Yeast.By A. RONMIER (Compf. rend., 99,879-880).-The author has extended his observations as to the effectof adding cultivated mine yeast to the must from different varieties ofgrapes, and has obtained results identical with those obtained withChasselas (Abstr., 1884,1399). The fermentation induced by addingthe yeast takes place much more rapidly, and is complete in a farshorter time than the natural fermentation. The yeast should beadded when it has attained full derelopment.J. F.C. H. B.Treatment of Syrups by Electricity. By L. H. DESPEISSTS(Dingl. poZyt. J., 254, 209-211).-The author proposes to separatethe alkalis and alkaline earths contained in saccharine juices bysubjecting the latter to the action of an electric current.He claimsto obtain an increase in the yield of sugar, and to recover the alkalis.The carbonates and saccharates of the juice are said to be decomposedby the influence of the electric current, carbonic anhydride and sugarbeing deposited at the positive pole, whilst the metals contained in thejuice decompose the water which surrounds the negative pole, and arerecovered in the form of bases.The practicability of this process is doubted owing to the difficultyof effecting the separation of the alkaline earths, inasmuch as theresulting hydroxides which are deposited on the negative pole wouldinterrupt the passage of the current in a very short time.Animal Charcoal in Sugar-refining.By H. PELLET ( B e d .Centr., 2884, 711-712).-Many refineries have ceased to use animalcharcoal, employing instead the Puvrez filtration system, but it isfound that the tubes soon become clogged, and the apparatus refusesto work ; the author attributes this to the presence of silicic acid, andas this is not found in the beet it evidently is derived from the limeused in clarification, limestone itself containing certain proportions,and some being present in the ash of the coke used in burning the lime.Having analysed the residues of the triple e f e t evaporation system,he found in the first 0.40 per cent., in the second 23-40 per cent., andin the third 69.80 per cent. of silicic acid.Filtration of the juicethrough bone char removes the silica effectually, but soon rendersthe charcoal useless ; the organic matter can be removed by reburning,but not the silica ; the charcoal should be frequently changed and usedas fresh as possible.Gawalowski has found in 12 samples of limestone examined by himquantities of silicic acid varying from 0*10 per cent. up t,o 29.76 nercent. J. F.I). B.Manufacture of Maltose by Dubrunfaut’s Method. By L.CUISINER (Bied. Centr., 1884, 71 7-718) .-Distilled water should beused, if possible. Should the water employed contain bicarbonate oflime or gypsum, it must be freed from them in order to avoid butyricfermentation ; for the production of crystallised sugar, the purestVOL. XLVIII.206 ABSTRACTS OF CHEMICAL PAPERS.starch should be used ; for syrups, flour, potatoes, and raw graiu maybe employed ; the aqueous malt extract is best made from p e n malt.The starch is made into an emulsion with twice its weight of water,and after adding 5 per cent. of malt or its equivalent in extra&,it is energetically stirred ; in another vessel, water equal to 20 timesthe weight of the starch is heated to go", and both liquors pouredsimultaneously through a strainer, steam being blown through to corn-plete mixing and solution ; the temperature on entering the vessel is13 , and when 90" is reached the mixture is as fluid as water andthe operation is completed. The liquor is then c d e d t o Po", maltextract added equal in maIt to 10-15 per.cent. of the starchoriginally used, and the temperature maintained R t 40-50" ; aftertwo or three hours, there is no reaction with iodine, and if syrupis wafited the process is interrupted at this point, but for solid maltosethe temperature must be contimed for 12 to 15 hours. If pure starchhas been used, one filtration is sufficient, but in the case of rice andother materials the residne should be pressed ; the liquor should nowshow a density of 4" Baum6 ; it is evaporated to 20" B., left to cool andclarify, and the cleap yeIlow syrup is then filtered through ignited andwashed charcoal from which it flows clear. I t is finally evaporated to40" B. in copper or tinned apparatus; at that density i t is perfectlyclear and mixes with water in all proportions without turbidity.Report on Glucose.By G. F. BARKER and others (ChPm. News,50, 196--198).-This is a report prepared for the Commissioner ofTnternal Revenue of the United States. The quantity of corn usedfor the manufacture of glucose in the States is estimated at 43,000bushels per diem. The commercial products are of two kinds:(u) liquid, including glucose, mixing-glucose, mixing-syrup, corn-syrup, jelly-glucose, confectioners' crystal glucose ; and ( b ) solid,including solid grape-sugar, chipped grape-sugar, grand ated grape-sugar, powdered grape-sugar, confectioners' grape-sugar, and brewers'grape-sugar. Its uses are for the manufacture of table syrnp; inbrewing, instead of malt ; in confectionery, instead of cane-sugar ; asan adulterant of cane-sngar ; for manufacturing artificial honey ; andfor making vinegar.The transformation of starch is generallyeffected by sulphuric acid; oxalic acid is, however, sometimesemployed, and the use of phosphoric acid has been suggested. Liquidproducts contain more dextrin and maltose than the solid ones. Thelatter contain from 72 to 73.4 per cent. of dextrose, and from 4.2 to9.1 per cent. of dextrin, whilst the glucoses (liquid products) havei34.3 to 49.8 per cent. of dextrose, and 29.8 to 45.3 per cent. of dextrin.The contention amongst workers in Germany with regard to the pre-judicial or non-prejudicial effect of the use of sugar (prepared frompotato-starch) in brewing, &c., is entered into in some length,although no decidedly definite results were obtained.The authorsthen describe their own experiments, which consisted in submitting tovery careful fermentation, with pure yeast, a t a low temperature,ordinary barley worts, cane-sugar, and various samples of glucose.Five litres of the beer obtained in each of these fermentations wasevaporated in most cases to 500 c.c., and tit different times 200 C.C.I-"CJ. FTECHNICAL CHEMISTRY. 207of each residue was taken internally by individuals, who did not sufferinconvenience in any of the cases investigated. From these results, i twould seem that the products of the fermentation of glucose preparedfrom maize are not injurious to health ; as, however, the experimeiitsonly lasted two months, it is still a question whether the continuousnse of tbis substance might not cause injurious effects.It is alsopointed out that although these products are not deleterious, it doesnot follow that beer brewed from glucose is as good as that made inthe tlsual way.Some Constituents of EmmenthaJer Cheese. By B. R ~ S Eand E. SCHULZE (Land-. Versuchs-Stat., 31,115-137).-This work is?t supplement to Weidemann’s paper on the changes undergone byErnmenthaler cheese during the process of decay, and is chiefly con-fined to a qualitative examination of the products formed. Etherextracts a fat which proved to be a glyceride, but was not furtheranalysed, also lactic acid and a small quantity of cholesterin. Theresidue, after treatment with ether, Consists mainly of albuminoldsand their decomposition prodncts, together with sundry salts.Leucine is obtained in quantity by treating the residue with 70 percent.alcohol, and may be purified by repeated crystallisation from~lcoholic ammonia; tyrosine and lactic acid are also t o be found inthis residue, although in small quantities, and the presence of otherorganic acids was also noted. Caseoglutin is found in the alcoholicextract in considerable quantity, and can be precipitated by theaddition of absolute ether and alcohol, as it is insoluble in a 90 percent. solution of tbe latter. Tts analysis gave the following results :-Carbon, 54.4 ; hydrogen, 7.34 ; nitragen, 15.29 : sulphur, 0.95 ; andoxygen, 22.02 per cent. Its alcoholic solution dries in the air to atranspapent mass having the appearance of glue. Phosphotnngstkacid and tannin throw down cnseoglutin completely from its solutions ;the latter are optically active, and kevorotatory.The products ofdecomposition of caseoglatin are glutarnic acid, tyrosine, leucine, andasparagine.The albumen left after treatment of the cheese successively withether and alcohol was found to differ very slightly from the purifiedalbumin precipitated from milk by rennet, and called by the authorsparacasein. Both, when treated with pepsin, throw down a precipi-tate of nuclei’n, and they yield nearly the same figures on analysis,the slight difference being probably due to their not containing quitethe same amount of nuclejin. J. I(. C.D. A. L.Action of Bisulphites on Chlorates.By PRUDHOMME (Di71g~.potyt. J., 254, ‘226) .-On treating sulphurous anhydride with chloricacid, sulphuric and hydrochloric acids are formed. The bisnlphitesof the alkalis, however, reduce the chlorates only in a very imperfectmanner, as shown by the following equation :-NaC10, + NaHSO,=HCIO1 + Na,SO, and NaClO, + 2NaHS0, = HClO + Na2S04 +NaHS04. The resulting hydrogen sodium sulphate may be madeto react with further portions of bisulphite, sulphurous acid being dis-engaged. On adding a solution of sodium bisulphite to a concentrate208 ABSTRACTS OF CHEMICAL PAPERS.solution of sodium chlorate (100 grams per litre), a violent actionoccurs, especially i€ the solution of chlorate is hot. A strong odourof chlorine oxides and of sulphurous acid is givenoff, and the solutionwill be found to destroy the colour of indigo and d h e r dye-stuffs, andconvert cellulose into hydroxycellulose.With salts of aniline, thesolution forms aniline-black, a reaction which confirms Rosenstiehl'stheory as to the formation of aniline-black. When chlorates andbisulphites act on one another in the presence of alcohol, chlorinatedethers are formed. D. B.New Chrome-mordanting Process. By H. KOECHLIN (Ding Z.polyt. J., 254, 132).--This pilocess depends on the fact that whensolutions of chromium salts saturated with alkalis are brought intocontact with the fibre, the chromium oxide is at once given up tothe latter without the necessitJy of drying.The fabric is digested for 12 hours in a bath containing 2 parts (byvol.) of chromium acetate (16" B.), 2 parts soda-lye (36"), and 1 ofwater.Ferric oxide mfiybe fixed on the vegetable fibre in a similar manner, but owing to theinsolubility of Fe,(OH)6 in alkalis, the precipitation of the hydroxideshould be prevented by adding certain organic substances. The fol-lowing mixture gives good results :-2 parts ferric nitrate (40"),2 soda-lye (36"), and 1 glycerol (28.). D. B.Formation of Hydroxy- and Chloro-cellulose Electrochemi-cally. By F. GOPPELSROEDER (Diwgl. polyt. J., 254, 42--43).-Theauthor gives the first results of an investigation of changes producedelectrochemically in cotton and linen fibre. A cotton or linen fabric,soaked in a neutral, acid, or alkaline solution of potassium nitrate o rsodium chloride, is laid on a similarly soaked cloth, resting on anegative platinum electrode ; on pIacing the positive electrode incontact with the fabric for a shorter or longer time, the products setfree at the positive electrode by the current, produce such a changein the fibre that certain dyes are much more readily fixed than in theunchanged portions. J. T.Preparation of the Sulphonic Acids of Methyl Violet.(Ding!. polyt. .J., 254, 140.)-To prepare the sulphonic acids ofmethyl violet (violet de Paris), an excess of sulphnric acid has to beused, which is subsequently neutralised with calcium hydroxide, theresulting solution being evaporated. During the process of eva-poration, the dye is partly decomposed. According to the Socie'te'Anonyme des MatiBres Colorantes et Produits C7Limipue de St. Denis inParis (Ger. Pat. 28,884, December, 1883), the excess of acid is com-pletely or partly converted into soluble sulphates such a s potassium,sodium, ammonium, magnesium, or zinc sulphate. The colouringmatter is then treated with a small quantity of water sufficient toform a paste therewith.It is then washed thoroughIy with water.D. B

ISSN:0368-1769    

DOI:10.1039/CA8854800198

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

20960" glass prism . . . . . .Rutlierford grating.. . 60 quartz prism.. . . . .General and Physical Chemistry.C. n ! ? ! E. 6 . F.2 .--------- ----+ 7-50 + 7.67 + 9 *83 + 7 -50 + 9.33+ 8-28 + 9.06 + 9.53 + 9.06 + 13.75- - 4'10 - 2-27 - 6.36 - 4.32Coloration of the Hydrogen Flame. By S. SANTINE (Gazzettn,14, 142--146).--Tt is generally stated that hydrogen burns with acolourless flame ; but it is here shown that under certain conditions theflame is coloured, and that this effect does not result from impuritiesin the materials used for generating the gas. The phenomenon is themore marked if a tube is placed over the flame, as in the chemicalharmonicon, when the various colonrs of the spectrum can be observedby varying t,he conditions of the experiment.I n general the centreof the flame is green, while the external envelope is of a violet-bluecolour; by reducing the pressure of gas, the blue colour becomesgreen, and then successively yellow, orange, and red. Thus, bydecreasing the intensity of the combustion, whether by the less directcontact of the oxygen with the hydrogen in the centre of the flame,or by st diminution of the pressure, the refrangibility of the emittedlight decreases. The author considers that the variations of thesolar mectrum mav arise from differences in the densitv. and conse-quentli of the lukinosity of the hydrogen contained wi<hin the solarphotosphere. V. H. V.Influence of Temperature on Spectroscopic Observationsand Measurements. By G. K R ~ ~ S S (Bey., 17,2732 -2739) .--In theexperiments described in this paper, the room in which the obser-vations were made was heated to various temperatures, a t which itwas kept constant for some hours, the observations being taken whenit was ascertained that the temperature of the spectroscope was thesame as that of the surrounding air.Comparative experiments aredescribed with a 60" glass prism, a 60" quartz prism, and a Ruther-ford grating, and these show that very appreciable errors may beintroduced by a difference in temperature of 25" :-The figures represent the amount of deviation in units of the scaleseniployed, the sign + indicating that the deviation is towards theviolet, the sign - that it is in the opposite direction ; the mean errorof observation is about 0.31 unit, whilst the deviation for 1" is0.366 unit.The following table shows a comparison in wave-lengths,T being the scale-number :-!I VOL. XLTlII 210 ABSTRACTS OF CHEMICAL PAPERS.I l-T.1169 -41432 -91801 -51863 *121M -8656 -8589 -7527 -4517 -7486 -5658 *9592 *O529 .O519 -2488 ‘0A. K. M.Specific Refraction in Reference to the Double Bond. ByR. NAS~NL (Gaxzetta, 14, 150--156).-The author, in association withBernheimer, has shown, principally from experiments on the naph-thalene-derivatives and cinnamic acid, that Bru hl’s hypothesis thateach pair of carbon-atoms, combined together as in the olefines (theso-called double bond) increases the molecular refraction (Gazzetta,13, 137) is incorrect.Recent experiments by Kanonnikoff on thesame class of derivatives tend, however, to confirm this hypothesis.The cause of this discrepancy is examined in the present memoir.The difference in the results arises from the fact that Kanonnikoffused solutions of those substances, whereas Nasini’s and Bernheimer’sexperiments were conducted with the solids or liquids themselves, aprocess more likely to give trust worthy results.On a comparison of the results obtained with cinnamic acid, naph-thalene, bromonaphthalene, and a-naphthol, the difference of the valuefor A is in one case more than 2 units, or practically equal to the sup-posed difference produced for each pair of double-linked carbon-atoms.Kanonnikoff’s experiments, however, show that the difference of2 units is not constant, but in certain naphthalene-derivatives adifference of 3.6 units is noticed, a result which is explained away bythe great dispersive power of these substances (see Gladstone, Trans.,1884, 254-259).In the case of naphthalene tetrachloride, whosedispersive power is certainly riot greater than that of many benzene-derivatives, the increase of specific refraction A is 8.66 instead of6 units as required hy Briihl’s hypothesis. The only argument whichmigllt tend to explain these abnormal variations is the want of exact-ness in the constant A, but even this would militate against ratherthan support Kanonnikoff’s views; for the values f o r A and ofP k1 increase with the number of constants used for their calcu-tion, as for example:-dP A A (two P A-2 (three A (two con- A (three d d&ants>.constants). constants). constants).Dimethylnaphthalene 1.5637 1.57476 87.02 88.73Methyl-a-naphthol . . 1.5721 1.58953 82.44 84.29In conclusion, Kanonnikoff’s views regarding the const,itution offurfuraldehyde and pyromucic acid, based on the determinations oftheir molecular refraction, are criticised, for the formuh assigned tGENERAL AND PHYSICAL CHEMISTRY. 21 1ma.0AI 1 HC-CHHC=CHOH.C=C.COH] I , respectively point to a them, HC-C.COOH andwide difference of constitution, although, in its reactions, furfuraldehydecomports itself its the aldehyde corresponding with pyromucic acid.V. H. V.Refractive Power of the Hydrocarbon C,,H,,.By A. ALBITZKY(J. pr. C'hem. [Z], 30, 213--214).-This hydrocarbon was preparedfrom ally1 dimethyl carbinol by Nikolsky and Sayt'zeff's method(Abstr., 1879, 214). The sp. gr. and refractive indices were deter-mined with a portion boiling at 195-199'. The specific refract'ionshows that in this hydrocarbon three of the carbon atoms are unitedby double linkage.The following a1.e the results of the determinations :-Sp. gr. a t0" = 0 8512, a t 9.8" = 0.8449, at 21.4" = 0.8349, at 18.4" (calc.) =0.8381 (water a t 0" = 1).Refractive indices for hydrogen lines a, (3, y, and for sodium line Da t 18.4" are:-w. 9- A. B.____---,--- ---1 '48537 1 -49369 1 *45667 0 -69829~~~ ~ ~ ~~P. P. B.Dispersion of Sodium Chromate. By G. WYROUBOFF (Juhrb.f.Xin., 1885, 1, Ref., 25).-This salt, sodium chromate with 4H20,described by the author in 1880, is remarkable for its strongly inclineddispersion of the bisectrices and strong dispersion of the axes. Theacute positive bisectrix forms with &, in the obtuse angle p, an angle of10" 21' for red light, and 7" 49' for green light. The angle of theaxes is 16" 10' for red, and 32" 22' for green (in air). Well preparedspecimens in Canada balsam last for a considerable time.B. H. B.Electric Conductivity of Amalgams. By C. L. WEGER (Ann.Phys. Chern. [2], 23, 447-476). -The experiments of Matthiessenand Vogt on the influence of a foreign metal on the conductivity ofmercury, led to no satisfactory results, owing to the difficulty ex-perienced in the production of a homogeneous material.The experi-ment herein detailed, shows that the conductivity of amalgams of tinand mercury increases with increase of temperature, and vice verm ;212 ABSTRACTS OF CHEMICAL PAPERS.but that these changes are regular when a small percentage of tin onlyis added.The thermoelectric positions of various amalgams of copper arealso compared with t h a t of pure mercury: the presence of the foreignmetal in all cases diminishes the difference of potential. Thoseexamined may be arranged in the following series (if 0.5 gram of themetal be added to 100 grams of mercury) : tin, silver, lead, zinc,cadmium, and bismuth. The specific resistance of the combinationdecreases with increase in the amount of metal added.A comparisonof the galvanic resistance and thermoelectric difference of potentialshows that in all cases, with the exception of cadmium, increase ofthe former is correlated with increase of the latter.In conclusion, the author remarks on the advantage of mercuryas the metal for comparison in thermoelectric series, as reproduciblein a homogeneous state, and as the only metal which shows no differ-ence of potential when one portion is warmed and the other cooled. v. 11. v.Electric Conductivity of Solution of Carbonic Anhydride.By E. PFEIFFER (AWL Phys. Chem. [2], 23, 625-650).-The ex-periment.s of Hittorf on .the migration of the ions during electrolysispoint to the importance of electric functions in deciding the chemicalconstitution of solutions of gases i n water.Kohlrausch has alsoproved by experiments on the electric conductivity of solutions ofammonia, that these do not contain the hypothetical combination-ammonium hydrate. I n t h i s paper, an account is given of experi-ments on solutions of carbonic anhydride under increased pressuresyarying from 1 to 25 atmospheres. The following are the principalresults :-(i.) A 601UtiOn of carbonic anhydride in water forms one of theworst conductom known .: the aonductivity under normal conditionsbeing about one-twentieth of that of spring-water.(ii.) Although it is commonly assumed that a solution of carbonicanhydride in water contains the hypothetical carbonic acid, H&O, inthat it possesses an acid reaction, yet according to Kohlrausch’s ex-periments the conductivity of such a combination should be equal to202,000 = C.G.S.units, or more than a thousand times greaterthan the highest value fmnd.(iii.) Change of pressure produces no alteration in the conductivity,which would appear to show that the carbonic auhydride is liquefiedin the process of solution.(iv.) Carbonic anhydride is soluble in water a t temperatures aboveits critical point; if then the solution were a mixture of water andliquid carbonic anhydride, it is probable that irregularities in its con-dactivity would be observed at the critical point, but this is not thecase.(v.) The curve of the conductirity as a function of the femperd-ture is analogous to the curves dacribed by Kohlrausch for oxalic,tartaric, and acetic acids, in that it ascends rapidly for increase ofdilution. This would seem to point to an analogy of constitution ofu solution of carbonic anhydride in water with these acids.V.H. VGENERAL AND PHYSICAL CHEMISTRY. 213Influence of Magnetisation on the Resistance of MagneticLiquids. By F. NEESEN (Ann. Phys. Chem. [a], 23, 482-493).-Former experiments on the influence of magnetisation on the conduc-tivity of magnetic liquids have led to negative results. I n this paper,an account is given of an investigation on the effect produced by thernagnet'isation of ferrous sulphate as regards its electric conductivity.It would appear, so far as the experiments would permit of a conclu-sion, that if the lines of the magnetic field are normal to the direc-tion of the electric current, no effect is produced, but if the two areparallel to one another, the electric conductivity is increased andeventually the electromotive force of the polarisation of the liquidappears to be diminished.V. H. V.Diathermancy of Esculin. By K, WESEENDONCK (Ann. Phys. Chem.[2], 23, 548--553).-Lommel has concluded from his researches thatfluorescent substances are divisible into two classes ; the members ofthe one display marked absorption-bands in the visible part of theBpectrum, but do not follow Stokes' law, while those of the other,although in accordance with that law, do not shorn these absorptionphenomena in such a marked degree. The author has examinedwhether in substances of the second class, of which aesculin wasselected, absorption-bands cannot be detected in the ultra-red portionof the spectrum, but the results obtained were negative.V. H.V.Tension of Aqueous Vapour of Hydrated Salts. By W.SIISLLER-ERZBACH (Ann. Phys. Chem. [el, 23,607--625).-The experi-ments of Naumann and Kraus on the tension of water-vapour evolvedin a Torricellian vacuum from hydrated salts, led to unsatisfactoryresults, owing to the reabsorption of the emitted water by the par-tially dehydrated salt, when the tension of the former had reached acertain point. The observations are also complicated by the con-comitant alterations of the tension of the vapour of mercury. Thomethod described in this paper is based on a comparison of the lossexperienced, by two suitably constructed tubes of the same dimen-sions, the one containing the salt to be examined, the other distilledwater, both enclosed over sulphuric acid.I n the experiments hereindescribed it is shown that there is practically a constant ratio betweenthe diminutions in weight experienced by the tube for each definitecombination of the salts with their water of crystallisation. Thus a,convenient method is presented for determining the nature and degreeof combination of the molecules of water with the molecules of salt.The following results were obtained :-There are three definite com-pounds of disodinm hydrogen phosphate, with 2, 7, and 12 rnols. H,Orespectively ; two compounds of' sodium carbonate with 1 and 10 mols.H20 ; two compounds of sodium borate with 5 and 10 mols.H,O. The10 mols. H20 of crystalline sodium sulphate seem to be combinedin an equal degree. The last molecules of water of crystallisation ofsodium phosphate and carbonate are removed by a saficiently longexposure over sulphuric acid (comp. Abstr., 1884, 952). V. H. V214 AESTRAOTS OF CHEMICAL PAPERS.Condensation of Carbonic Anhydride on Glass. By H.KAYSER (Ann. Phys. Chem. [ S ] , 23, 416--426).--Runsen’s researcheson the condensation of carbonic anhydride on glass are in directopposition t o former observations (comp. Abstr., 1884, 146), in thathe found that the phenomenon was incomplete after three years, thatalteration of pressure was without effect, and that the condensationincreased with rise of temperature.The author has repeated theseexperiments with the following results :-(i.) The condensation iscompleted a short time after the introduction of the gas, provided thatthe glass surface is perfectly free from other gases; other less con-densible gases are ousted by the carbonic anhydride. (ii.) The qnan-tity of gas condensed increases with rise of pressure and decreaseswith diminution of pressure; it increases with diminution of, butdecreases with rise of temperature. These results are i n accordancewith former observations with other gases. The author remarks onthe inadvisability of applying the name “ diffusion ” to this phenome-non of the condensation, or “ absorption ” of gas on glass : for theformer term is applied to the most various phenomena.The name“ penetration ” is proposed as more applicable and suggestive.V. H. V.Combustion of Hydrocarbons and their Oxides and Chlo-rides with Mixtures of Chlorine and Oxygen. By G. ScHLEGEr,(Annalen, 226, 133--174).-1t has been shown by Botsch (Abstr.,1882, 456), that in the explosion of a mixture of hydrogen, oxygen,and chlorine, water is formed only when the chlorine is present inamount insufficient to unite with the whole of the hydrogen; thisresult is important, inasmuch as it does not agree with the generallyaccepted rule that when several substances react simultaneously onone another those reactions always occur in which t’he greatest amountof heat is developed. The author has extended these researches to theproducts of the explosion of mixtures of chlorine and oxygen withgaseoub organic compounds.Experiments were made with excessboth of chlorine and oxygen, with an excess of oxygen and an amountof chlorine insufficient to unite with all the hydrogen present, andfinally with an excess of chlorine, but with an amount of oxygeninsufficient to convert the whole of the carbon into carbonic: anhy-dride. The organic substances employed were methane, ethane, pro-pane, butane, methyl ether, methyl chloride, ethyl chloride, acetylene,and carbonic oxide. NG results could be obtained with ethylene,as it unites with chlorine in the dark, and so prevents the formationof an uniform mixture for expIouion. The following are the conclu-sions drawn from these experiments:-(1.) If it hydrocarbon bemixed with excess of chlorine and excess of oxygen and the mixtureexploded by the spark, the whole of the carbon is converted intocarbonic anhydride and all the hydrogen into hydrochloric acid.Hydrogen does not unite with oxygen nor carbon with chlorine.(2.) If excess of oxygen be employed together with Sn amount ofchlorine insufficient to combine with all the hydrogen present, thenthe remainder of the hydrogen unites with oxygen.(3.) If withexoess of chloriue the amount of axygen is insufficient to convert allt,he carbon into carbonic anhydride, there is then also formed carboniINOROANIC CBE MISTRY. 215oxide, the proportion of this latter increasing with the deficiencyof oxygen. (4.) If neither chlorine nor oxygen is present in siiffi-cient quantity for complete combustion, carbon is separated.(5.) Theorganic chlorides and oxides experimented with behaved in likemanner to the hydrocarbons.Determination of Specific Gravity of Carbonic Acid Solu-tion. By A. BLUMCKE (Am. Phys. Chem. [ a ] , 23, 404-415).--Observations on the change of volume in a liquid produced by theabsorption of gases have for the most part been made under normalnOmospheric conditions. In this paper a method is described, on thehydrostatic principle, by means of which the sp. gr. of solutionsof carbonic acid under increased pressure can be determined. Aseries of these determinations are given, made under pressuresvarying from 2 to 37 atmospheres ; in all cases i t appeared that theabsorption of the gas was the more marked the greater the initialpressure.The results point to the following empirical formula forthe sp. gr. of solutions of carbonic acid: S = ____0.001965 is the weight in granis of 1 C.C. of carbonic anhydride,and 0.001568 is the constant deduced from the experiments. Hencethe addition in volume by the absorption of carbonic anhydride isdirectly proportional to the gas absorbed, if the compressibility of theliquid by increase of pressure is neglected. Although the results showR remarkable diminution in volume experienced by the carbonicanhydride in its absorption by water, yet no conclusive proof isoffered of the liquefaction of the gas in the course of solution,especially as Andrews’ experiments show that the critical point O E agas is lowered by its admixture with another gas or vapour of avolatile liquid. V. H. V.A. J. G.1 + n.001965, in which1 + n.001568Crystallisation. By C. MARIGNAC (Bey., 17, 2831-2832), and by0. LEHMANN (Bey., 17, 2885-2886) .-Replies to Briigelmann (thisvol., p. 114).Lecture Experiments. By A. VALENTINI (Gazzefta, 14, 214-218).-In this paper various forms of apparatus are described for thecombustion of substances in oxygen, and chlorine ; the preparation ofozone by Schonbein’s method ; the preparation of chlorine ; the com-bustion of ammonia in oxygen, a,nd chlorine; and the oxidation ofammonia. Drawings of thk-various pieces of apparatus are given.V. H. V

ISSN:0368-1769    

DOI:10.1039/CA8854800209

出版商:RSC    

年代:1885

数据来源: RSC

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INOROANIC CBE MISTRY.In o r g a n i c C h e m i s t r y.215Action of the Induction Spark on Phosphorus Trifluoride.By H. MOISSAN (Compt. rend., 99, 970--972).-When carefully driedphosphorus trifluoride is subjected to the action of induction sparks,the volume of the g m diminishes, and phosphorus is deposited on th216 ABSTRACTS OF CREMICAL PAPERS.sides of the eudiometer. The glass is not attacked, and the gas con-tains no trace of silicon fluoride. When brought in contact withwater, about 6-7 per cent. of the gas is dissolved, yielding a solutionwhich contains phosphoric acid, whilst the residual gas has all theproperties of phosphorus trifluoride. It would seem, therefore, thatthe induction spark partially decomposes phosphorus trifluoride intophosphorus and fluorine, but that the latter at once unites with unde-composed trifluoride, forming phosphorus pentafluoride.If the passageof the spark is continued for several hours, the deposit of phosphorusiucreases, and the volume of the residual gas continues to diminish ;after some time, however, a condition of equilibrium is attained anddecomposition ceases.If the phosphorus trifluoride is not completely dried, but is simplybubbled through strong sulphuric acid and then subjected to theaction of the spark, phosphorus is liberated and the volume of the gasdiminishes, whilst the eudiometer is corroded, and after an hour theresidual gas contains as much as 20 per cent. of silicon fluoride. Thesmall quantity of water in the gas is decomposed by the spark, andthe hydrogen unites with some of the fluorine of the trifluoride,forming hydrofluoric acid, which acts on the glass and thus pro-duces silicon fluoride and water.This water is decomposed in thesame manner, and the same series of reactions again takes place, asmall quantity of water being thus sufficient to convert a relativelylarge quantity of phosphorus trifluoride into silicon fluoride. Thisconversion is, however, never complete, a condition of equilibriumbeing established after some time. The mixture of gases resultingfrom the action of the spark on moist phosphorus t'rifluoride gives adeep blue coloration when brought in contact with potassium iodideand starch. No similar coloration is given by the products of theaction of the spark on the dry gas.Density of Sulphuric Acid.By G, LUNGE (Ber., 17, 2711-2715).-A reply to Mendelheff.Pyrosulphates. By H. SCHULZE (Ber., 17, 2705--2709).-Byheating normal sulpli ates with sulphuric anhydride in sealed tubes,Weher obtained octosulphates (this vol., p. 121); these are con-verted by heat into pyrosulphates. The author finds that manysulphates combine with sulphuric anhydride without the applicationof heat, and that when the excess of anhydride is distilled off a t100-120", pyrosulphates remain more or less pure. Potassium,ammonium, silver, and thallium pyrosulphates may thus be obtainedpure, and also those of the alkaline earths and of magnesium,but the product from sodium sulphate contains only 85 per cent.pyrosulphate.The sulphates of lead, zinc, cobalt, nickel, andmanganese also absorb sulphuric anhydride to a greater or lessextent.Attempts to prepare barium and magnesium pyrosulphates byheating their hydrogen sulphates yielded negative results. Hydrogenammonium sulphate heated at 250-300" gave a product contaming74.44 per cent. SOa (calculated for pyrosulphate, 75-47), BetterC. H. BINORGANIC CHEMISTRY. 217results are obtained by heating sulphates with chlorosulphonic acid(see Schiff, AnnuZen, 126, 168); the author has prepared sodium,ammonium, and barium pyrosulphates in this way.Comparative Oxidation of Solutions of Sulphurous Acidand of Sodium Sulphite. By C. L. REESE (C'liern. News, 50, 219),-In these experiments, solutions of sodium sulphite and of snl-phurous acid of various strengths were exposed to daylight and airin green glass bottles, the neck of each beiug closed by a cork throughwhich a short open tube 2 mm.wide passed, and was bent outside toexclude dust. The solutions of sodium sulphite were of strengthequivalent to 21-10, 3.77, and 0.765 parts of sulphurous anhydride to1000 of water respectively, whilst the solutions of sulphurous acid con-tained 6.00 and 1.063 parts of sulphurous anhydride in 1000 parts ofwater. During the experiments, the temperature varied frequentlybetween 50" and 90". It was found that the weaker solutions oxidisemore rapidly than the more concentrated ; that with vFeak solutionsthe sulphite is oxidised more rapidly than the sulphurous acid ; thatwith stronger solutions the smaller rate of oxidation of the sul-phurous acid was more than compensated by loss due to the diffusionof sulphurous anhydride into the air.Atomic Weight of Cerium.By H. ROBINSON (Proc. Roy. SOC.,37,150-156, and C'hem. News, 50,251-253).-The author has madeseven very careful determinations of the chlorine in a very pure pre-paration of cerium chloride ; the mean of the results obtained gives139.9035 as the atomic weight of cerium, the atomic weight ofhydrogen being taken as unity and Stas's ratios employed ; if oxygenis taken at 16, the above number becomes 140-2593. Much care andlabour was bestowed on the preparation of the cerium chloride, whichwas made from pure cerium oxalate by passing pure hydrochloricacid over it, first at a temperature of about 123", subsequently at ared heat.The purification of the oxalatc was only effected by manylaborious operations. A f u l l description of these operations and ofthe method of determining the chlorine is given in the paper.D. A. L.Action of Lead Hydroxide and Silver Oxide on AqueousSolutions of Sodium Pentasulphide and Sodium Thiosul-phate. By A. GEUTHER (Amnalen, 226, 232-240). - When anaqueous solution of sodium pentasulphide is vigorously agitated withlead hydroxide at the ordinayy temperature, lead sulphide and sodiumhydroxide are formed and sulphur liberated, according to the equa-tion : 3N&S5 + Pb,O,H, + 2H,O = 6NaOH + 12s + SPbS ; a traceof thiosulpbate is also formed.Silver oxide, under like conditions,behaves similarly to lead hydroxide, but some quantity of sulphate isalso formed, owing to the powerful oxidising action exerted by thesilver oxide on sulphur. Sodium dithionate in aqueous solution, whenagitated in the cold with silver oxide, is first decomposed according tothe equation 2S,0,Naz + Ag20 + H,O = S2O3Na2,SZO3Agz + 2NaOH,only a trace of sulphuric acid heing formed; after a time, the alka-linity of tho liquid diminishes, owing to a further reaction, in whichA. K. M.D. A. L218 ABSTRACTS OF CHEMICAL PAPERS.silver sulphide and sodium sulphate are formed. The author pointsout that these results confirm the opinion expressed by Bottger(Abstr., 1884, 342), that the pentasulphides and thiosulphates cantiotbe correctly regarded as sulphates in which oxygen has been replacedby sulphur.A. J. G.Action of Hydrogen Phosphide on Bismuth Trichloride.By A. CAVAZZT (Gazzetta, 14, 219-220) .-If a current of hydrogenphosphide is passed into a solution of bismuth trichloride in hydro-chloric acid, and water added from time to time, a black precipitate isproduced containing chlorine, phosphorus, and bismuth. I n anexperiment cihed, the quantity of hydrogen p hosphide absorbed, cor-responded with the production of a bismuth phosphide containingone atom of each element. The author considers it probable that ahydrochloride of this compound is first formed, but that this ondesiccation loses hydrogen without a t the same time losing chlorine.On frequent boiling with water, it yields metallic bismuth, and isconverted into the sulphate and nitrate of the metal by treatmentwith sulphuric and nitric acids.When heated, it ignites at a compara-tively low temperature, leaving a residue of bismiith.Action of Tellurous and Telluric Acids on Paratungstates.By D. KLEIN (Bull. Xoc. Chiin., 42, 169-170). --ellureus acid,H,TeO,, dissolves readily in solutions of sodium, ammonium, or potas-sium paratungstate, yielding in the first case micaceous crystals and adense mother-liquor. This mother-liquor gives no precipitate withhydrochloric acid in the cold, and is only decomposed after severalsuccessive evaporations to dryness with this acid. The mother-liquorcontains tellurous acid, which is only precipitated by siilphurous acidor hydrogen sodium sulphite in the cold, after addition of hydro-chloric acid.The action of tellurous acid on ammonium or potassium para-tnigstate yields no crystalline products, but only a pulverulentdeposit, which contains tungstic and tellurous acids, and behares likea tungstotellurite.When telluric acid, HaTeOd, acts on potassium paratungstnte, acrystalline compound is formed which contains tungstic and telluricacids and potassium.It is evident that the behaviour of the acids of t,ellurinm towardsthe alkaline tungstates is very different fiom that of the acids ofs ul p hu 1’.V. H. V.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8854800215

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

218 ABSTRACTS OF CHEMICAL PAPERS.M i n e r a 1 o g i c a 1 C h em i s try.Determination of the Coefflcien t of Cubic Dilatation ofMinerals. By J. THOULET (Jahrb. f. Min., 1885, 1, Ref., 16--17).-Thoulet has already employed with advantage the high sp. gr. (3.2)of a concentrated aqueous solution of potassium mercury iodideMINERAL001CAL CHEMISTRY. 219From this, solutions may easily be prepared with sp. gr. 3.2 to 1.0.I n the meantime, V. Goldschmidt has estimated the cubic dilatationof mercury iodide solution a t various degrees of concentration, andthe table he has drawn up is employed by Thoulet for a method ofdetermining the coefficient of cubic dilatation of isotropic minerals i nsmall fragments.A funnel-shaped vessel is closed below by a cork, and in this isplaced a thin test-tube, about 110 mm.high and 35 mm. in diameter.The vessel is placed on a sand-bath and heated by a gas burner. Thetest-tube serves for the reception of the small fragments of mineraland a solution of mercury iodide of rather lower density than thah ofthe mineral at the maximum temperature employed. The surroundingspace, enclosed by the walls of the funnel, serves as a water-bath.The vessel is slowly cooled, and the temperature t1 observed, at whichthe mineral fragment, placed at t'he bottom, begins to float. Thedensity of the mineral D1 a t the temperature tl may then be deter-mined from the density of the solution D a t the temperature of thelaboratory t and froni Goldschmidt'a table. In a similar way, thedensity d is taken a t the minimum temperature t.The solutions ofmercury iodide employed a t the temperature t and tl will vary butvery slightly, so that to both solutions the same coefficient of dilata-tion a may be assigned. Then-D1 - 1D - 1 + a(t1- t )D' - D - _-d d(1 + a(tl- t ) ) .The coefficient of dilatation of the mineral is then1 + a(tl - t ) d - D k = ~~ (tl - t ) DAs a rule, the coefficient of dilatation is given for O", so that theD1 formula for .- would be DFor all practical purposes, the approximate formula given abovewill be enough. B. H. €3.Silver Amalgam from Oberlahnstein. By V. DECHEN (Jahrb.f. &fin., 1885, 1, Ref., 1Gj.-The amalgam occurs as a moss-like massin nests in the quartz of the Fiiedrichsegen vein.Three assays gave :42.47, 42.80, and 44.9 per cent. of mercury. I n addition to silver,0.06 per cent. of copper was found. This composition correspondswith the formula AgI2Hg5. Sp. gr. 12.703. Very ductile, and acquires,under the hammer, a metallic lustre. On heating, a porous mass ofsilver remains in the form of the original mineral. B. H. B220 ABSTRACTS OF CHEMICAL PAPERS.Crystallised Copper from Schneeberg. By H. v. FOULLON(Jahrb. f. Min., 1885, 1, Ref., 23).-Numerous small crystals ofnative copper occur planted on quartz at Schneeberg in Saxony.They are crystallised only in octahedra. Simple crystals are rare,twin crystals are more frequent, and groups of four most frequent.The forms usually unite by a face of the octahedron. B. €3.B.Siegburgite. By H. KLINOER and R. PITSCHKI (Bey., 17, 27'42-2746).-The physical properties of this fossil resin have been de-scribed by v. Lasaulx (this Journal, 1875, 615). The amount of sandfound by the authors is much higher than is stated by v. Lasaulx ; thopowdered resin dried over sulphuric acid yielded 72.07- 72-42 percent. ash. When siegburgite is slowly distilled, a light yellow mobileliquid first comes over, then a thick dark-coloured distillate, the mas8in the flask first melting and then becoming solid, whilst finally agrey-black sandy residue remains. The distillate contains cinnamicacid and cinnamene, which may be separated by agitation with sodasolution ; the lower fractions were also found to contain toluene anda littJe benzene, whilst the fractions 120-140' and 150-360", havenot yet been examined.On treating siegburgite with aqueous soda, very little cinna*mic acidiis extracted ; alcohol, ether, and benzene take up a small quantity ofa resinous and amorphous substance ; chloroform extracts a resinwhilst the concretions swell up, the sand settles t o the bottom coveredwith a gelatinous mass, which probably is principally metacinnamene,as when dried and distilled, it jields a considei*able quantity of cinna-mene together with cinnamic acid.It appears from these results thatsiegburgite is a fossil storax. A. K. M.Hatchettine from Seraing. By G. DEWALQUE (Jahrb. f. Min.,1885, 1, Itef., 21).--The melting point of this mineral is not fixed; atabout 5 6 5 8 ' it begins to melt, but does not, become perfectly fluiduntil a temperature of 62--64O is reached.Its behaviour on coolingis quite similar. Crystallisation begins at 59O, and at 56-5-57' thewhole mass becomes solid. Hatchettine is, therefore, probably not asimple substance but a mixture.Mineralogical Notes on the Environs of Pontgibaud. ByF. GONNARD (Jahrh. f. Min., 1885, 1, Ref., 26).-The author gives alist of the numerous minerals occurring near Pontgibaud. In additionto the usual lead ores (galena, cerussite, anglesite, pyromorphite,mimetesite), the following are worthy of note :-Fluorspar in largecrystals from Pontgibaud and Martineehe. Small crystals of bourno-nite, from the Roure Mine, with the forms OP, Pdj, mP&, 4P, P&,mP& ; larger crystals occur at Barbecot.Tetrahedrite from Pranalin large crystals,in which the usual forms 202 ~ - predominate; the2 ' 2composition is as follows :-B. H. B.5. Sb. Cu. Fe. Zn. Ag. Total. Sp. gr.24.35 22.30 23-56 6-53 2.34 19-03 98.11 5.0MINERALOGICAL CHEMISTRY. 221Zinkenite (argentiferous) from Peschadoire, in which the percentagesof antimony and lead (45 and 28 respectively) do not agree with theusual analyses. The chlorophyllito occurring near the town of Pont-giband is described somewhat in detail.By E. DOLL (Jahrb. f. Min., 1885, 1, Ref., 18-21).-The author describes a new pseudomorph, and several rarepseudomorphs from new localities. The pseudomorphs described arefhe following :-1. Marcasite after blende from the talc-like nacrite ofSchonfeld near Schlaggenwald. 2.Iron pyrites after marcasite fromRapnik. 3. Blende after galena and barjtes in the quartz-andesiteof Nagyag. 4. Quartz and red hamatite after garnet from Carinthia.5. Talc after quartz and dolomite from Oker in the Harz.B. H. B.Pseudomorphs.B. H. B.Stibnite from Japan. By J. A. KRENNER (Juhrb. f. Mi%., 1885,1, Ref., 6-10) .-The complexity of form observed among Japanesestibnite crystals is very remarkable. Of the 45 planes known pre-vious to the publication of Dana’s memoir (Abstr., 1884, 22), 30 havebeen observed on these Japanese stibnites, and, in addition to these,40 new planes were determined by Dana. Krenner has now intro-duced 10 new svmbols, 7 of which are identical with those found bvDana.The thiee new planes are the following : &P, AP, &P.B. H, B.A Crystal of Stibnite from Japan. By A. BRUN (Jahrb. f.Min., 1885, 1, Ref., 10-ll).-The aut,hor has measured a crystalfrom the island of Shikoku. The following forms were observed :-wp&, wP$, P, %P#, SP, &P, %Pi. a : b y c = 0.99839 : 1 : 1.01127.B. H. B.Japanese Minerals. By WADA (Jahrb. f. Min., 1885,1, Ref., 11-13).-1ron pyrites occurs as cubes a t Kiura, in the island of Kin-Shiu, as 0. [?] at Kiso in the province of Shinano, and as0.mOm at Utesan in the province of Idsumo. Copper pyrites occursits tetrahedra from the veins in the diabase or diabase-tufts of Ani,province of Ugo, accompanied by galena, blende, quartz, and theusual vein minerals.Stibnite occurs in crystalline schists, i n veins0.63 metre wide and filled with compact ore, in cavities in which arefound the crystals described by Dana and Krenner. The localitygiven by Dana (Abstr., 1884, 22) is incorrect. It should be thestibnite mine of Ichinokawa, near Saijo, province Jyo, in the island ofShikoku. The author next describes a long and thick crystal ofapatite from the granite of the Kympusan Mountain, in the provinceof Kai. It is weathered on the surface, and has a sp. gr. of 3-19.Splendid specimens of topaz occur i n the pegmatite veins in thegranite of Otani-pma, near the town of Kioto. The crystals arecolourless, yellow, and greenish, and are of great size. One of averagedimensions is 77 mm. long in the direction of the axis c, and 75 mm.and 120 mm.in the direction of a and 6. The following forms wereobserved:-mP, mP2, mP&, OP, P, iP, QP, 2P&, Pij, $P&,Pfi, $Pa. Similar crystals occur at Nakatsu-gama, province o222 ABSTRACTS OF CREMlCAL PAPERS.Mino. The author next describes toiirmaline from four localities,three of which are in granite or gneiss, and the fourt,h specimen wasbrought to Tokio, with pale green beryl, from the second of the topazdeposits mentioned above. The first three are black, and the last isazure-blue. One locality of black tourmaline is the KimpusanMountain, where for centuries rock crystals have been worked. Asecond locality is the granite of the Kirishima-yama, province ofOsurni, in the island of Kiu-Shiu. The third black tourmaline occurswith potassium-mica, and felspar, as a constituent of a pegmatite ofthe province of Hidachi.Garnet occurs in three localities ; at Kuro-yuwa, in the province of Etchiu, as reddish-brown crystals, ~00,202,with decomposed felspar and quartz ; a t Wnda-mura, province ofShiuano, reddish-brown to black crystals, 030.202, occur ; and in themica schist of Yamao-muro, province of Hidachi, brown icositetra-hedrons, 202, with the characteristic striation are met with. Zeolitesare found in the cavities of a diabase amygdnloid from Mase-mum,province of Echigo. Milk-white apophyllite, similar to the crystalsof Punah, and coloudess crystals (202) of analcime, on a radiated crustof natrolite, occur. From the first of the above-mentioned topazlocalities, a number of potash felspars come, similar to those ofStriegau. B.H. B.By J. D.BRUCE (Ghem. News, 50, 220).-The specimen had the usual appear-ance cf marmalite, but contained an exceptionally large quantity ofantimony. Analysis gave :-Marmalite from Himmelfahrt Mine, Freiburg.InsolubleZn. Fe. Cu. Sb. Mn. S. residue.50.82 14.52 2.35 1.14 trace 31.67 0.14 = 100.64D. A. L.Twin Crystals of Zircon. By FOOTE (Jahrb. f. Min., 1885, 1,Ref., 15-16) .-At Eganville, Renfrew County, Canada, small butdistinct twin-crptals of zircon occur. They are formed exactly likethe well-known rutile and tinstone twin-crystals. The twinning planeis here, also, PGO.(Jahrb. f. Min., 1885, 1, Ref., 21--23).--The author gives a detaileddescription of the crystallised pitchblende from Mitchell Co., NorthCarolina, and adds, for the sake of comparison, an account of theother occurrences of pitchblende and its alteration-products.Thecrystals examined consisted of cubes with subordinate octahedron.The crystals from Mitchell Co. are mostly pseudomorphs, frequentlycontaining a, core of pitchblende. The exterior is lemon-yellow, andconsists of uranophane ; beneath this is an orange-coloured layer ofgummite. The gammite represents the first stage of the decom-position of pitchblende, nranophane the second. Both products aredescribed by the author as independent minerals. The chemicalcomposition of the unaltered pitchblende is :-B. H. B.Products of the Alteration of Pitchblende.By H. V. FOULLONU,O*. PbO. Fe203. Total.95.49 3.83 1-09 100.4MISERALOGICAL CHEMISTRY. 2235-02 -74.670.46 -- -1-063-389-80--Analyses of gummites and similar minerals are given in theannexed table :-1 and 2, orange-coloured exterior of crystals fromMitchell Go. ; 3, gutninite from Joachimsthal ; 4 and 5 eliasite fromJoachimsthal ; 6, pittinite from Joachimsthal ; 7, coracite from LakeSuperior.5.035 *5174.920-36- --1-063.019.91-SiO, .........PbO .........uo3 .........l?e203 ........Al,03 ........MgO .........BaO .........CaO.. ........H20 .........Bi203 ........Insoluble.. ....MnpO3.a e . * a .PpO, .........co, ...........9.--13-2456-96trace --7 -0013’17I -1. I 2.10.13.4764-360.47--7 -4913’32--I- --- I - - I -4.4 -925 *0463.388 -641 *920 *854 -5410 ‘24----- -5.6.--5 .oo2 -5168 -454.54--0 -552 ‘2710 9 62 ‘673 -20---7.4 -355 ’3659 -302 *240 *90---14 ‘444 *64 --7 *47 -In discussing these analyses, the author concludes that in Kersten’sanalyses of gummite ( 3 ) the lead oxide was overlooked, and thatall these products of the alteration of pitchblende agree with gum-mite, and that the names eliasite, pittinite, and coracite should there-fore be dropped. From analyses 1 and 2 the formula RUySiO,, + 6H,O is calculated. This mineral is of an orangs colour, is notamorphous but crystalline, has a hardness of 3, and a sp.gr. of 4.7-4.84.8, 9, and 10 are lemon-yellow products of the alteration of pitchblende from Mitchell Go. ; 11,uranophane from Kupferberg, in Silesia ; 12, uranotile from Neustadtl,near Schneeberg.Analyses of uranophane are also given.SiO, .............Fe203 ............Al,03 ............MgO .............CaO .............H20.. ............P,O, .............K,O. .............uo, .............11.--17 -0853’336 *lo1-465 -0715 -111 -85--12.13-7866 T5 } 0.515 *2712 -670 -54--13.13 *0263.933.03 { trace5.1314 -55---It is remarkable that, in this mineral, the lead oxide is absent.The author is of opinion that the name “uranotile” must, b224 ABSTRACTS OF CHEMICAL PAPERS.dropped.The formula is, according to Boricky, CaU3Si,01d + 9H,O ;according to Rammelsberg, ChU6Si,0, + 15H20; and according toGenth, CaU,SizOll + 6Hz0. B. H. B.Listwaenite from the Poroschnaj a Mountain, near Nischne-Tagilsk. By M. v. MIKLUCHO-MACLAY (Jahrb. f. Min., 1885, 1, Mem.,69-73) .-In Macpherson’s account of the rocks from the Spanishprovince of Galicia, a description is given of a crystalline schist,locally known as duelo, which appears to correspond with a rock fromthe Ural, described bv G. Rose as listwaenite. In order to test howfar the analogy extends, the author examined a number of Rpecituensin the Heidelberg collection, from the Poroschnaja Mountain, nearNische-Tagilsk in the Ural.The examination of the specimens of listwaenite showed that therock consists mainly of reddish-brown magnesium carbonate andgreenish-white talc, with grains of chrome iron ore.The analysis ofthe carbonate gave the following results :-MgCO,. FeC03. CaC03. Total.73-47 19.94 7.47 100-88The carbonate, therefore, is a lime-breunnerite. The analysis of thetalc gave the following results :-SiO,. FeO. MgO. H,O. T3t&l.62.61 3 4 29-55 5.18 100.78The Poroschnaja rock, like Macpherson’s dueh, is free from quartz,but listwaenites from it number of localities in the Ural are describedby Rose, as being rich in quartz. A comparison of the quartz-freelistwaenite wit’h the Galician dueZo, shows that the two rocks ayeidentical. For the Galician rock, therefore, the correct name wouldbe quartz-free listwaenite.Accidental Formation of Cerussite Crystals on Roman Coins,By A.LACROIX (Jahrb. f. Ma’n., 1885, 1, Ref., 27).-Cerussite waafound on Roman copper coins from Algiers, containing 16.20 per cent.of lead and 3.97 per cent. of tin. The coins were cemented togetherby copper carbonate, and the geodes, formed between them, containedcerussite, small cubes of cuprite, with malachite and azurite. Theauthor is of opinion that the cerussite was formed by the action of solu-tions which had taken up alkali carbonates from the masonry.B. H. B.B. H. B.Colernanite. By G. v. RATH (Jahrb. f. Min., 1885, 1, Mem., 77-78).-An analysis of colemanite (named after W. T. Coleman, ofSa,n Francisco, the founder of the borax industry in the Pacific States),gave the following results :-B203.CaO. H20. A1203 and Fe?O,. SiOp.48-12 28.43 22.20 0.60 0.65After subtracting the impurities, t h i s gives :MINERALOGICAL CHEMIST R T. 225B,O,. CRO. HzO. Total.48-72 28.79 22-49 100-00This corresponds very closely with the priceite from Curry County,Oregon.The new crystals recently found in the neighbourhood of the DryLake are transparent aud extraordinarily rich in planes, forming one( ~ f the finest monoclinic combinations known. The following formswere observed : -P, P, -3P, - 342.3, 2P, 233, gm, Ssm, 2Pm, cap,mg2, ~ P w , m%!cm, OP. The sp. gr. is 2-41:? aiid the hardness 5.B. H. B.Fluorapatites. By A. DIT~E (Compt. r e d . , 99, 967--97O).-Thephosphoric acid in Auorapntites can be replaced by arsenic or vanadicacid, with formation of strictly analogous compounds.Fluorarsenates are obtained by the same methods as the fluorphos-phates, substituting a metallic arsenate or arsenic acid fop the phos-phate or phosphoric acid.Ammonium arsenate may be used insteadof arsenic acid, but in this‘case a platinum crucible cannot be employed,hince it is attacked by the free arsenic which is liberated. A porcelaincrucible, however, is oiily very slightly corroded by the fused fluoride.The reactions which take place are strictly analogous to those whichoccur in the formation of fluorphosphates, and the apatite obtainedis quite free from chlorine.Calcium Jlzco ra rsenate, 3 Ca, As,O,, CaF,, forms brilliant transparenthexagonal prisms, terminated by hexagonal pyramids, the faces ofwhich are striated parallel with the base.The crystals dissolvereadily in dilute acids, especially ou beating, and they are decomposedby sulphuric acid with evolution of hydroflnoric acid. Barium,strontium, and magnesium fluorarsenates, prepared in like manner, arevery similar to the corresponding phosphorus compounds.Fluorvanadates can be obtained by the same methods, but the yieldis not so satisfactory. Better results aye obtained by using an excessof calcium fluoride, bnt part of the vonadic acid is always convertedinto a soluble compound, which yields a yellow solution when thefused mass is treated with water. Moreover, any apatite which maybe formed is decomposed by the fused salts, unless the fluoride is inexcess.A very small quantity of undecomposed fluoride is sufEcientto ensure the stability of calcium fluorvanadate. 10 the case of stron-tium, however, and still more in the cases of barium and magnesium,this does not hold good. I f only a small proportion of fluoride isused, no fluorvanadate is obtained, whilst if the fluoride is in largeexcess, the vanadate is attacked and converted into a soluble compound.uomanadate, 3Ca3V2O,,CaF, forms thin white hexagonalneedles, .with hexagonal terminations. It can also be obtained byfusing 1 molecular proportion of vanadic acid with 3 of calcium oxide,nad then fusing the calcium vanadate thus formed with a large excessof potassium chloride and a small quantity of fluorspar, for 15-20hours.Sts.ontiurn Jluorvanadate is obt,ained by the first methods in verysmall quantity, and intimately mixed with strontium vanadate.Nobarium or magnesiua fluorvanadate could be obtained.VOL. XLVIII. TCaZciunzC. H. B226 ABSTRACTS OF CHEMICAL PAPERS.Artificial Gypsum Crystals. By A. LACROIX (J. Pham. [ 5 ] , 9,lll-ll3).-Small monoclinic prisms of gypsum, about, 2 mm. long.were formed in a Briiner's lead pan, which had been out of use f o ~about four months. When last used, a little water had been placed inthe pan and thrown out again, so that a paste of undecomposed fluor-spar and some calcium sulphate remained. The pan had not bee11exposed to a temperatnre greater than 13" C. At the end of the foul,months, the little liquid left in the pan when last used liadcompletelyevaporated, and a beautiful incrustation of crystals had formed overthe fluoride, and the sides of the pan.Their composition agreetlclosely with that required by CaS04 + 2H,O.The crystals bore a striking resemblance in form to those obtainedfrom the salt deposits of Bex (Canton Vaud), Switzerland.J. T.A New Hydrous Manganese Aluminium Sulphate fromSevier Co., Tennessee. By W. G. BROWN (Amer. Chem. J., 6, 97-lOl).-This mineral and its locality are mentioned by Dana underkalinite. The mass analysed contained in cavities small silky needles,apparently monoclinic; H. = 1.5; sp. gr. = 1.78. Analysis showsthat this mineral is not kalinite, but is related to apjolinite antimore nearly to bosjemanite (Dana), and the author suggests thatthese two minerals may perhaps be identical.The analytical resultsobtained were -A1203. MnO. FeO. MgO. (CoNi)O. CuO. SO,. H,O. Insoluble.10.03 8.73 0.39 0.30 0.30 0.02 35.47 44.78 0.06 = 100.08H. B.Occurrence of Linarite in Slag. By P. DUDGEON (ETz. Mag., 5,33).-Well-formed crystals of linarite, 3 mm. long, were found insome of the cavities in slag from an old lead-smelting place, evidentlyof Roman origin, on the farm of Martingarth, in the parish ofTroqueer, in Scotland. There were no other crystallised mineralsin the cavities. B. H. B.Wulfenite from Beaujolais. By A. LACROIX ( J a h ~ b . .f. lUi?z,,1885, 1, Ref., 27).-Wnlfenite is found in numerous places near theabandoned mines of Beaujolais, especially abundantly at illonsols.It is generally accompanied by pgromorphite.The crystals a1-etabular, and the colour varies from orange-yellow to deep red. Inthe latter crystals, however, no trace of chromium could be found, tothe presence of which Fournet ascribed this colouring. The author isof opinion that the colour is due to long exposure to the a,tnio-sphere. [Groth and Jnst ( Z e d s . .f. Kyyst., 7, 592) have already shownthat the presence of chromium is not the cause of the colour of wulfe-nite, and Ochsenius (ibid., 7 , 59;3) found that red wulfenite crystalsbecome lighter on exposure t o air and light.]Amphibole from the Aranyer Mountain. By A. FRdNZEh'Ali( J & T ~ . f. Mi%., 1885, 1, Ref., 17--18).-Up to the present time, 18planes have been observed in amphibole crystals : of these, 14 havebeen detected on the Aranyer crystals. I n addition to these, theB.H. BMINERALOGICAL CHEhIISTR Y. 227a u t h r has added the following five new planes: mP2, -2Pv3,-3Pq -5P$, -4P. a : b : c = 0.54812 : 1 : 0.29455. @ =74' 39.7'. The crystals are of a green colour, and occur in a redclislitracbpte. Twin crgstals were not observed. B. H. R.By H. C. Lwrs ( J d ~ . b .f. Nin., 1885, 1, Ref., 15).-Helvine occurs in orthoclase in the mica,mine near Amelia Court House, Virginia, in sulphur-yellow crystalliiiemasses along with topnzolite. H. = 6 ; sp. gr. = 4.306 ; lustre, resi-nous ; partially translucent ; fusible. An analysis of the raw material(I) is given, together with the results without the mother-rock im-purities (11).An American Locality for Helvine.Si02.BeO. MnO. Fe203. A1,0,. CaO. K,O.I. 23.10 11.47 45.38 2.05 2.68 0.64 0.3911. 25.48 12-63 39-07 2-26 2.95 0.71 0.43Na,O. 5. Mn. Rock. Total.I. 0.92 4.50 - 9-22 100.35TI. 1.01 4.96 8-66 - 9 ~ ~ 1 6The substance is decomposed by hydrochloric acid. The miiiei*a,lhas without doubt much in common with helvine, but the composi-tion is very different, for helvine contains about 32.5 per cent. ofsilica. The sp. gr.., too, is different, that of helvine being but 3.2.Further investigation is therefore necessary, more especialfy as to thepurity of the material. B. H. B.Hyalophane from Jakobsberg. By T,. J. IGELSTR~M (Jahrh. f.Nin.. 1885, 1, Ref ., 2G).-Hyalophane occurs at Jakobsberg, Werrri-land, Sweden, in slaty beds in limestone containing hansmannite axidmanganese epidote. The principal mass is white, but in the middleoccur reddish, and at the edges, bluish-green spathic masses.Thelatter gave on analysis the following results :-SiOs. A1,03. RaO. NgO. MnO. Alkalis. Total.53.53 23.33 7.30 3.23 trace 11.71 99.10This varietydiffers in composition from the red variety from Jakobsberg, andfrom the variety found in Binnenthal, in Wallis. B. H. 12.Garnet (var. Spessartite) from Amelia Co., Virginia. ByC. M. BRADBURY (Chern. News, 50, 220).-The specimen is from t h emica mines G f Amelia Go. ; it is of a pale pink t80 flesh colour, re-sembling rliodonite more than the usual form of garnet.Its hardnessis 6.5, its sp. gr. 4.20. From the following results, it will be Been thatthe manganese is higher, whilst the iron and aluminium are lowerthan usual :-The absence of rubidium and czesium was proved.SiO,. A1203. FeO. MnO. CaO. MgO. OH,.36.34 12.63 4.57 44.20 1.49 0.47 trace = 99-70D. A. L.r 228 ABSTRACTS OF CHEJIICAL PAPERS.Kaslinite from Calhoun Co., Alabama. By G. H. ROWAN(Chenz. News, 50, 220).-The specimen is unusually pure, and comesfrom near Jacksonville. It is white with a creamy tinge, earthy withclayey odour, adheres to the tongue, and is slightly greasy to thetouch. The following are the results of its an-alysis :-I t s sp. gr. 1=: 1.688.SiO,. A1,03. CaO. HzO. Mg0,Fe20,.45.77 39.45 0.79 13.96 trace = 99.97D.A. L.pended :-SO,. AIZO3.75.68 9.88The wateiInfusorial Earth from Richmond, Virginia. By J. M.CABELL (Chem. News, 50, 219).---As previous analyses of this sub-stance have apparently been made on impure specimens, a specimenwas procured composed almost exclusively of distinguishable infu-soria. It is white with a tinge of yellow, is slightly harsh to t,hetouch, and has a sp. gr. of 2.321. The results of analysis are ap-NitrogenousmatterFe20,. CaO. MgO. KzO. Na,O. (X x 6 ) . OHz. Total.2.92 0.29 0.69 0.02 0.08 0.84 8-37 = 98.77r and silica were made up in the following manner :-Silica dissolved by boiling 1 hour with 20 per cent. soda. 29.607, 9 9 ,, 2 hours ,, 7 9 1 9 4.79,, undissolved 9 9 9 7 9 41.2975.68Loss by drying over H2SOa ..............3.37Loss a t 100". ........................... 1.17Loss by ignition (less N) ............... 3.83Water ................................ 8-37D. A. L.Description of a Crystal of Euclase. By M. GUYOT (illin..JPug,, 5, 107--108).-The crystal comes from the mining district BoaVista, near Villa Ricca, Brazil, where alluvial strata containingdiamonds occur with chlorite schist. The weight of the crystal is15.45 grams ; sp. gr. 3.087. It is 35 mm. long, sea-green like beryl,with vitreous lustre, nacreous on the cleavage planes. One termina-tion is perfectly developed, the other fractured. The prism mP gavethe angle 144" 37'. The following planes were present :--mPm,WPm, OP, mP, mP2, 33?3, 3P3, 2 9 2 . The crystal is one of thefinest crystals of euclase which has ever been discovered.B.H. B.Variety of Chloropal from Albemarle Co., Virginia. By1;. N. CHAPPRLL (Cl~ern. Xews, 50, 219--220).--The mineral is foundiu leaf-like pieces of various sizes in a ferruginous clay ; the neighMINERALOGICAL CHEAlISTRY. 229bouring rock is largely composed of quartz, felspar, and epidote.When dug out, it is massive and soft ; when dry it becomes harderand brittle with earthy fracture. It can be cut with a knife, givinga slightly lustrous surface, greasy to the touch. It does notadhere to the tongue, and is of a light yellowish-green colour. Itshardness is about 1 ; its sp. gr. = 2-06. When treated with hydro-chloric or sulphuric acid, it is decomposed with separation of silica.Its composition is-Si02.A1,0,. Fe20,. FeO. CaO. MgO. OHz. Total.38.64 20.06 22.18 0.04 1.09 0.44 15.71 = 98.15which nearly corresponds to that of pinguite, a variety of chloropal,2AIZ0,,3SiO2 + 4&HZ0.By G. A. K ~ N I G (Juhrb. f. Min., 1885,1, Ref., 14).-In the mica mine near Amelia Court House, Virginia,two specimens of orthite were found. They were pitch-black andhard, but covered with a thin reddish-brown incrustation. Sp. gz'.3.368, The mineral fuses with intumescence to a black slag, and isdecomposed by concentrated hydrochloric acid and dilute sulphuricacid. The analyses gave-SiOP A1,03. Fe,03. Cc02. La,O, + Di20,. FeO. CaO.32.90 17.W 1-20 8.00 14.20 10.04 11-32MnO. HZO. Total.1.00 3-20 99.66D. A. L.Orthite from Virginia.together wit.h a trace of uranium, but neither yttrium nor beryllium,B. H.B.Variety of Saponite. By J. 5. DOBBIE (&fin. 2clccg., 5,131-132).-The variety of saponite described is of a deep chocolate-browncolour. It was obtained from the dolerite of the Cathkin Hills, nearGlasgow. It occurs in irregular lenticular patches, or in horizontalveins. It has a concho'idal fracture and soapy feel. H. = 2. Sp. p.8.214.Si02. A1203. Fe203. FeO. CaO. MgO. CO,. HzO. Total.I. 40.07 6.61 4.16 8.69 2.67 19.24 0.38 17.16 98.9811. 39.90 6.941 3.75 8.91 2-32 19.28 0.40 17.28 98-76111. 40.81 6-77 4.28 8.73 2.09 19*i6 0.36 17.11 99-91The Cnthkin Hillsmineral differs from other saponites in containing a larger percentageof ferrous oxide, and a smaller percentage of total water.The analyses gave the following results :-At loo", 13.02 per cent.of water is given off.B. H. B.Relation between the Optical Properties and Chemical Com-position of Pyroxene. By C. DOELTER (Jahrb. f. JIhz., 1885, 1,iXem., 43--68).--The admixture of FeCaSi?O, with the silicateCaMgSi2O6, causes an increase in the value of the extinction angle inthe plane of symmetry, and in the prism faces. I n the same way,this increase is brought about by the admixture of silicates of th2 30 ABSTRACTS OF CHEMICAL PAPERS.formula R‘R”’2Si06, and the same amount per cent. of the lattersilicate effects a greater alteration in the extinction angle than iseffected by CaFeSi206. If the sums of all these silicates (CaFeSi20Gand R”R”,SiO,) be taken as abscissae, and the values of the extinc-tion angles be taken as ordinates, the curve obtained is y = a + bx + 6x2.If, however, for abscissae the values of FeO, Fe203, and A1,0,(together or separately) are taken, a less regular curve is obtained.The curve for the diopsides (combinations of CaMgSi206 andCaFeSi,Oc) does not coincide with that for the alumina augites. Forthe lime-magnesia silicate, theoretically perfectly free from iron andalumina, the extinction angle is about $2” 30’. The value of theangle formed by the perpendicular to the orthopinacoid and an opticaxis, increases, as a rule, in proportion to the total amount of theiron and aluminium silicates present.New Mineral from Godemas. By LODIN (Jahrh.f. Jfin., 1885,1, Ref., as).-At Godenins (Hautes-Alpes), two ore veins occur inthe masses of finely -granular mnscovite granite, stratified conform-ably to the gneiss beds. One vein contains quartz, iron pyrites,copper pyrites, blende, and a little argentiferous galena ; the othercontains quartz, blende, and antimonial fahlerz, rich in silver. Theanalysis of the mass filling tlie second vein gave the followingresults :-SiO,. S. Sb. As. Cu. Pe. Zn. Pb. Ag. Total.66-31 9.93 3.85 0.15 5-98 2.09 8.67 0.80 0.15 97.93From the same vein, the author obtained a compact, homogeneousmineral of a dark bluish-grey colour and fibrous texture, with sp. gr.6-17. It fuses at a dull red heat, and gives grains resenibling theoriginal mineral. The composition is as follows :-SiO,.8. Sb. As. Cu. Fe. Pb. Ag. Total.0.25 1i.54 0.62 trace 44.52 0.79 35.87 0.11 99.70This corresponds to the formula 2CuS + PbS. As the mineral con-tains but little antimony and silver, although the vein-mass is com-paratively rich in these nietals, the author is of opinion that it wasformed by the action of the fahlerz on the galena, poor in silver.By J. E. WOLFF(Jnlzrb. f . Min., 1885, 1, Mem., 69).-The author collected in theCrazy Mountains, Montana, peculiar eruptive rocks, which in veinsand masses penetrate the horizontal sandstone and conglomerate ofthe Cretaceous formation. These rocks consist of nepheline, amineral of the sodalite group, augite, magnesia mica, olivine, magne-t ite, apatite, and the usual accessory constituents.These eruptiveiiiasses, therefore, belong to the nepheline rocks, a class hithertoundiscovered in the United States. B. H. B.Meteorite from Durango. By L. H ~ P K E ( J ~ h y b . f. Nin., 1885, 1,Ref., 32-33).-In the autumn of 1882, a new meteoric iron wasfound near DLIMI~~O, in Mexico, a t a depth of 25 to 30 mi. FromB. H. B.B. H. B.Nepheline Rocks in the United StatesMINERALOGICAL CHEJIISTRT. 231the slight depth, it WAS concluded that the meteorite had reached thatspot during the year 1882. The iron has a prismatic-pyramidalshape, and weighs 4tj kilos. The analysis gavethe following results :-Sp. gr. 7.74-7-89.Fe. Ni. C O . P and C.91.78 8.35 0.01 tracesThe meteorite has been purchased by the British Museum.B.H. B.Meteoric Sand. By F. MAUGIKI (Gazzetta? 14, 130--136).--Thepeculiar glowing appearance of the sky at dawn and twilight observedduring the winter months of 1883-1884, was attributed by some toparticular atmospheric conditions, such as general stillness, and anextraordinary quantity of aqueous vaponr diffused a t high elevations ;but by others to the volcanic dust of the Krakatoa eruption. Yung,in Geneva, and Nordenskiiiid, in Stockholm, have observed thepresence of iron in meteoric dust which fell on snow. On the 16thand 19th February, and March loth, 1884, the author collected somered-coloured dust at Reggio, in Calabria, M hich, when examined underthe microscope, seemed to consist of mica, quartz, and irrcgularpolyhedric crystals.The plowing phenomenon, accompanied byrain, was observed on these dates. An incomplete analysis of thisdust, when freed from organic matter, gave the following results :-Magnetic iron oxide ............ 6.4Insoluble in acids . . . . . . . . . . . . . 38 75Soluble in acids. ............... 54.85The insoluble portion contained sulphui-ic and phosphoric acids, silica,calcium, magnesium, arsenious mid ferric oxides ; and the soluble por-tion, aluminium, nickel, and manganous oxides. This dust differsfrom that obtained a t Stockholm, in containing no cobalt and onlytraces of nickel. The dust mas not derived from Etna, for the direc-tion of the wind on the days in question was opposite ho that in whichNtna and Reggio are situated ; and further, the volcanic ashes of$:tila are black.It also differed frorri dust carried from the deserts ofSahara by the sirocco in containing iron (see Abstr., 1884, 165), so itwould appear to be of peculiar origin. V. H. V.Mineral Water of Salies-du-Salat. By P, SABATIER (Bull.&Voc. Chim., 42, 98-99) .-The foliowing results were obtained 0 1 1analysis of the mineral water of Salies-du-Salat (in the departmentof Haute-Ga,ronne), the outflow of which has been known for severalcenturies :-1 kilogram of the water contains-Sodinm chloride ......................Potassium chloride. . . . . . . . . . . . . . . . . . . .Sodium sulphate ......................Calcium sulphate ....................Magnesium sulphate ..................Calcium carbonate ....................Sodium silicate ......................Grams.31.4940.51650.49242.67850.55920 * 3 1360.009232 ABSTRACTS OF CHEMICAL PAPERS.There were also found traces of bromine and iodine, nitric andboric acids, together with aluminium, lithium, strontium, iron, manga-nese, and zinc. As these results are not in accordance with t h eanalyses of Bories and Pilhol, it is probable that there are irregularo r periodic variations in the composition of the spring.V. H. V.Water from the Red Spring of Zacaune (Tarn, France). ByL. SOUBEIRAN and G. MASSOL (Jour. Pharm. [ 5 ] , 9, 8S-P9).--Thisferruginous spring rises on the flank of a mountain composed oftalcose schist of the transition period.1020 C.C. of the water gave 38 C.C. of gas containing CO, = 6 c.c.,0 = 5 c.c., and N = 27 C.C. A slight effervescence a t the springresults entirely from the disengagement of nitrogen. The water wasfound to contain-in grams per litre :-FeC09 .. 0.026 Na,C03 .. 0.033 SiO, .. .. . . . . 0.031CaC03 , . 0.053 NaCl . . . . 0.001 Organic matter tracesMgCO,. . 0.013 NazSOl.. traces Total.. . . 0.156A deposit formed by the spring consists mainly of iron oxide andsilica ; it moreover contains magnesia and lime, and effervesces withacid. J. T.Arsenic in Mineral Waters. By J . LEFORT (JOZW. Ph,nmz. [51,9, 81--85).-1n all analyses of mineral waters, the arsenic is repre-sented as being in the higber state of oxidation, as ai*senates, and notas arsenites. The author recommends the well-known remtions withhydrogen sulphide, in slightly acidified solutions, as sufficient todetermine the question. It is quite possible that arsenic may occurin natural water as arsenate if the mineralisation of the water hastaken place under oxidising conditions ; but if under reducing condi-tions, then arsenites rould be produced. 5. T

ISSN:0368-1769    

DOI:10.1039/CA8854800218

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

232 ABSTRACTS OF CHEMICAL PAPERS.0 r g a n i c C h em is try.The Hydrocarbon, C,H,,, prepared from Ally1 Diethyl Car-binol. By s. REFORMATSKY (J. pr. Cham. [2], 30, 217-224).-Thehydrocarbon, C,H,,, is obtained by heating ally1 diet,hyl carbinol withsulphurio acid; this reaction yields a liquid boiling a t 120-140",from which, by a method similar to that employed in the purificationof the hydrocarbon C,,H,, (Abstr., 1883, 1073), the hydrocarbon isobtained as a colourless liquid, insoluble in water, but easily solublein alcohol, ether, and benzene, and boiling at 122--123". It is oxi-dised by exposure to the air, forming tho compound C8HI4O2. Itssp. gr. a t 0" is 0.7734, andat 15.4" 0.7588 (water at 0" = l), at 15.4"0.7395 (water a t 20" = l), and 0.75856 (water at 4" = l), at 18" iORGANIC CHEMISTRY.2331 . . . .2 . . ..0.7572 (water a t 20" = l), and calculated for water a t 4" as unit, itis 0.75662. I t s vnpour-density is 3.81. The determination of itsrefractive index gave the following results, which are not in accordwith the rule laid down by Briih1:-%D.I%a.t P. 1 t. d-.110 , 15.4' 0.75856 1.44340 1.44687 1.45577--- -- --- -- --1l0 1 18" o.7~t;ci2 1-44171 .44477 1.45386 1.46143I l -tau - 1 A. B.1 . . . . . . 1 -4269'75 0.63546 0 *5841 64-25 58.22 . . . . , . 1'42839 0 -64696 0 -5845 64 *29 58 -2Diff.6.056.09~~1 . . , . . . . .2 ........Bromine unites with this hydrocarbon to form a heavy thick oilyWhen oxidised, the hydrocarbon yields chiefly propionic andIf' the constitution of this hydrocarbon is represented by the formulaliquid.acetic acids, together with a small quantity of formic acid.C,H, : CEt.C3H5, the formation of these acids is easily explained.P.P. B.A Reddish Coloration of Cyanide Solutions. By L. HABET,(Ber., 17, 2840-2841) .-A reddish colo~ation has been frequentlyobserved on adding potassium cyanide t o cuprammonium solution,but the cause of ?ti is unknown to the author. A. K. 31.IDiEerence. A - 1 ~ 1 P ( q ) * I RA.d -0 -5646 I 62.11 56 -94 5 *170.5647 I 62.12 56 -94 5 a18Hydroferrocyanic Acid and its Derivatives. By A. I ~ R Dand C;. B~MONT (C'ompt. rend., 99, 972-975 and 1024--1026).-Theproduct of the action of hydrochloric acid on a concentrated solutionof potassium ferrocyanide in presence of ether is not, as is commonlystated, hydroferrocyanic acid, but a compound of this acid with ether,H4FeCy6,2Et2O.This compound is also obtained when dry ether isadded to crystals of anbjdrous hydroferrocyanic acid obtained byslow evaporation. It slowly loses its ether when exposed to the air,and if the compound is treated with sodium hydroxide the ether is a tonce liberated, and can thus be recovered perfectly free from alcohol.When dry hydroferrocyanic acid is heated at 440" (in sulphu234 ABSTRACTS OF CHENICAL PAPERS.vapour), it loses only 46 per cent. of hydrocyanic acid, and yields achamois-coloured crystalline residue of hydro-difei-rous pentacyanide,(1) Fe (CN)$eH.If ammonium ferrocyanide is heated a t 440" until the product hasa constant composition, it loses 62.4 per cent.of water and hydrocyanicacid, and a homogeneous insoluble compound is obtained of the com-position Fe(CN),FeNH4. This is the ammonium salt of the pre-ceding compound. On further heating, it is decomposed into nitrogen,:LIimionium cyanide, and a dense black carbide of iron, FeC,.When hydroferrocyanic acid is boiled with water in a vacuum, itloses hydrocyanic acid, and yields a dense crystalline citron-colouredcompound, (2) FeCy6Fe& t 2H20, which is the acid correspondingwith Williamson's salt, FeCy,FeK,.If the boiling with water is eff'ected in presence of air, instead of ina vacuum, a dark blue precipitate is obtained ; this, however, is notPrussian blue, but has the formula (3) n(FeC,N,H20). From itsbehaviour with potassium hydroxide it seems t o be a hydrated ferroso-ferric ferrocyanide.If hydroferrocganic acid is boiled with ammonium chloride andwater in a vacuum, a sulphur-yellow crystalline powder is obtained,which, when dried out of contact with air, has the composition(4) FeCy,,FeN&H + 3H20.If this compound is exposed to moist air, or if the original boilingis effected in presence of air, it is oxidised t o a dark blue compound,(5) (FeCy6)$e2(NH4), -k 6H,O.When this salt is heated a t 440°, it loses water and ammoniumcyanide, and yields the insoluble cyanide, (6) (FeCy5),Fe2, corre-sponding with (1).These reactions are easily understood if it is assumed that hydro-ferrocjanic acid is a tetrabasic non-saturated acid with the con-st itutionN:C.CNH.CNHFe/ 1 I\N:C.CNH.CNH.The compounds (I), (6), &c., for example, differ from the corre-sponding ferrocyanides by a t least CNR'.A7itroprussides may be classified with the pentacyanides (l), (6),&c., described above.When sodium nitroprusside is heated at 440"in a vacuum, in an apparatus arranged a s if for an estimation ofnitrogen by Dumas' met,hod, it reaches a limit of dissociation when ithas lost 29.9 per cent. by weight. The decomposition is representedby the equation FeCy,Na,NO + 2H,O = FeCyjNaz + NO + CN + 2H,O. The three gaseous products, howewr, react on one anotherwith formation of black compounds. B'erroso-sodium tetracganide,FeNa,Cy4, is a chamois-coloured crystalline compound which ishcarcely altered a t a dull red heat, but loses a little cyanogen a tbright redness.It is evident that the compounds formed by the union of metallicc.yanidea furnish a t least three definite and distinct types, viz.:-It is insoluble in, and is not decomposed by, water.F eCyGR4, FeCy,Rj, FeCycR2. C. H. BORGANIC CHEMISTRY. 235Derivatives of Cyanethine. By C. RTESS ( J . pr. Chem. [el,30, 145-1 71) .-Monobromoc!/aizethine, C3HI4BrN3, is prepared byheating bromine and a solution of cyanethine hydrobromide in sealedtubes a t 80-100" ; the product of the reaction is rnonobromocyanetliinelwdrobrornide, from which the free base is obtained by decompositionw i t h ammonia. It crystallises in small needles, is sparingly solublei n water, and easily soluble in alcohol, ether, and chloroform; itmelts a t 153".Monobromocyanethine is a base formirig salts whichare soluble in water and alcohol, and easily obtained in well-definedcrystals. The hydrochloride forms a sparingly soluble compound withmercuric chloride, an aurochloride, CgHl4BrN3,HAuCl4, ci-ystallisingin yellow shining needles, and a pZatinochZoride, ( CgHl,BrN3),,H,PtCls,crystallising in rhombic octahedrons.Ethoxycyanetfiine, C,H,,N,.OEt, is obtained by heating mono-bromocyanethine with an alcoholic solution of sodium ethylate ; thebase is extracted from the product of the reaction by ether, fromwhich it separates on evaporation as a solid mass consisting ofrhonibic leaflets. It melts at 11S0, commences to snblime even a tloo", and can be distilled unchanged a t over 300"; it is soluble incold water, forming an alkaline solution, from which when heated thebase separates as an oil; this solution precipitates copper and leadsalts as hydroxides.The base is easily soluble in alcohol, ether,chloroform, and acids. Its salts are easily soluble in alcohol andwater, and crystallise well; i t forms crystallime double salts withsilver, platinum, and gold salts. Mercuric chloride produces a whiteprecipitate in solutions of the hydrochloride ; when heated, this meltsto form an oil.E'thoxyhydroxycycLncon~ne, CgH,,(OEt)N2.0H, is formed by treatingthe above compound, dissolved in glacial acetic acid, with nitrousacid. From ether, it separates as a radiated crystalline mass, meltinga t 51" ; it exhibits great resemblance to ethoxycyanethine, itsaqueous solutions have a neutral reaction, and with silver &rate givea white precipitate of the compound CgHl,Ag( OEt)N,.OH.Whenethoxycyanethine is heated with concentrated hydrochloric acid insealed tubes a t 180-200", a compound is produced which is ap-parently the dihydroxy-base C9H12N,( OH),. It crystsllises fromether in needles melting a t 151" ; its aqueous solntion has a neutralreaction. The nitrate gives with silver. nitrate a precipitate of thecompound C,H,,AgN,(OH), + H20. The hydrochloride forms ayellow oily compound with gold chloride. With chlorine-water andbromine-water, its aqueous solutions give wLite precipitates of poly-chlorides and poly bromi des respectively.Methoxycyanethine, C9HI4N3.OMe + H20, is obtained from mono-hromocyanethine by acting on it with sodium methylate.It crystal-lises from ether in rhombic crystals, which effloresce, and melt at 130".It exhibits a great resemblance to the ethoxycyanethine, and like itis converted into a hydroxy-base, C9H,,( OMe)N,.OH, wheu treatedwith nitrous acid.1Cl;~nobronzol~~/droxyc~~anconine, CgHI2BrN2.OH, is obtained byheating monobromocyanethine with hydrochloric acid in sealedtubes at 200". It is identical with that obtained by E. v. Meye236 ABSTRACTS O F CHEMICAL PAPERS.(Abstr., 1883,3;3) by the action of nitrous acid on monobromocyan-ethine.Ardidocyaneth&ae, CgH,4N,3.NHPh, is formed, together with aniline-hydrobromide, by heating monobromocyanethine with aniline in sealedtubes at 200-230".It is insoluble in water, and slightly solublein alcohol, from which it crystallises in groups of shining leafletsmelting a t 125". It is a base easily soluble in acids, from whichsodic hydroxide and ammonia precipitate it. Bromocyanethine,when carefully fused with zinc ammonium chloride, yields a base,probably C9H14(NH2)N3. Potassium cyanide converts the mono-bromo-compound in to cyanethine.Tribrornocy anethine, C9H,,Rr3N3. I n the presence of water, theaction of bromine on cyanethine produces chiefly monobromo- togetherwith a small quantity of tribromo-cyanethine. When a solutionof cyanethine and chloroform is heated with bromine in sealedtubes at, lOO", the latter compound is formed; it crystallises fromalcohol in lustrous rhomhic leaflets irielting at 126".It is easilysoluble in ether and chloroform, but insoluble in water, and is solnblein strong acids, the salts formed being decomposed by water. Theanrochloride forms yellow, lustrous, silky needles.Illribromhydroxycyanconins, CgHloBr3N2.0H, is formed by treatingthe tribromo-compound with nitrous acid ; it melts a t 149", crystal-lises in white needles, insoluble in water, and resembles the mono-bromo h y droxy- base.TrichZoroc~arLethine, CgH,,C1,N3, is obtained by the action of chlorineon a solution of cyanethine in chloroform ; the residue obtained afterevaporating the chloroform solution is dissolved in absolute alcohol,and on addition of water yields the trichloro-compound in lustrous,pearly, rhombic leaflets, melting a t 110".This compound resemblesthe tribromo-derivative, and like it is converted by the action ofnitrous acid into a h ydroxy- base, C9HloC13N2.0H, which crystallisesin needles melting a t 132".An alcoholic solution of sodium ethylate converts trichloro-cyanethine into a brown oil, probably the triethoxy-base.Triarnidoclyanethine seems to be produced by the action of alcoholic.ammonia on trichlorocyanethine in sealed tubes a t 130". It is a baseand forms the platinochloride [ CgH,2(NH2)3N3]2,H2PtCls.Tetrachlorocyanconine, CgH1,,Cl3N2Cl, is formed by the action ofphosphorus pentachloride on the trichlorhydroxy-base. It is an oil ;when treated with concentrated sulphuric acid, it is reconverted infothis same hydroxy-base.Hydroxycyanconine is formed by the action of hydriodic acid onthe trichlorohydroxy-base.iVoniodocynnethine, C9Hl4IN3, is formed when a solution of cyan-cthine in dilute sulphuric acid, heated on a water-bath, is treated withnitric acid until all iodine disappears.On adding caustic soda,the compound is precipitated in small white needles. The base iseasily soluble in acids and caustic alkalis, and melts at 152". Itforins an aurochloride, (C9Hl4IN3),HAuCl~, which crystallises fromalcohol in orange-yellow leaflets.i~~oniodohydrolL.ycyartconine, C,H121N,.01T, is formed by the action oORGANIC CHEBIISTRT. 237fuming nitric acid on the iodo-base dissolved i n glacial acetic acid.It is solnble in acids and alkalis, water, and ordinary solvents ; itcrystallises in aggregates of needles, resembling the correspondinghromo-derivative, and melts a t 157".By the further action of nitricacid hydroxycyanconine is obtained (Zoc. cit).Action of Ally1 and Isobutyl Iodides on Zinc and Acetone.By E. SCHATZKY (J. pr. C'hem,. [el, 30, 216-217).-These bodiesreact on one another, producing allyl dimethyl carbinol and a smallquantity of a liquid of the composition C,,H,,O, boiling at 192-196". This compound the author regards as isobutylallyl dimethylcarbinol, a homologue of the bye-product obtained by Dieff in thepreparation of allyl dimethyl carbinol (Abstr., 1883, 1076).Composition of a Bye-product obtained in the Preparationof Diallyl Carbinol.By W. SCHESTAKOFF ( J . pr. Chem. [2], 38,215).-This substance, which has the composition CloH180, is probablyanalogous to that obtained by DiefE (Abstr., 1883, 1076) in the pre-paration of dimethyl carbinol ; it may be regarded as propyl diallglcarbinol. P. P. B.P. P. B.P. P. B.Derivatives of Symmetrical Isodichlorethyl Ether (Ethyl-idine Chloride). By A. GEUTEER (Arinalen, 226, 223-231).-Ilaatsch has lately shown (Abstr., 1883, 788) that the substanceknown as ethylidine oxychloride has t'he formula O(CHClMe),; thepresent paper describes derivatives prepared from it by double decorn-position with metallic salts of organic acids.The acetate, O(CHMe.OZ),, a colourless liquid of faint etherealodour, boils a t 191-193", has sp. gr.1.071 a t 16", and 1.067 a t 20".When agitated for a long time with cold water, it is decomposed intoaldehyde and acetic acid. It is not decomposed by aqueous sodiumcarbonate in the cold; on heating, aldehyde resin separates. Thepropionate, 0 (CHMe.C,H,O,),, a colourless liquid of faint, etherealodour, boils a t 210-215", and has a sp. gr. of 1.027 at 26". TheImfyrctte, C12B2205, a colourless liquid of ep. gr. 0.994 at 20", boils at.235-240", and does not seem to be decomposed by water. Theformnfe,CGHC1,O5, is a colourless liquid of penetrating odour; i t boils a t 175-185" with partial decomposition, and has a sp. gr. of 1.314 a t 31".When heated at 150" in sealed tubes, it is decomposed with separationof a brown resin and formation of carbonic oxide, formic acid, andaldehyde.The benzoate, ClsHI8O5, crystallises in slender, colourlessneedles. The succinate, CRHI2O5, is a colourless viscid substance,sparingly soluble in water, but readily soluble in very dilute aqueoussoda.Attempts to prepare a mixed acetate and butyrate were not, success-ful. When the acetate is heated with butyric anhydride a t 180-190",in sealed tubes, the butyrate and acetic anhydride are formed ; thereverse reaction could not be effected. A. J. G.Optical Inactivity of Cellulose and the Rotatory Power ofPyroxylin. By A. BBCHAMP (Conzpt. rend., 99, 1027'-1029) .--Th238 ABSTRACTS OF CHXJIICAL PAPERS.author criticises Levallois' paper (Abstr., 1884, 1288), and gives arks:'sume' of his own earlier researches (Compt. rend., 42, 1210, and 51,255).According to his results, insoluble cellulose and the solublecellulose obt'ained by the action of sulphuric acid, are both opticalljinactive. Prolonged action of varioiis reagents, such as snlptiuric orhydrochloric acid, however, converts the cellulose into substanceshaving a high dextrorotatory power, but these substances can becompletely converted into dextrose. Many specimens of pyroxylinare optically inactive, but others hare a dextrorotatory power whichvaries considerably with different samples. The cellulose obtained byreduciiig these pyroxylins is optically inactive. It would seem, there-fore, that any rotatory power possessed by deriTatives of cellulose isdue to some molecular transformation resulting from the action oftha reagents employed.Grevillea Gum.By c*. F r J m R Y (,TOW. Pharm. [ 5 ] , 9, 479-480).-An exudation occurs frequently upon the trunk of the Gwidleccrobusta (Proteaceae), similar in appearance to t8he gum of the cherrytree. The author has examined a product from Algeria. It isyellowish-led, slightly translucent, and slightly friable. In water itswells a litttle, and slowly produces a very persistent white emulsion,which passes through all filters. It contains no starch, but gives3 per cent. of ash, principally calcium carbonate, with a little potash.The emulsion treated with absolute alcohol gives a copious precipitateof gum proper. When the alcoholic solution is evnpoiated, itj gives 5.6per cent.of a reddish transparent resin, with slightly acid properties ;this is soluble in alkalis and carbon bisulphide. The gum proper isgrey ; does not appear to give a true solution in water, the liquid beingturbid and viscous ; it gives no prscipitate with ferric chloride. Thegum already soaked in water, dissolves immediately if a little potashlime, or potassium carbonate be added, and the solution gelatinisesunder the influence of a ferric salt. This characteristic reaction dis-tinguishes this product from all other known gums. The gum islaevorotary, and has no action on Fehling's solution. Lead acetategives a white precipitate, copper sulpliate a blue gelatinous one.Nitric acid converts it into mucic acid, mixed with a little oxalic acid.Dilute sulphuric acid after long boiling produces a sugar similar tothat obtained from Senegal gum.Ethenylamidoxime and its Derivatives.By E. NORDMANS(Ber., 17, 2 i46--C2756) .-In continuation of Tjemann and Kruger'swork (Abstr., 1884, 734 and 1325), the author has studied the com-pound obtained by the actlion of hydroxplnmiii e on acetonitrile.Btheny Zamidoaime, C,H6Nz0, was obtained by acting on acetonitriIewit>h hydroxylamine. The ltydyochloride, C,H,N,O,HCI, forms glisten-ing, white, hygroscopic scales which melt a t 140°, and are very stahlewhen pure. Care must, however, be taken during the process ofpurification to avoid the presence of free hydrochloric acid, as other-wise milch decomposition takes place. The hydrochloride is easilysoluble in water and alcohol, insoluble in ether, chloroform, &c.Thefree base is very unstable, and is best prepared by the addition of thecalculated quantity of sodium ethjlate to a dilute alcoholic solution ofC. H. R.J. TORGASIC CHEMISTRY. 2 39the hydrochloride, separation of the sodium chloride by the additionof ether, and eTaporation of the solution a t the ordinary temperatureunder reduced pressure. Even then, slight decomposition alwaystakes place. The free base crystallises in long colourless and odour-less needles, which melt a t 135", and are stable i n dry air. It isinsoluble in benzene, ether, and chloyoform, easily soluble in alcoholand water, and the aqueous solution gives a deep-red coloration withferric chloride.It is more easily decomposed by heat than theanalogous benzenylamidoxime, b u t resembles the latter in its pro-perties and reactions. Its constitution is probably NH,.CMe : NOH.It possesses both basic and acid properties. The sulphate is veryhygroscopic, and scarcely crystallisable ; the alkali salts are veryunstable. The free base is decomposed by water, more readily byacids, into acetamiile and hydroxylamine, NH,.CXle : KOH + H20 =KHz.OH + NH2.COMe. Sodium nitrite decomposes the hydrochloridethus : NH,.CMe : BOH + HN02 = NH,.COMe + NzO + H,O, bntthere appears alwajs to be a small qnantity of a very volatile sub-stance formed, which the author thinks is perhaps diethenylazoxime,CMe<F'z>CMe. The nzethyZ and etliyl ethers of ethenplnmid-oxime are very unstable, hygroscopic compounds.EfhenyZa?izidc;z~~2ehenzyl ether, NH2.CMe : N0.C7H7, is obtained by adding the calculatedquantity of sodium ethylate to a solution of the hydrochloride inabsolute alcohol, and then digesting 13 ith benzyl chloride. It forms apale yellow oil, which cannot be distilled evenin a vacuum, and a t theordinary pressure decomposes a t 200". Benzaldehyde and ammoniaare amongst the products of decomposition. The ether is almostinsoluble in water, easily soluble in alcohol, ether, &c. This ether ismuch more stable towards acids than cthenylamidoxime, and has lostthe acid properties of the latter. The hydrochloride forms smallwhite flakes which melt at 16S0, and yields a platinochloride crystal-lising in brownish-red prisms.When ethenylamidoxime is gently warmed with aniline ethenylani-lidoxime, NHPh.CMe NOH, is formed.It is very stable, formslarge brownish-yellow flakes and melts a t 121". It is soluble inalcohol, ether, benzene, and boiling water, almost insoluble in coldwater. It forms acid and basic salts, and yields a crystalline platino-chloride. An alcoholic solution, when treated with ferric chloride,turns deep violet, and with excess of the reagent olive-green : whenthe solution is heated, both coloiirs change to reddish-brown.When ethenylamidoxime hydrochloride is heated with benzoicCMe chloride, etlLerLyZazoximebenzenyl, N<o.e p 2 N , is formed. Thiscompound forms long white needles, melts a t 57" to an oil whiclldistils readily in a current of stteam, and begins to sublime a t 70-80".It is soluble in alcohol, ether.and benzene, insoluble in water. It isisomeric with Tiemann and Kriiger's benzenylazoximethenyl, meltingat 41°, and is similar to i t in properties.When ethenylamidoxime is heated with acetic anhydride, a Fellowsyrup is obtained, which probably coiitains diethenylazoxime, but theauthor has not yet succeeded in isolating the latter cornpound240 ABSTRACTS OF CHEMICAL PAPERS.PropenyZa.midoxime is formed by the action of hydroxylamine onTrioxymethylene. By L. PRATESI (Gazzetta, 14, 139-141).-The formula (C,HO), generally assigned to the polymeride of meth-aldehyde is based on its conversion of hydrogen sulphide into thecorresponding sulphur compound thiomethaldehyde, whose composi-tion is shown to be (CzHS)B from a determination of its vapour-density and the composition of its crystalline compounds with silvernitrate, This argument cannot, however, be considered final, forethaldehyde, under similar conditions, is converted not into itssulphur analogue, but into a substance easily transformed intoparathioethaldehyde ( C2H4S),.In order to tlirow some light upon this question, the author hasheated oxymetliylene in sealed tubes, with a trace of sulphuric acid,in such a way that the resultant material can sublime in a cool partof the tube, A sublimate is formed which, when resublimed, can beobtained in long flexible crystals 10 cm.in length ; they are very diffi-cult to pulverise, have the irritating odour of methaldehyde, andsublime slowly at ordinaq temperatures.They melt a t 60" and aresoluble in water, alcohol, and ether, the solutioiis reducing amrnoniacalsolutions of silver nitrate in presence of potash. Vaponr-densitydeterminations gave results corresponding with the formula (CH,O),.This substance mag be designated a-trioxymethylene. It is proposed tocarry on investigations regarding the transformations of this substance.V. H. V.popionitrile, and is now undergoing investigation. L. T. T.Action of Hydrocyanic Acid and of Dilute Sulphuric Acidon Aldol. By C. A.. LOBRY DE BRUYN (BdZ. XOC. Chim., 42, 161-166) .-A slightly acid solution of potassium cyanide was mixed withan ethereal solution of aldol in the proportion of 1.5 molecular propor-tion of cyanide to 1 of aldol, sufficient hydrochloric acid added to de-compose the cyanide, and theliquid allowed to remain two hours.Theethereal solution was then removed and evaporated, the syrupy residuetreated with water two or three times to remove unaltered aldol, and theproduct dried over calcium chloride. I n this way, a colourless liquidis obtained, containing 6.5 per cent. of nitrogen, aresult agreeingwith the formula (C,H802)2,HCN. The same compound is obtainedwhen one and the same quantit,y of aldol is subjected to four succes-sive treatments with nascent hydrocyanic acid. When this compoundis boiled with concentrated barium hydroxide solution, a salt is formedwhich could not be obtained pure.Analysis showed. however, thatj t s composition more nearly approaches that of an acid containing C9than C5. Other salts were obtained, but they are very unstable, anddo not crystallise.When 1 vol. of aldol is mixed with 2 vols. of pure liquid hydro-cyanic acid, and the mixture allowed to remain, a heavy oily liquidseparates and finally crystallises in small needles. When theseneedles are purified by washing, drying, and recrystallising fromether, they melt a t 113-114", have the composition C8R,103,and are identical with the isodialdaiie described by Wurtz. LiquiORGANIC CHEMISTRY. 241hydrocyanic acid, therefore, acts towards aldol as a, dehydratingagent.If aldol is mixed with nbcmt six times its weight of sulphuricacid of sp.gr. 1-82, a flocculent precipitate gradially form;, verysolublein alcohol and ether. This precipithte is a mixture ofCsHl,03 (2C1H,02 - H20) and C,H,O, (:JCaHBO, - 2H,O) in propor-tions varying with the conditions. When the solution from which theseflocculent precipitates hare separated is exhausted with ether, theethereal sohition evaporated, and the product dried in a vacuam, thecompound Cl,H,,OJ is obtained as a colourless liquid.The facts that 2 mols. of aldol combine with only 1 mol. of hydro-cyanic acid, and that the aldol forms isodisldane in contact withliquid hydrocjanic acid, would seem to indicate that the aldol hasundergone condensation with formation of dialdol. C. H. B.Some New Sulpho-derivatives of the Fatty Acids.By J.31. LOVBN (Ber., 17, .2817-228.L5).-Tl~iodigl~~~l21~c acid is readilyobtainsd by the action of sodium sulphide on sodium monochloracetate,hotli in concentrated solution ; the product is acidulated with sul-phuric acid and extracted with ether. The properties of the acid soobtained agree with those of the thiodiglycollic acid prepared bySchulze (Zest. f. Chem., 1865, 73), Schreiber (this Journal, 1876, ii, 398),and Andreasch (Abstr., 1880, 236). The lead salt has tho formulaS (CH,.COO),Pb. When thiodiglycollic acid is neutralised wihh analkaline carbonate and a 5 per cent. solution of potassium perman-gamate gradually added, heat is developed, whilst sulphonediaceticmid, SO,(CH,.COOH),, is produced ; this crysta.llises in rhombicplates melting at 182", is very readily soluble in water and alcohol,less so in ether.When it is heated to about 2@0°, it decomposesinto carbonic anhydride and dimethplsulphone. The barium salt,SO,(CH,.COO),Ba + 5H20, readily parts with 4 mols. H20, but itcannot be obtained anhydrous, heat decomposing it with formation ofdime thyls ulphone. Ethy I sdphonediace tate, S 0, ( C H,. C 0 OE t ) ,, formsa thick oil, nearly insoluble in water, and is decomposed by distillation ;it yields a voluminous amorphous precipitate, SO,( CHNn. COOE t),,with sodium ethylate, and is converted by aqueous ammonia into theanzide, SO,( CH,.CONH,),. Sulphonediacetamide forms lustrousscales, sparingly soluble in cold, readily in hot water ; it turns browna t 220" without fusing. Sul@honedipropionic acid, SO (C,H,.COOH,),olhined by the oxidabion of thiodilactylic acid (Abstr., 1884, 1298),crystallises in four-sided plates, melts at 155-156", and is extremelysoluble in water, alcohol, and ether.It may also be prepared bythe action of methyl iodide on ethyl sulphonediacetate and sodiumethylate. XuZphonetiihutyric acid, SO,( C,H6.COOH)2, may be obtainedby heating together ethyl sulphonediacetate (1 mol.), sodium ethylate(2 rnols.), and ethyl iodide (2 mols.) at 120-130", and saponifyingthe ether produced by baryta-water ; it crystallises in well formedoctahedra melting a t 152". When the product of the action of methyliodide on ethyl sulphonediacetnte and sodium ethylate described aboveis treated in the same way with a second quantity of sodium ethylatcand methyl iodide, and the product decomposed by means of hotVOL.xLvIrI. 242 ABSTRACTS OF CHEMICAL PAPERS.bar1 ta-water, barium sul phonedii sobutyrate, S 0, (C,H,. C 0 0) ,Ra + 2+H20, is obtained; it forms yitreous needles, sparingly solubleiii cold, moderately in hot water. The free acid melts a t 188".A. K. M.p-Dipropylacrylic Acid. By A. ALBITZKY ( J . pr. Clzem. [Z], 30,209-212) .-This acid is obtained from 13-dipropylethylenelacticacid by acting on it with phosphorus pentachloride or sulphnric acid ;the crude acid is purified by conversion into its zinc and other salts.It forms a hard white crystalline mass, is soluble in alcohol, ether, andbenzene, and crystallises from the latter in needles meltling at 80-81". I t s constitution is expressed by the formula CPrZa CH.COOH.The sodium and potassium salts are easily soluble non-crystallinesubstances, the lithium salt crystallises from alcohol in rounded masses,and has the composition C9HI,,02Li + 2H20.The calcium and bariumsalts are sparingly soluble in wt%ter, crystallising from alcohol with1 mol. H20. Thecopper and Zead salts are both insoluble in cold water, but soluble inhot water, the latter crystallises from alcohol in bundles of needlescontaining 24 mols. E,O.The zinc salt is insoluble in water and alcoholThe siZver salt is insoluble in water.P. P. B.Propenylglycollic Acid. By C. A. LOBRY DE BRUYN (Bu71. SOC.Chim., 42, 159--161).-When crotonaldehyde is mixed with aqueoushydrocyanic acid in the cold, no reaction takes place even after severalweeks, but if the mixture is heated in a sealed tube a t 70-80" forabout 10 days, the crotonaldehyde disappears and the liquid becomessomewhat brown.The liquid product is placed in a vacuum forseveral days to remove the excess of hydrocyanic acid, and is thenmixed with moderately strong hydrochloric acid, no attempt beingmade to isolate the cyanhydrin. The ammonium chloride whichformed is separated after some days, the liquid diluted with water,extracted with ether, and the ethereal solution eva.porated, when abrown strongly acid liquid is obtained, miscible with water. Ifthis liquid is dissolved in water, nentralised with baryta, and con-centrated, it yields a white crystalline salt, which, after being purifiedby repeated recrystallisation, has the composition Ba(C5H,03)2. Accord-ing to its method of formation, this acid will have the constitutionCH,.CH CH.CH(OH).COOH, and may be called propenylglycollioacid, a name which is preferable to that of angelactic acid, proposedby Rischoff and Pinner (Ber., 5,212).A solut'ion of the acid or of its barium salt rapidly decolorisesbromine- water.When the aqueous solution of the acid is neutralised with barytn,and the barium salt allowed to crystallise, the mother-liquor has anacid reaction, and if it is again neutralised and still furtherconcentrated, the acid reaction reappears.These facts point to theexistence of an internal anhydride. The last mother-liquor, whenconcentrated first on a water-bath, and finally over sulphuric acid,yields a solid amorphous residue, which is pribably a sdt of a pols-acid.C. H. BORGANIC CHEMISTRY. 243Formation of the Anhydrides of Mono- and Di-basic Acids.By R. ANSCH~~TZ (Annden, 226, l-l3).-The anhydrides of mono-basic acids can be prepared by heating for several hours a mixture ofthe acid chloride with the acid ; €or example, acetic chloride and aceticacid, benzoic chloride and benzoic acid, &c. The yield varies from50 to 90 per cent. of the theoretical. Better vesults are obtained bythe action of a dibasic acid on the corresponding chloride.Moller ( J . pr. Chcrn. is], 22, 194) has recently shown that analmost theoretical yield of succinic anhydride is obtained by heatingequivalent quantities of succinic chloride and succinic acid, and thendistilling the product.Attempts to prepare a mixed anhydride by acting on benzoic acidwith acetic chloride were unsuccessful.A large number of anhydrides of dibasic carboxylic acids have beenobtained by the aut'hor and others, by the action of acetic chloride onthe dibasic carboxylic acids, namely, the ail hydrides of succinic,monochloro-snccinic, monobromo-succinic, maleic, acetomalic.cli-aceto-tartaric, diaceto-racemic, citraconic, and itaconic, camphoric,phthalic, and diphenic acids.I n preparing the anhydrides of succinic, camphoric, phthalic, anddiphenic acids, the acetic chloride may with advantage be replaced byacetic anhydride. w. c . w.Racemic Acid from Furnaric Acid and the Calcium Saltsof the Four Isomeric Tartaric Acids.By R. ANSCH~~TZ (Annnlen,226, 191--201).-KekiilB and the author have shown (Abstr., 1881,156) that the racemic acid obtained by the oxidation of fumaric acid,is crystallographically identical with the racemic acid prepared formdextrotartaric acid. Proof of its chemical identity is now given byshowing that its sodium ammonium salt, like that of ordinary racernicacid, can be resolved into a mixture of the salts of dextrotartaric andlaevotartaric acids. The salts of these latter acids were identified bothby chemical and crystallographical examination.Calcium racernate alwaj s crystallises with 4 mols. HzO in microscopicneedle-shaped prisms. Crystals suited for measurement could not beobtained.Calcium mesotartrate, C,H,06Ca + 3H20, was preparedfrom inactive tartaric acids derived fi*om the three sources, namely,from dextrotartaric acid, from dibromosnccinic acid, and from maleicacid. The three preparations were found to be crystallographicallyand optically identical. It crystallises in the triclinic sptem ; a-xialr2tios: a : b : c = 0.886 :J : 0.96764; observed faces: mPm, mPm,Calcium dextrotartrate, C4H40,Ca + 4Hz0, and calcium levotartrate,C4H406Ca + 4Hz0, crj-stallise in identical forms and do not showhemihedric faces. They crystallise in the rhombic system-; axialratios : u : b : c = 0.87157 : 1 : 0.90834; observed faces, Pm, Pm.,P'm, 'P,m, mp;, w:e, mP$.A. J. G.Ethylidenethenyltricarboxylic Acid.By E. HJELT (Ber., 17,2833--2835).-The triethyl salt of this acid is readily obtained bythe action of ethyl sodomalonate on ethylic a-chlorocrotonate. It boilsJ 244 ABSTRACTS OF CHEMICAL PAPERS.a t 285-287". The free acid, CHMe: C(COOH).CH(COOH)?, ismoderately soluble in water, more sparingly in ether, and melts a t185" with evolution of cai-bonk anhydride. The barium and calciumsalts dissolve readily in cold, lcss so in hot water; the silver salt,CiH50fiAg3, forms a flocculent precipitate. The monethyl-derivative,C9Hl2O6 + 3H,O, obtained by saponifying the normal salt with aslight excess of alkali and crystallising. the oily product from water,forms large well-formed crystals melting at 70". When placed in adesiccator this loses 2 mols.H,O, and the residual compound C,H,,O, + H,O melts at 145". A. I(. M.Ethyl Acetylenetetracarboxylate. By C. A. BISCHOFF andC. RACH (Bey., 17, 2781--2788).-This ether, prepared by the actionof iodine on ethyl monosodomalonate. nielts at 76". When sufficientsodium is employed to form the disodium-derivative, ethyl dicarbon-fctracarboxylate, C,(COOEt), (Conrad and Guthzeit, Abstr., 1884,297) is formed. This crystallises in short thick hexagonal prismsmelting a t 56". When two atomic proportions of sodium are dissolvedin the smallest possible quantity of alcohoj, and then added to ethylrnalonate, ethyl disodomalonate is precipitated. This is quickly fil-tered and washed with ether, and then forms a white powder, but theauthors were never able to obtain it quite pure, as slow decompositiona t once sets in. If the precipitate first formed is not filtered off, it isvery soon redissolved, and the addition of ether then precipitates amuch more stable white powder, which gives numbers agreeing withtii e formula CO ONa.CHNa. COO E t. E thy1 propenyltricarbox ylateyields a similar compound, COONa.CNa(COOEt).CHMe.COOH.Attempts to obtain the salt, CH( COOEt),.C(COOEt),.CH(COOEt),,by the action of sodium ethylnte on a mixture of ethyl malonateand ethyl chloromalonate, proved unsuccessful. Etkylic nzonethyZ-ncetyZe,i etetracadwxylate, CEt (COO Et),. CH( COOEt),, was obtained byacting on ethylic sodethylmalonate with ethyl chloromalonate. It forms;t viscid colourless oil which boils a t about 200" under 150 mm.pres-snre. When treated with chlorine a t 70--80", it forms the mono-cltloro-derivtrtive, an oil possessing an irritating odour and a sp. gr. of1.076 a t 20" compared with water a t 15". Unlike most monosub-stituted malonic derivatives, ethyl acetylenetetracarboxylate does notform chloro-derivatives. If the temperature is raised to 200", regularabsorption of chlorine takes place, but carbonic anhydride is given03, and ethyl dichloretheiLyltricarboxylate is formed. An attempt toobtain ethyl dichloracetylenetetracarboxylate by the action of iodineon ethyl sodochloromalonnte proved also unsuccessful. The iodinesolution was a t once decolorised, but after a time, iodine was againliberated and ethyl dicarbontetracar boxylate formed. The authorshave found that the chlorine in ethyl chloromalonate is capable ofliberating iodine from sodium iodide, and it is probable that in theabove reaction the compound wished f o r was first produced, bnt thenBy F. CASZO-NERI and V.OLIVERI (Gaxzettu, 14, 172-180).-Schiff and Tassinaridecomposed by the sodium iodide formed. L. T. rr.Monobromo- and Dibrorno-pyromucic AcidsORUANIC CHEMISTRY. 245have described two isomeric monobromopyromucic acids prepared bythe action of potash on the addition-product of bromine on ethyl pyrc-mucate, and fractional crystallisation from boiling water. In thispaper, a description is given of a repetition of these experiments? boil-i n g benzene being used as the fractionating menstruum.The crudeproduct of the above reaction was by this means separated into amonobromo-pyromucic acid melting at 155", identical with one of theacids described by Schiff, and a dibromopjromucic acid meltinga t 183", identical with an acid described by Tonnies.A better mekhod for their separation is based on the differentdegrees of solubility of their barium salts in cold water, in which thatof the former is readily, but that of the latter sparingly soluble. Itwould thus appear probable that by the liniited action of bromine onpyi-omucic acid there is produced, besides the dibromide, a certainquantity of the tetrabromide of pyromucic acid ; the former yields t'hemonobromo-, the 1:ttt er the dibromo-substituted acid. 1MonoFro.i)zo-pyroinucic acid cryota1:ises in clinorhonibic prisms soluble in alcolic.1and ether, its buriunz salt in quadrilateral scales ; its silver salt is anamorphous precipitate.Dibromopyro~r~ucic acid crystallises in hexa-gonal laminae soluble in ether and alcohol, sparingly soluble in water ;its barium salt in prismatic needles ; its silver salt is a white amor-phous powder. Experiments were made on the dry distillation of theammonium salts of these acids with a view of obtainitig pyrroliriefrom them, but, owing to the small quantity of material, the resultswere far from satisfactory. V. H. V.Action of Hydrogen on Acetamide. By J. C. ESSFER (Rd?.SOC. Chim., 42, 98).--Acetamide, when treated with sodium amalgamin the presence of sodium bicarbonate? is converted into alcohol andsodium acetate. With the copper-zinc couple, it yields alcohol,together with small quantities of aldehyde, and an oil decomposing ondistillation.The simultaneous formation of alcohol and aldehyde maybe expressed by the following equations :-C2H30.NH? + 2H, = NH, + C2H60 and CzH30.NH2 + Hz = NH, + C,H,O. The evolution ofammonia was very marked. V. H. V.Occurrence of Leucine and Tyrosine in Beet Molasses.By E. 0. v. LIPPMANN (Ber., 17, 6835--2840).-A considerable yuan-tity of the alcoholic liquors employed in treating lime sucrate bythe elution method, was neutralised with sulphuric acid, and afterremaining for some time the solution was separated from the pre-cipitate. The liquor was then freed from alcohol and evaporatedto a small bulk, but no further separation took place.On dissolv-iug the product in hot water and adding lead acetate, an abundantprecipitate was produced. This was filtered off, the solutiontreated with hydrogen sulphide, concentrated to a syrup, andintroduced into alcohol, which produced a sticky tough precipitate,probably containing dextran. The alcoholic solution was evaporated,treated with lead acetate and with animal charcoal, and on evapora-ting the filtrate and allowing it to remain for a time, crystals wer246 ABSTRACTS OF CHEMICAL PAPERS.obtained, the first crop of which consisted of tyrosine,and the second a,mixture of tyrosine with Zeucine, the latter being readily separated bycrystallisation from alcohol. The specific rotatory powers of thetyrosine and leucine so obtained were found to agree with those ofanimal tyrosine and of leucine obtained from case'in, with which theyare no doubt identical, A.I(. M.Derivatives of Carbamide. By R. BEHREND (Bey., 17, 2846-2847).-The author recently described a compound obtained by theunion of carbamide with ethyl acetoacet'at'e (Abstr., 1884, 583).When the sodium salt, C5H7N20,Na, of this compound (Zoc. cit.) isdecomposed by acids, a molecule of water is eliminated, and a sub-stance, C,H,N20,, formed. When this is treated with nitric acid, themethyl-group is oxidised to carboxyl, and a nitro-group introduced ; aclibasic acid is obtained, the hydrogen potassium salt, C,H,N,O,I( +H20, of which can be split up into carbonic anhydride and thepotassium salt of a new nitro-compound, C4H,N,01.When reduced,this yields a base which combines with cpnic acid to form a com-pound C5H6N40, ; this is distinguished from xanthine by containingin addition the elements of a molecule of water, but it readily yieldsthe murexide reaction. The investigation is being continued.A. K. M.Action of Hydroxylamine on Pyrroline. By G. L. CIANICIANand M. DENNSTEDT (Gazzetta, 14, 156--157).-0n boiling an alcoholicsolution of equal parts of hydroxylamine hydrochloride, sodium carbo-nate, and pyrroline, there is formed, besides ammonium carbonate, awhite crystalline substance, C4H8N202, melting at 173". The reactionmay provisionally be represented thus :-CIH4NH + 2(NH2.0H) =C,H,(NH.OH), + NH, ; but the authors propose to examine the re-action more completely, and to extend their investigations to otheri mido-compounds.v. H. v.Pyrroline a-Carboxylic Acid. By Q-. L. CIAMICIAN and P. SILBER(Gazzetta, 14, 162--173).-0n heating together a mixture of pyrro-line, ammonium carbonate, and water in sealed tubes a t 130-140°,a-pyrrolinecarboxylic acid, C,H,N.COOH, is formed, identical withtlliat obtained by Schwanert from ammonium pyromucate (Abstr.? 1882,212). The reaction is however very incomplete, a large proportion ofpyrroline remaining unaltered. If the reaction be effected above 140°,a small quantity of an acid is produced probably identical with p-pprro-linecarboxylic acid. The calcium salt of the a-acid forms sparinglysoluble white scales of the composition CloH,N,O4Ca ; when perfectly(lry, it yields pyrroline on distillation.The silcer salt, obtained by theaddition of silver nitrate to an aqueous solution of the barium salt',forms small needles, sparingly soluble in water ; the methy1 sult, formedby the action of methyl iodide on the silver salt, crystallises in longneedles or large prisms having an aromatic odour. It melts a t 73", isreadily soluble in etlier and in alcohol, sparingly soluble in water.The ethyl saZt, obtained in a similar manner, melts a t 39", boils aORGANIC CHEMISTRY. 247230-232", is readily soluble in alcohol, ether, and petroleum, but onlysparingly in water If the vapour of bromine is passed into st boil-ing aqueous solution of methyl a-pyrrolinecarboxylate, a whiteflocculent precipitate is formed : this is a tribromo-derivative,CaBrJNH.COOMe, which crystallises in long needles melting at 209",and is readily soluble in ether and boiling alcohol, sparingly in water.Thus a-pyrrolinecarboxylic acid differs in its reaction with brominefrom pyromucic acid, which forms an additive-product containing4 atoms of bromine. The a-tribromopyrrolinecarboxylic acid crys-tallises in long needles soluble in ether, alcohol, and acetone ; whenheated a t 140-150" it is completely decomposed without fusion.Bythe action of acetic chloride on silver a-pyrrolinecarboxylate, an ncetyl-derivative is obtained ; this forms scales which melt a t 75", but aredecomposed a t the point of fusion into acetic acid and pyrocoll(Abstr., 1881, 29:).The introduced acetyl-grouping may yplacc anatom of hydrogen in the imido- or carboxyl-group :-C4H3NAc.COOHor CaH3NHCOG. Either of these substances might be decomposed inaccordance with the above change ; the authors, however, considerthe latter formula to be the more probable, inasmuch as their experi-ments tend to show that the hydrogen in the imido-group cannot bedisplaced by acetyl if a hydrogen-atom in the pyrroline nucleus isdisplaced by the ncetyl- or carboxyl-group.When methyl a-pyrrolinecsrboxSlate is heated with excess of aceticanhydride in sealed tubes a t 250-260", the methyl salt of acetyl-a-pyrrolinecarboxyiic acid, C4H&NH.COOMe, is formed, which crys-tallises in long needles melting at 113", soluble in alcohol, ether, andboiling water.By the action of silver nit'rate, a silver derivative,C8H3NOzSg, is obtained as a white precipitate. On saponifying themethyl salt and subsequently acidifying, the corresponding acid,C4H,GNH.COOH, is obtained ; this forms shining white leafletsmelting at 186", soluble in water, alcohol, and ether. I t s silver salt,C~H&.NH.COOAg, is a sparingly soluble precipitate ; its l e d saltforms glistening needles, and its calcium salt, ( C;H6N03)2Ca,70H2,forms large prisms belonging to the triclinic system.Synthesis of Furfurane -derivatives from E thy1 Diacetosuc -cinate. By L. KNORR (Bey., 17, 2863-2870) .-Ethyl carbopyrotri-tartrate is formed when ethyl diacetosuccinate is heated a t 200" ortreated with concentrated hydrochloric acid, the product being iden-tical with the compound CloHl2O5 described by Harrow (Trans., 1878,433).It dissolves readily in alkalis and in sodium carbonate solution,acids reprecipitate it unchanged; i t is saponified by boiling withaqueous or nlcoliolic potash or with dilute sulphuric acid, as stated byHarrow. By the action of concentrated sulphuric or phosphoric acidon ethyl diacetosuccinate in the cold, a molecule of water is eliminatedand diethyl ca?..bo~y1.otl.itart?.nte, CI2Hl6O5, is obtained, showing thatcarbopyrotritartaric acid is a dicarboxylic mid. This diethyl-derivativehas not the character of an ethyl salt of a ketonic acid, is insoluble inalkalis, and does not react with either phenylhydrazine or hydroxyl-amine. Its properties, mode of formation, and also the conversion ofcarbopyrotritartaric acid into pyrotritartaric acid indicate it to beV.H. V248 ABSTRACTS OF Cl3ERlICAL PAPERS.,CMe C.COOEtpyrotritartaric acid is therefore dinzeth~lf~~~furanedicarboxy7ic acid.Uiethyidirnethylfurfuranedicarboxylate boils at 275.5" (bar. 735 mm.).When ethyl carbopyrotritartrate is warmed with an excess of alcoholicpotash, the rLormal potassium salt is obtained, and by action of bariumnitrate on this, the barium salt C,H6Ba05. The acid liberated from thepotassium salt forms slender white needles melting at 230", and a8greesi n its physical and chemical properties with Harrow's carbopyrotri-tartaric acid. When heated with soda-lime, it yields an oil (probablydimethylfurfurane) insoluble in water, and when heated with water at200" a substance soluble in water.According to Harrow, carbopyro-tritartaric acid does not yield normal salts, but is converted, whenboiled with an alkali, into the normal salt of a n acid, C8H,,-,06; theauthor, however, obtains normal carbopyrotritartrates in this way.When the acid is dissolved in ammonia and the excess of the latteris expelled by boiling, the hydrogen ammonium salt is obtained. Thehydrogen silver salt, Cs?3,Ag05, is stable, and the normal salt,C8H6Ag206, unstable when exposed to light.It would seem that the acid obtained by Baeyer and Perkin(Abstr., 1884, 838) from ethyl dibenzoylsuccinate is also a furfurane-derivative, namely, diphenylfurfuranedicarboxplic acid.By t h e action of aqueous or alcoholic ammonia on etbyl diaceto-,CMe : C.COOEtis produced, isomeric with the compound obtained by the reduction ofethyl isonitroso-6-imidobntgrate.Analogous pyrroline-derivatives areformed by the action of aniline, paratoluidine, and p-naphthylamine.A. I(. M.Derivatives of Ethyl Acetophenoneacetoacetate and of EthylAcetonylacetoacetate. By C. PAAL (Bey., 17, 2756-2767) .-Bythe dehydration of acetophenoneacetone the author obtained twoisomeric compounds of the formula C11Hlo03 (Abstr., 1884, 1177).The one melting at 82-83" the author names dela2Jdracetophenoizace-tone, and ascribes to it one of bhree formule: CPh i C.CH2.COble;COPh.CH2.C i CMe; or COPh.CH,.CH,.C i C H : the other, meltingat 41-42', he considers t o be phanlylmethylf urfkane (phenylmeth ylfe-truphenol), t o have the formula <CH : cph>o, and to be formedaccording to the equations :-C H : CMeCH,.GOMe - CH: CMe.OH - CH : CMe<CH,.COPh -<CHI CPh.OH - <CH CPh>o+Hao*A better yield of phenylniethylfurfurane is obtained when fuminghydrochloric acid is substituted for acetic anhydride: when this isdone no dehydracetophenone-acetone is formed.Ethyl acetophenone-acetoacetate yields analogous dehydrated derivaORQdNlC CHEMISTRT.249tives. When poured into boiling alcoholic potash it yields an acid,C,,H,,O,, already described. This compound, which shows the pro-perties of an unsaturated ketonic acid, the author designates dehyd1.o-acetophenone-acetonecar boay lie acid, and believes t o be the carboxylicacid of dehydracetophenone-acetone just described.This acid is not astable compound, and when boiled with mineral acids is converted intoa stable isomeric acid, which forms white glistenirig needles meltingat 180-181"; when the new acid is heated m-ith water i n sealed tubes a t340-250", it splits up into phenylmethylfurfurane and carbonic anhy-dride, and is therefore undoubtedly phen~lmethyIfurfuranecarboxy7Icacid, I \O. I t s formation from the ketonic acid isprobably t o be explained by supposing an addition of water to thelatter when treated with the mineral acid, and a simultaneous coiirer-sion of the ketonic groups into unsaturated alcoholic groups. Thecompound so formed would then again give up the elements of waterand form an internal oxide :-CO0H.C : CMeCH: CPh'CO0H.C CMe.OH CO0H.C : CMe1 \O + HzO.- -CH: CPh'ICH.CPh.OHThis acid begins to sublime a t loo", and yields long needles of theunchanged acid : it is easily soluble in alcohol, benzene, ether, &c. Itis also decomposed into the furfurane by long-continued boiling withmineral acids, arid very easily and completely by distillatioil over zinc-dust. It does not combine with phenylhydrazine. The alkali saltsare easily soluble in water, the others less so.Ethyl acetonylacetoacetate, already prepared by Weltner (Abstr.,1864, 746), when treated with fuming hydrochloric acid yields ethylpyrotritartrate. The acid obtained from this ether was proved to beidentical with pyrotritartaric acid.From analogy with the above reac-tions the author believes pyrotritartaric acid to have the constitutionCO0H.C : CMe,,O, and not to be a ketonic acid as hitherto believed.This view is strengthened by the fact that, this acid does not combinewith phenylhydrazine. If this view is correct, carbopyi*otritarta,~*icacid must be looked upon as dimethylfurfuranedicarboxylic acid,<c(cooH) C(CO0H) i CMe>O. CMe The author considers it very probable thatall compounds containing the -C0.CH2.CH2.CO- group arc?readily convertible into furfurane-derivatives. Pyrotritartaric acidwhen heated with water a t 150-160" undergoes a peculiar reaction,yielding a ketone, C6Hlo02, which boils a t about 1S7", is easily solublein water, and combines readily with phenylhydrazine to form a c r ptalline compound.Bromophenylnaethylfairjurane tetrabrornide, CllH9Br50, is obtained byadding the furfurane to an excess of cold bromine : during the reac-tion, the temperature should be kept low enough to keep a part of thebromine frozen.This compound forms bronze-coloured, metallic-ICH : CMeThe author believes i t to be acetonylacetone250 ABSTRACTS OF CHEMICAL PAPERS.looking scales, which are insoluble in the usual solvents in the cold,and decompose on heating. It blackens at 200" and melts a t 208-210". Tetrahydrophenylmethylfurfurane ~phenylmethyltetrnmethylenlsoxide) is obtained by the reduction of an alcoholic solution of thefurfurane with sodium.It forms a coloiirless mobile oil which distilswithout decomposition a t 230". It is insoluble in water and alkalis,but miscible in all proportions in alcohol, ether, &c. It does not reactwith phenylhydrazine, and can be boiled with sodium without decom-position : it, therefore contains neither ketonic oxygen nor hydrosyl.With hydroxylamine, dehydracet'ophenone-acetoacetic acid forms acompound, C12H12N30s, which crystallises in white scales soluble inether, alcohol, mineral acids, and alkalis, but only very sparingly inwater. It turns brown at 150°, and melts with decomposition a t 172".This reaction is remarkable as, although the acid contains only onecarbonyl-group, it enters into reaction with 2 mols. of hydroxylamine.J%-ith pheaylhydrazine, this acid forms a very unstable compound,Cl,H,,N2O2, which crystallises from water in small yellow needles.When phenylmethylfurfuranecarboxylic acid is boiled with a largeexcess of acetic anhydride, a compound, C14H1204, is formed, whichcrystallises in flat plates soluble i n alcohol, ether, and benzene: itmelts at 80-8.3".It is a t once dissolved by aqueous caustic soda withre-formation of the original acid. The author is now investigatingthis compound.Besides ths compound, CI,HlsNa, already described (loc. cit.), theauthor, by the action of phenylhydrazine on an ethereal solution ofwetophenone-acetone, has obtained another compound, C17H18N20,which crystmallises in well-formed prisms easily soluble in ether andbenzene.It melts a t about 105", but is exceedingly unstable, even atordinary temperatures.When ethyl acetophenone-acetoacetate is boiled with dilute hydro-chloric acid, it yields phenylinethylf urfzranecarboxylic acid togetherwith a small qiJantity of phenylmethylfurfursne. The oil obtainedby Weltner was probably a mixture of these two compounds.L. T. T.The Thiophene Group. By V. MEYEK and 0. STADLER (Ber., 17,2778--2779).-The authors have endeavoured to obtain amido-deriva-tives of thicphene by the reduction of the nitro-derivatives, butalthough they have tried a great variety of reducing agents, theyhave up to the present been unsuccessful ; entire decomposition hasalways set in. They find, however, that the thiophene-derivativeshave much more intense colouring properties than the benzene-deriva-tives.When mononitrothiophene is boiled with alkalis, it dissolves toa brownish-red soluti9n. Mononitrothiophenesulphonic acid is at onceconverted into n magcnta-coloured solution by the action of ammoniumsulphide. When dinitrothiophene, in alcoholic solution, is treatedivith a very small quantity of potash, it gives a very brilliant dark-redsolution ; this is due to the presence of a potash salt which the authorshave obtained as a reddish-violet varnish, by precipitation with ether.Excess of alkali or acid destroys the colour. The magenta coloration(first observed by Hofmann) obtained when a drop of caustic potashis added to an alcoholic solution of commercial diiiitrobenzene, is duORGANIC CHEMISTRY.251to the presence therein of dinitrothiophene ; dinitrobenzene, preparedfrom benzene free from thiophene, does not show this reaction.L. T. T.A Simple Method of obtaining Thiotolene and Thioxylene.By K. E. SCHULZE (Bey., 17, 2852--9854).-This method consists insubmitting the acid used in the puritlcation of xylene and toluene todistillation with steam. If the acid be first diluted with water, lesssulphurous anhydride is evolved, whilst the yield of oil is greater : 90per cent. of t,he oil distilled between 135-138", and contained 44 percent. thioxylene. The oil obtained from the acid used in purifyingtoluene yielded, on rectification, a product boiling at 111-112" andcontaining 22.3 per cent. thiotolene ; a portion also boiled at about SO",and from its reaction with isatin and sulphuric acid evidently con-tained thiophene.The author intends to examine the acids used in the purificationof benzene, naphthalene, and phenol.A. K. M.The Benzene Theory. By E. LELLMANK (Ber., 17,2719-2723).-The author describes comparative quantitative experiments on thereadiness with which the hydrochlorides of ortho-, meta-, and para-nitranilines are decomposed by water, the result being that the ortho-compound is the most readily acted on, the para-compound coming next,whilst metanitraniline hydrochloride is least acted on. The introduc-tion of a nitro-group into aniline is thus seen to diminish the basicityof the latter, least of all when it takes up the meta-position, and mostof all when it occupies the ortho-position. The author also refers tomany well-knowu observations that show the greater influence of theortho- and para- over the meta-position on certain reactions, and thatby the introduction of a nitro- or hydroxyl-group into a simple ben-zene-derivative, the chemical properties of the latter are affected to aless or greater extent, according as the group introduced is in themeta-, para-, 01- ortho-position.The diagonal formula of benzeneappears to offer a better explanation of the above relation thaneither Kekulb's or the prismatic formula. A. I(. M.Monochlorethylbenzene. By ISTRATI ( B d . SOC. Chim., 42,111---116).-1f a current of ethylene is passed into a mixture ofphenyl and aluminium chlorides, there is formed a mixture of thethree monochlorethylbenzenes, CsH4C1Et.On fractional distillation,the greater part passes over between 179-182", and consisted of theortho-, meta-, and para-derivatives in the proportion 7 : 10 : 3. Theportion of the liquid boiling between 180-181" is an agreeablysmelling liquid of sp. gr. 1.Oi5 ; when exposed to a freezing mixturesmall crystals are deposited, probably the para-derivative. Withsulphuric acid, this liquid forms three sulphonic acids, differingin appearance and solubility ; it is proposed to make these the subjectof a future memoir. V. H. V.Monobromoparaxylene. By P. JANNASCH (Rer., 17, 27'09-The properties pre- 2711).-A reply to Jacobsen (this vol., p. 144)252 ABSTRACTS OF CHEMICAL PAPERS.viously assigned by the author to this compound are confirmed (see(Awnaleib, 171, 79).Acetyltoluene.By J. C. ESSNER and E. GOSSIN (BulZ. SOC.Chim., 42, 95--98).-Acetyl chloride and toluene, when heated withsmall quantities of aluminium chloride, form acetyltozuene, an aromaticliquid boiling a t 224-225" ; sp. gr. a t 22" = 0.9891. As this sub-stance on oxidation with potassium permanganate yields metaphthalicacid, together with only the smallesgraces of the ortho- and para-acids,it must have the constitution C6H4AcMe (& : Me = 1 : 3). On oxida-tion with nitric acid, it seems to form a tolnic acid.A. K. 31.V. H. V.Action of Phosphoric Chloride on Ethers of the BenzeneSeries. By A. COLSON (Compt. rend., 99, 975-977, and Bull. Sod.Chim., 42, 152-156) .-Paraxylene monethylin dissolves in dilutehydrochloric acid even below loo", yielding dichloro-xylene, alcohol,and water. Other ethylins of the benzene series behave in the sameway, but the reaction is slower.If the paraxyleiie inonethylin isallowed to remain in contact with phosphoric chloride in the cold, thesame product is formed, but if 10 grams of the ethylin are heatedwith 12-14 grams of the chloride until the latter just melts, animpure oily chlorethylin is formed, which after some months depositsterephthalic acid. When paraxylene monethylin is heated with t w oand a half times its weight of phosphoric chloride, hydrogenchloride, phosphorus trichloride, phosphoryl trichloride, and monochlor-ethane are giveik off, and the liquid i n the flask acquires a wine-redcolour.If this liquid is thrown into water., heat is developed, and asthe solution cools colourless needles of terephthalic aldehyde aredeposited, identical in their properties with the terephthalic alde-hyde described by Grimaux, but the greater part of the product sinksto the bottom as a heavy liquid which soon crystallises. By con-tinually treating this liquid with boiling water, the yield of terephthalicaldehyde is considerably increased. The fact that the compoundthus obtained readily reduces tin salts and ammonio-silver nitrate,shows clearly that it is a true aldehyde, and not a phthalide.Methylbenzyl oxide when heated with phosphoric chloride in thesame way, yields benzaldehyde, and hence it would seem that thereaction is general amongst the ethers of the benzene series.In all probability, the phosphoric chloride in the cold, or a t about loo", acts simply as a ch1orinat)ing agent, and forms dichloro-xylene,but a t a higher temperature (about 175") it dissociates into phos-phorus trichloride and chlorine, and the latter attacks the methyl-groups in the dichloro-xylene, and converts them into methylenedichloride, thus producing the compound (AH4( CHCl,),, which isdecomposed by water with formation of terephthalic aldehyde andhydrochloric acid.It must be observed, however, that when thechlorethylin is heated with phosphoric chloride, it yields no tere-phthalic aldehyde, hence possibly the reaction is more complicated thanthat j u s t indicated.I n any case it is evident that when phosphoricchloride acts on the ethers of the benzene series, it attacks the lateralchains. C. H. BORGANIC CHEMISTRY. 253Action of Benzoic Chloride on Isodurene in Presence ofAluminium Chloride. By J. C. ESSNER and E. GOWN (Bull. Soc.C'him., 42, 170--174).-The action of benzoic chloride on durene hasalready been studied by Friedel, Crafts, and Ador (Abstr., 1879, 713).The isodurene employed by the authora was obtained by the action ofinethyl chloride on toluene. The portion of the crude product boil-ing a t 185-195" was rooled repeatedly to 20", in order to separate thegreater part of the durene, and the portion remaining liquid was thenconverted into sulphonic acids, and the sodium salts were treated withhydrochloric acid a t about 210".I n this way, tolerably pure isodureneis obtained, the greater part of which boils a t 185-190".Isodurene is mixed with half its weight of benzoic chloride, andtiluminium chloride added. The reaction takes place readily in thecold, with development of heat, and when all evolution of hydrochloricacid ceases, benzene is added, and the product washed with water.On distillation, the crude product yields a yellow viscous liquid, boilingbetween 250" and 360". After some days, this liquid deposits a massof crystals, which are washed with alcohol to remove the adheringliquid, and purified by recrystallisation from boiling alcohol. Thefirst alcoholic washings deposit a further quantity of the crystals byspontaneous evapoi-ation.These crystals are beazoylisodurene, C6HMe4.COPh ; they melt a t62-63', and boil a t about 300", When treated with potassiumhydroxide, they yield potassium benzoate and isodurene.Benzoyl-isodurene dissolves readily in sulphuric acid, forming a sulphcnic acid,which is only slightly soluble in cold water, but very soluble in ether.When treated with nitrosulphuric acid, benzoylisodurene yields aellow ow liquid nitro-derivative, and a product which dissolves in water,aiid seems to be a nitro-derivative of some acid formed in thereaction.Benzoylisodurene in alcoholic solution combines with hydrocyanicacid, and when the product (which is ditficult to purify) is boiled withalcoholic potash, ammonia is evolved, and if the solution is neutralisedwith hydrochloric acid, evaporated to dryness, and the residue ex-tracted with absolute alcohol, an acid is obtained, which forms a whitepowder soluble in water, alcohol, and ether.The sodium salt crystal-lises in lamella. The silver salt on analysis gave numbers agreeingwith'the formula C6HMe4.CPh(OH).COOAg. The acid is therefore~,he~ylisodurylglyco/7ic acid. When benzojlisodurene is heated a t250" with fuming hydriodic acid, it yields benzylisodurene or benzyl-tetramethylbenzene, C6HMe4.CH2Ph. Ador and Rillet have shownthat the isodurene obtained by Friedel and Crafts' method is identicalmi th Jannasch's /3-durene, so that in benzylisodurene and benzoyl-isodurene the methyl-groups miist be in the positions [2 : 3 : 4 : 61.When an ethereal solution of benzoylisodurene is placed above anaqueous solution of hydrogen sodium carbonate, and treated withmetallic sodium, it yields a yellow oil, which boils above 360", and iseither an alcohol or a pinacone, but its composition approaches mostnearly to that of phenyl isoduryl carbinol.Wben this substance isheated wT.jt>h benzoic acid, and the crystalline product washed withwater and then crjstallised from ether, phenyl isoduryl carbinol ben254 ABSTRACTS OF CHEMICAL PAPERS.zoate, C6HMe,.CPh.0E, is obtained in colourless crystals, which meltat 75". The acetate is obtained by heating the crude product withacetic anhydride in sealed tubes at 100". It is a yellowish oil, boilingabove 360".When oxidised by a hot or cold solution of potassium permanganate,benzoylisodurene yields an acid, which appears to be benzoyl benzene-tetracarboxylic acid, COPh.CBH(COOH)4.No penhcarboxylic acid isformed even when the permanganate is in very large excess.Durene when treated with benzoyl chloride under the above con-ditions is only very slightly attacked, and a mixture of durene andisodurene yields benxoylisodui*ene and unaltered durene, without anymixed ketone. C. H. B.Carbonates of Bivalent Alcohols and Phenols. By 31.WALLACH (Annalen, 226, 77-87). - Isohydrobenzoirz carbonate ISformed when ethyl chlorocarbonate acts on the sodium compound ofisohydrobenzoh. The bicarbonate could not be obtained. Hydro-benzoin carbonate is prepared by ail aaalogous reaction.The sodiumcompound required for its preparation, can only be obtained by theaction of sodium amalgam on a solution of hydrobenzoh in benzene.The carbonate crystnllises in needles melting a t 12Go, which dissolvefreely in alcohol and ether.Ethyl ethylenebicarbonate, C2H4( O.COOEt),, is formed by the actionof ethyl chlorocarbonate on the sodium compound of ethylene alcohol,but it has not been obtained in a state of purity. It is decomposed ondistillation, apparently yielding ethylene carbonatle arid ethyl car-bonate. The author bas repeated Bender's (Ber., 13, 696) expe-riments on the action of ethyl chlorocarbonate on bivalent phenols,but has in some instances arrived a t different results ; namely, fromresorcinol he obtained ethyl resorcinylbicnrbonate, C6H4( O.COOEt),, athick oil boiling between 298" and 302", miscible with alcohol andether.It is decomposed by prolonged boiling into monoethylresorcinol.Orcinol also yields an analogous compound, C,H,Me(O.COOEt),,which boils at 311". It is decomposed by continuous boiling, yieldingm one th ylorcinol. w. c. w.Action of Phosphorus Trichloride on Aniline. By C. L.JACKSON and A. E. MENKE (Artier. Chern. J., 6, 89, and Chem. News,50, 280).-In 1865 Tait described the product of the action of phos-phorus trichloride on aniline as a white salve-like mass, of the corn-position ( NHPh),P3,HC1, easily soluble in water, alcohol, and ethey,and yielding n platinochloride and several doable salts. The authorshave investigated this subject, and have cogent reasons for contestingthe above statement.The action of phosphorus trichloride on aniline is very energetic,when 3 molecular proportions of aniline are added to 1 mol.of tri-chloride. The product is a hard white solid, which is a mixture o€substances, and obstinately resists all att,empts at purification ; alarge number of solvents were tried, in all of which, witli the excep-tion of water, methyl and ethyl alcohol, and acetone, it is insolubleORGANIC CHEMISTRY. 255When, however, the trichloride is added to a large excess of aniline,Tait's salve-like mass is obtained. This contains, amongst other sub-stances, aniline hydrochloride ; and as Tait purified his substance bysimply washing it with water, it is evident that the aniline hydrochloridewould remain mixed with it.With excess of trichloride, the productis a white compact mass. Both the latter products are, to a con-siderable extent, soluble in ether ; this the authors consider to be dueto their respective solubilities in the excess of aniline in one case, andthe excess of trichloride in the other. When the original product isheated in a dish over a naked flame, it turns orange-red, and anilinehydrochloride and a gas containing phosphorus volatilise, whilst theresidue yields a colourless solution with alcohol, and an orange-colouredor red insoluble substance containing 81.73 per cent. of phosphorus. Onthe addition of water to the alcoholic solution, a white precipitate of(NHPh),PHO is formed, aniline hydrochloride and phosphite remainingin solution.Attempts to obtain (NHPh),PCl were made, but withoutsuccess. Phosphorus anilide, (NHPh) ,PHO, prepared as describedabove, forms, after purification, a white amorphous substance, readilysoluble in cold alcohol and ether, insoluble in cold water ; it melts a t87", has no acid or basic properties, and is not affected by acids oralkalis in the cold. Alcoholic soda attacks it with difficulty; bntboiling with strong hydrochloric acid for 12 hours decomposesit completely into aniline hydrochloride and phosphoric acid ;whereas by gently heating it wit,h nitric acid, a red solution is pro-duced, from which water precipitates a red resinous body containingphosphorus, whilst a witropheiLoZ remains in solution ; in one casetrinitro-, in another metadinitro-phenol were obtained. By heatingit with acetic anhydride and fused sodium acetate, a c e t a d i t l e isformed.Froin these results, the authors conclude that the productof the action of phosphorus trichloride on aniline, which is solublein water, consists of aniline hydrochloride and NHPh.PC1,. When thismixture is heated, the two substances act on one another, producing(NHPh),PCl, which in its turn is converted into the insoluble(NHPb),PHO by the combined action of alcohol and water. If theoriginal product is boiled for some time with excess of aniline, amixture of substances is obtained, amongst which are cr@allinesubstances melting a t 150" and 208", and apparently a substance witha higher melting point.The substance melting a t 208" forms small white prisms, apparentlymonoclinic, or long radiating needles.It is freely soluble in hot, lessso in cold alcohol, insoluble in water and in ether. Aqueous potashor sulphuric acid does not act on it in the cold, but when boiled witheither of them, it is gradually decomposed. Heated with hydro-chloric acid at 140" under pressure, it yields phosphorous and phos-phoric acids, aniline hydrochloride, some carbon, and gives an odouieof phenol ; its formula is possibly (NHPh),P,O,H,. The substancemelting a t 150" has been very imperfectly examined ; it crystallisesin rather thick white radiating needles. D. A. L.Derivatives of Amidoethylbenzenes. By H. PAUCKSCH (Ber.,17, 2800--2806).-The ortho- and para-compouuds are best separate256 ABSTRACTS OF CHEMICAL PAPERS.by means of the different solubilities of their acetyl-derivatives ;ace tylparamidoe th ylbenzene is sparingly soluble, the ortho-componn dvery easily soluble in water.The para-compound solidifies a t-8" to -lo", and remelts a t -5"; the ortho-compound does notsolidify a t these temperatures. Both bases resemble the correspond-ing toluidines in character.Benzoylortharnidosthylbenxene is obtained by heating the base onthe water-bath with benzojic chloride. It crystallises in small flakesmelting a t 147". BenzoyZparamidoet~~Zbenzene forms long needlesmelting at 151". Wheii heated with phosphoric acid, orthophenyl-ethylthiocarbamide is decomposed, yielding the phosphate of thebase and orthophenylethylthiocarbimide.The latter is a colonrlessmobile liquid, which boils with partial decomposition a t 240-245".Orthn~idoeth!jlbenze?aes?Llphonic acid is formed by the action of con-centrated sulphuric acid on acetylorthamidoethylbenzene. It formsFlistening white needles. With potassium nitrite and dimethylaniline,i t forms a colouring matter crystallising in dark-orange scales. Theanalogous diethylated compound is amorphous.Di~arethylphenylcarbamide, CO(NH.CsH4Et),, is formed by theaction of carbonyl chloride on paramidoethylbenzene. It crystallisesi n long needles, and melts a t 217". Dzpareth?llp?Lenylguaniaire,CNH( NH.C,H,Et), is formed by heating diparethylphenylthio-carbamid e, dissolved in alcoholic ammonia, with excess of lead oxide.I t crystallises in large plates melting at 137-135".It is easilysoluble in alcohol, ether, and carbon bisulphide. It dissolves readilyin concentrated hydrochloric acid, and yields a platinochloride whichcrystallises in scales.When 1 molecular proportion of dichloracetic acid is heated onthe water-bath with 4 of paramidoethylbenzene in alcoholic solution,a mixt8ure of two compounds is obtained. The one is a colourlesRcompound, which is soluble in alcohol, insoluble in boiling water orhydrochloric acid, and sublimes a t 220-225". The other is un-doubtedly parethy lpheny lparethylimesatin, analogous to the compoundobtained by P. J. Meyer (Abstr., 1884, 47), although the author wasunable to entirely free it from the other substance. When heatedwith hydrochloric acid, it dissolves, ethylisatin being formed, whichcrystallises in red needles melting at 137".There is thus no doubtas t o the identity of the imesatin.L. T. T.Action of Cyanogen on Aromatic Diamines. By J. A. BLADIN(Bdl. Xoc. Chim., 42, 104--111).-Cyanogen combines wit,h aromaticdiamines t o produce compounds of the general formula CnHzn--BNd,which form two series of salts, containing 1 and 2 mols. of a mono-basic acid respectively. These substances, when heated with hydro-chloric acid a t the temperature of boiling water, give off one NH-groupin the form of ammonia ; at a higher temperature, two NH-groups areseparated, thus : (I) CnHZs-8N4 + H,O = C,H?,-,NSO + NH, a d( 2 ) CnHznesN1 + 2H,O = C,H,,-,oN,O, + 2NH3. I n this paper,the derivatives of oi thophenylene and metaparatoluenediamine aredescribedORGANIC CHEMISTRY.257Dicy anon? etaparatoluened iamine, C9H,,N4, obtained by saturat8in ga solution of met(aparato1uidine with cyanogen, forms colourlesscrystals containing 1 mol. of water. The following constitutionalformula is assigned to it :-CH NH1 II I fHC C C : N H 2J(h&Its hydrochlorides, C9H,,N4,2HCl and CgHloN4,HC1, crystallise incolourless needles ; its platinochlorides, ( C9H,oN4)2,H,PtC16 + 2H20and CgHI0H4,H2PtCl6 + 2Hz0, crystallise in small needles and tabletsrespectively ; the sulphate, CgHloN4,H2S04 + H,O, forms a white crys-talline powder. On heating the base with hydrochloric acid a t loo",there is obtained a substance of formula C9H9N30, which crystallisesin small needles, melts a t 290°, and is sparingly soluble in water andalcohol ; its hydrochloride, nitrate, and snlphate crystallise in needles ;its platinochloride is amorphous.When heated with hydrochloric acid at 150": the base yields twosubstances of the composition C9H,N,0 and CgHaN202, of which theformer is probably isomeric with the above-mentioned compound ; thelatter crystallises in silky needles, and is probably a dihydroxy-toluquinoxaline.DicZlano-orthophenil~eizedia?nine, obtained by passing cyanogen i n toan alcoholic solution of orthophenylenediamine, forms pale yellowrhombic tables, sparingly soluble in water, and melts a t 280".I t sconstitutional formula is written thus : C6H4<Its platinochlorides, (C8H,N,),,H2PtCI, -t 3H,O and (C8H8N4),H&C1, + H20, crystallise in yellow needles.When heated with hydro-chloric acid at loo", i t yields a compound of the formula CAH7N30,cryst'allising in needles which melt a t 280"; but if the reaction beeffected a t 1 50°, there is formed a di/~~~dro~~/quinoxaZine, C8H6N2O2 ;this crystallises in long needles, melts a t 280°, is sparingly soluble inwater, and forms metallic salts.By E. PISCHER (Bey., 17,2841-2846).-1n this paper the author shows that the hydrazineshave the constitution represented by the formulse NHPh.NH2 andNPhMe.NH2, and not NH,Ph : NH and NHPhBIe : NH, as assumedby Erlenmeyer (Abstr., 1883, 1103).Decomposition of Diazo-compounds by Alcohol.By E.WIIOBLEWSKY (Ber., 17, 2703-2704).-A question of priority.Action of Quinones on Amidophenols. By T. ZINCEE and A .HEBEBRAND (Annaleti, 226, 60-76) .-By the action of benzoquinonef This formula, together with others, is incorrectly written in the originalmemoir.-V. H. V.VOL. XLVIII. tNH.C(NH)NH.C(NH)>-V. H. V.Constitution of the Hydrazines.A. I(. M258 ABSTRACTS OP CHEIIICAL PAPERS.on orthamidophenol in hot alcoholic solution, quinol and a base ofthe composition C2,HI8N4O4 are produced. The latter is deposited inneedle-shaped crystals of a violet colour, but the former remains insoliltion. The crystals melt a t 250", and a t a higher temperature yielda red crystalline sublimate. The compound is soluble in aniline, but8is dissolved with difficulty by the usual solvents. It is decomposedby hot potash or eoda lye with evolution of ammonia.It dissolvesin dilute acids, forming salts which dissociate in the presence of alarge quantity of water. The hydrochloride, C24H18N404,'2HC1, has a,green metallic lustre. I t dissolves freely in alcohol, and is sparinglysoluble in water. It yields crystalline double salts with mercuric,stannic, zinc, and platinum chlorides. The ptatirwchloride formsbroad needle-shaped crystals of a brownish-red colour, which dissolvein hot water. The sulphnte is a green crystalline powder ; the oxdutt?forms green needles soluble in alcohol, and the picrate steel-blueneedles melting a t '235" with decomposition.The acety I-derivative, C2J€16Ni04G,2, crystallises in brown needles orplates (melting a t Z S S O ) , and dissolves freelyin benzene and in glacialacetic acid. The benzoyl-derivative, c24H16N404E2, forms yellowneedles which melt a t 264*5", and are soluble in hot acetic acid andin benzene.Cautious oxidation with nitric acid converts the acetyl-derivativeinto oxalic acid and a nitro-product, C2,H,,(N02)N206, which isdeposited from it's solution in acetic acid in golden plates.Thecrystals begin to blacken at 265", and melt between 275" and 280".The nitro-compound dissolves in alkalis, forming a violet solution,from which alcohol precipitates a crystalline compound. Tin andhydrochloric acid reduce the nitro-product, forming a crystallinedouble salt.Aniline unites with it to form a crystalline compound ofa dark blue colour, melting a t 229".On the addition of sodium nitrite to a solution of the hydrochloride,CzaHleN4O4,2HC1, a red crystalline compound is deposited which hasthe composition C24H,oN404(XO),.11. Benzoquinone has no action on the acetic derivatives of orth-amidophenol, but it enters into double decomposition with orthamido-phenyl methyl ether, according to the equation 3C6H,02 +20Me.CGH4.NH2 = CEH,(NH2.C,H,.0~~e),0a + '2C6K,(OH),.The substitution-product crystallises in reddish-violet needles whichmelt a t 230". It has neither acid nor basic properties.111. Benzoquinone acts on paramidophenol according to the equa-tion 3C6H40, + 2NH2.C,Ha.0H = C6H2(NHa.C6H3.0H),02 +2C6H,(OH),.The best results are obtained when a hot aqueoussolution of the hydrochloride is employed. The crystalline productdissolves freely in dilute alkalis, but is sparingly soluble in the usualsolvents.IV. The products of the action of benzoquinorie on the par-amidocresols are phenols. The orthamido-derivative of orthocresolyields a red crystalline base, meltiug a t 284", insoluble in alcohol.The hydrochloride, platinochloride, and the acetic derivatives of thebase are crystalline.It is a phenol, not a base.V. Amidothymol is oxidised to thymoquinone by benzoquinoneORGANIC CHEMISTRY. 259VI. No bases are formed by the action of benzoyuinone on amiilo-&naphthol, or on its hydrochloride. w. c. w.Methylene-blue and Allied Dyes. By A.RERNTHSEB (Ber., 17,2854-2862) .-In a previous paper (Abstr., 1884, 1156), reasons weregiven for concluding that Lauth’s violet and methylene-blue have thefollowing constitutions; in confirmation of these the author now bringsfurther proof :-N--CgH3.NH2 N--C6H3. NMe,NH2C1/ 1 I NMe,Cl/ I I‘C6H3. s ‘ C,H3. SNMeBy the introduction of two amido-groups into methglthiodiphenyl-amine, C6Ha<- -> C6H4, diamidomethylthiodiphenylamine,NH2.C,H,<Tfe> C6Hi.NH2, is produced, but owing to the presencc:of the methyl-group this does not yield R dye corresponding withLauth’s violet. By the action of filming nitric acid on methylthio-diphenylamine, a dinitrosulphoxide, NMe( C6H3.N0,),S0, is obtainedcrystallising in small needles; it is insoluble in dilute alkalis.Diamidomethylthiodiphenylamine hydrochloride,obtained on reducing the last compound, forms colourless prismsalmost insoluble in hydrochloric acid, but readily soluble in water.By the action of ferric chloride on a solution in dilute hydrochloricacid, a very instable bluish-green compound is produced.Lauth’sviolet can be obtained, not only by introducing amido-groups intothiodiphenylamine, but also by heating paradiamidodiphenylaminewith sulphur, and oxidising the product with ferric chloride,NH(C6H4.NH2), + 2s = NH(C6H3.NH2),S + SHz, and further fromparanitraniline and sulphur.I f thiodiphenylamine be treated with weaker nitric acid than waspreviously employed (Zoc. cit.), a mononitro-derivative is produced,together with the dinitro-compound.This mon.onitrodiphenyZamineszdp hozide, C6H4< zt > C&.NO2, yields nmidothiodipheny lam iw,c6H,<~~>c6H3.NH,, on reduction ; the latter crystallises in whitesilky scales, somewhat soluble in hot water, readily in alcohol andether; it oxidises readily, but is much more stable than Lauth’swhite ; the hydrochloride, C12Hs(NH2)NS,HC1, forms small scalesreadily soluble in water, very sparingly in concentrated hydrochloricacid. Amidothiodiphenylamine is converted by ferric chloride into a.N-C,H, ~-violet-red dye, the constitutionof which, HN/ I 1 , should cop- ‘ GH,. Srespond with that of Lauth’s violet. This imidoth,iod~~hen?,liinide formssmall, rusty-brown, spear-shaped crystals, moderately soluble in alcohol,t 260 ABSTRACTS OF CHEMICAL PAPERS.but less so in ether : the hydrochloride, C12H8N2S,HCI, is very solublein water and in alcohol ; the zinc double salt, 2C12H8N2S,HC1 + ZnCl,,is readily soluble.The salts of imidothiodiphenylimide dye silkviolet-red with a shade of brown. Amidothiodiphenylamine may alsobe obtained by heating paramidodiphenyla,mine with sulphur, hydrogensulphide being abundantly evolved.T h e n hydroxydiphenylamine is melted with sulphur, kydrozyfhio-cliphenylamz'ne, CsH4<i>C6H3.0H,. is produced. On extracting theproduct with dilute hydrochloric acid, dissolving the residue inaqueous alcohol and a little hydrochloric acid, and adding ferricchloride, a brown precipitate of oa?lthiod~henyZr~z~de, C,,H,NSO, isobtained.This substance dissolves very sparingly in the ordinarysolvents, more readily in toluene and cumene, and very readily inaniline. It has neither basic nor acid properties. H@roxythio-diphenylamine is re-formed on oxidising oxgthiodiphenylimlde. It hasno basic properties, but its ready solubility in alkalis indicates itsphenolic character. A. K. 31.Chrysaniline. By 0. FISCHER and G. K~RNER (Annalen, 226,175--191).-Nearly all the contents of this paper have been pre-viously published (Abstr., 1884, 748). C h r y s a n i h e , C9H,,N, +2H20, crystallises in long golden-yellow needles, or in yellowish-brown, flat,, spear-shaped crystals. When heated, it sinters togetherwith loss of its water of crystallisation at about 150", and melts a t267-270".A solution of chrys-aniline in hot benzene yields, after a time, golden-yellow plates of a,compound of the formula C19H15N3,C6-t16.Action of Phenyl Isocyanate on Amido-compounds. By B.KUHN (Ber., 17,2880-2885).-Amides of monobasic acids react withphenyl isocyanate according to the general equation NPh : CO +RCO.NH, = NPhH.CO.NH.COR.To prepare phenyZbenzoyIcur6umide7 NHPh.CO.NHBz, dry benzamideis heated with phenyl isocyanate a t 150°, until the odour of carbanilhas disappeared. The product forms long silky needles, melting at199" ; it dissolves readily in alcohol, sparingly in ether, and is inso-luble in water. When it is heated, it breaks up into phenyl cyanate andbenzamide. Pheizy lpropion y Zcarbarnide, NHPh. CO .NH.C,H,O, preparedfrom propionamide and phenyl isocyanate, crystallises in concentricallygrouped prisms, melts a t 137", dissolves sparingly in boiling water,readily in alcohol and ether, and is decomposed by heat into itsconstituents. Pheny Zacetylcctrbamide, NHPh.CO.NHZ, melts a t 183"(see also this Journal, 18 76, i, 400). D2iuhe77 yZacetylcarbu~?z~de,NHPh.CO.NPhZ (loc. cit.), may be obtained from acetanilide andphenyl isocyanate, whilst analogous compounds are also formed fromforrnanilide, benzanilide, acetonaphthalide, and benzonaphthnlide withphenyl isocyanate. The aromatic amido-acids also react with phenylisocyanate, although less readily than the acid amides. Phenylurumido-benzoic m i d , NHPh.C0.NH.C6H4.COOH, is prepared by heatingtogether metamidobenzoic acid and phenyl isocyanate for 1-2 hoursIt is sparingly soluble in alcohol.A.J. GORGANIC CHEMISTRY. 261at 100"; it is soluble in alkalis and in alcohol, sparingly also inether, but is insoluble in water; it crysta.ilises in concentricallygrouped prisms, melting with decomposition a t 270", but does not yielda, condensation-product like the corresponding uramidobenzoic acid.The fatty amido-acids react somewhat differently with phenjlisocyanate. a- Amid op ropionic acid yields di phenylcar bami de, and ap-parently also p h enylme thy1 h y dan toin : --NP h C 0 + NH,. CHMs. C: 0 0 H= KPhH.CO.NH.CHhfe.CO0H ; NPhH.CO.NH.CHMe.COOH +/NP h. C 02NPhCO = CO' + CO(NHPh), + CO,. The phenjl-\NH-b*Memethylhydantoin has not been isolated, but after boiling the productwith alcoholic potash, y 72 eny Zmet l ~ y Zhy darztoic acid,NHPh.CO.NH.CBMe.CO OH,was obtained ; this is insoluble in cold, readily soluble in hot water,also in alkalis, alcohol, and ether; it melts a t 170" with decornpo-sition.Phenylhydrazirie reacts with phenyl isocyanate with considerabkdevelopment of heat.NHP1i.CO.NH.NHPh ;it crystallises from dilute alcohol in stellate-groups of needles, issparingly soluble in hot water, readily in alcohol, and insoluble i i iether; it melts a t 1'70". Naphthylhydrazines yield similar compounds.Paraxylyl Phenyl Ketone. By R. ELM and E. LARSEN (Bey., 17,2847-2849) .-By the action of aluminium chloride (50 grams) on amixture of paraxylene (36 grams), benzoic chloride (47 grams), andcarbon bisulphide (80 -100 grams), paraxylyl phenyl ketone,C6H3Me2.COPh,is obtained.It melts a t 36", boils at, 3033 (uncorr.), and distilsextremely slowly in sheani ; it is insoluble in water, sparingly solublein glacial acetic acid, but very readily in alcohol, ether, acetone,chloroform, light petroleum, and benzene, and crjstallises from alco-hol in large well-formed prisms. I t s solution in glacial acetic acid isnot attacked by chromic acid even on boiling. Paraxylyl phenjlketone may be oxidised, however, by dissolving it in cold concen-trated sulphuric acid, adding chromic mixture and boiling ; the chiefproduct of the oxidation is benzoylparato Zuic acid. When the ketoneis boiled for several days in a reflux apparatus, methjlanthraceneis formed, with separation of water: C6H3Me2.COPh - H,O =C,H,Sle' 1 >c6fl.The product is cEipheny Zsemicarbuzzide,A.K. M.CH'CH A. K. M.Disulphones. By R. OTTO and H. DAMKOHLER (J. pr. Chem. [2],30, 171--208).-BthyZsue diphenylsulphone, C2H4(S0,Ph),, is obtainedby a method similar to that employed by Otto in the preparation ofthe disulphoxides (hbstr., 1882, 831), namely, by heating a solutionof sodium henzenesulphinate with ethylene dibromide and alcohol fo2 62 ABSTRACTS OF CHEMICAL PAPERS.some time in a reflux apparatns. The unaltered ethylene dibromide andalcohol are distilled off ; the disulphone separates from the residue oncooling, and is freed from sodium bromide and sodium benzenesulphi-nnte by washing with water.By crystallisation from alcohol, ethylenediphenylsulphone is obtained in long, colourless, odourless needles ; itis sparingly soluble in hot water, soluble in boiling alcohol andin benzene, very easily soluble in hot glacial acetic acid, and meltsa t 179.5-180'. Nascent hydrogen in presence of acids has no actionon ethylene diphenylsulphone, whereas in alkaline solutions (bysodium-amalgam and water), it is converted into sodium benzene-sulpliinate and ethyl alcohol, thus :-C,H4(W2P1i), + 2NaOH + H, = 2PhSOrKa + EtOH + H20.Chlorine acts on ethylene diphenysulphone, producing sulphurylchloride, benzenesulphonic chloride, ethylene dichloride, and chloro-benzenes ; the action of chlorine in direct sunlight is somewhatdifferent, the products being various chlorobenzenes and sulphurjlchlorides.Bromine does not attack the disulphone.Phenylsulyhoneth~y I aZcoho7, PhSO,.CH,.CH,.OH, is obtained byheating ethylene-diphenylsulphone with aqueous potash on a water-bath, and subsequent extraction of the liquid with ether. On eva-poration, the ethereal solution leaves this compound as a colourlesssyrupy liquid, which has a neutral reaction and an intensely bittertaste; it is miscible with alcohol and benzene, and but sparingly solublein water. Its formation is explained by the following equation :-C,H,(SO,Ph), + HOH = PhS02.CZHd.OH + PhS02K.This alcohol has also been prepared synthetically by heating anaqueous solution of sodium benzenesulphinate with ethylene chlor-liydrin in sealed tubes a t 120" ; its formation is represented by theequation-C,H,Cl.OH + PhS0,Na = PhSO?.C,H,.OH + NaC1.It is not acted on by nascent hydrogen in acid solutions, but nascenthydrogen in alkaline solutions converts it into ethyl alcohol andbenzenesulphinic acid or thiophenol.The following derivatives of this alcohol have been prepared by theordinary methods :-The acetafe, PhSO,.C,H,.O~c, is a s y ~ u p y colour-less liquid, having a bitter taste ; i t does not solidify at - 12", and ismiscible with alcohol, benzene, and ether.PhSO,. C,H4.0g,forms white, shining, silky needles melting a t 124-125"; it is in-soluble in water, but easily soluble in aIcohol and chloroform, lessemily soluble in ether.Plt en y lwlp ho.netliy 1 hydrogen su@ h ate, P h S 0,.C,H4. S 04H, is formedby mixing the aIcohol with mlphuric acid ; on diluting with water,phenylsnlphonethyl oxide separates out. The filtrate from this isneutralised with barium carbonate, and after removal of the bariumsul ph ate yields, on spontaneous evaporation, barium phenylsulphon-ethyl sulphate, (PhS0,.C2H4.S04),Ba + 3+H,O, which crystallises inneedles having a vitreous lustre. The salt is soluble in water, itsThe benzoateORGANIC CHERllSTRY. 263aqueous solution is decomposed by boiling, with formation of bariumsulphate, sulphuric acid, and the alcohol.PhenylsulphonethyZ chloride, PhS02.CzH4C1, is obtained by actingwith phosphorus pentachloride on phenylsulphonethyl alcohol ; alsoby acting with hydrochloric acid on the alcohol in sealed tubes a t150".It crystallises from hot benzene in iustrons six-sided tablets,is soluble in benzene and alcohol, but sparingly soluble in water, andmelts at 55 -56". I n all its properties, this compound resembles thealkyl chlorides ; when heated with sodium benzenesulphinate, i tyields ethylene-diphenylsulphone, and when acted on with sodiumEaratoluenesulphinate, eth=j-Iene-phenylparatolylsulphone,is obtained ; this crystallis'es in small, white, lustrous needles meltingat 162".Sodium-amalgam, in presence of alcohol, converts phenylsulphon,ethyl chloride into ethyl alcohol and sodium benzenesulphinate ; zincand hydrochloric acid do not, act on it.D ~ h e n ~ l l s z L ~ h o n e t l ~ y Z oxide, (PhS02.CZH4)20, is obtained by actingwith silver oxide on phenylsulphonethyl chloride : it is also producedby the action of dehydrating ageuts on phenylsulphonethyl alcohol.It is almost insoluble in water, slightly soluble in ether, and easilysoluble in benzene and alcohol, from which solutions it separates insmall, white, lustrous needles, or by slower evaporation in yellowishhard prisms melting at 69-70'.This compound is also formed irsmall quantities by the action of potassium hydroxide, and alsoof b a q ta, on ethylene diphenylsulphone.Replacement of two Chlorine-atoms in Chlorides byOxygen, by Means of Anhydrous Oxalic Acid. By R. ANSCH~TZ( A n n n l e n , 226, 13--22).-The anhydrides of mono- and bi-basic acidscan be prepared by heating the acids with the theoretical quantity ofanhydrous oxalic acid.The chlorides of aromat'ic aldehydes a r e converted into aldehydesby the action of anhydrous oxalic acid, for example, benzal chloride,Ph.CHCI2, yields benzaldehyde, P h .CHO, and chlorobenzal chloride,C6HiCl,CHCl?, yields chlorobenzaldehyde, C,H,CI.CHO.Benzotri-chloride, Ph.CC13, under similar treatment, yields a mixture of benzoicanhvdride and benzoic chloride, but if an excess of oxalic acid (3 mols.PhSO2 CzH4.S02C7H,,P. P. B.The method yields excellent results.1 - to 6) is used, the products consist of the pure anhydride. w. c. w.Derivatives of Orthonitrobenzoic Acid. By C. A. BISCHOFFand C. RACH (Bw., 17, 2i88--2800) .-Orthonitrobenzoic chloridewas prepared from t<he nitro-acid by Claisen and Shadwell's method,and purified by crystallisation from ether.During this process,small quantities of a substance forming colourless needles wereseveral times obtained. This substance proved to be orthonitrobenzoicrrnhydride. 'It is very sparingly soluble in water and ether, moresoluble in alcohol, and melts a t 135". It is re-coilverted into theacid by alkalis. By the action of orthonitrobenzoic chloride onethyl monosodomalonate, the authors obtained ethyl dinitrobenzoyl-matonate, (COOEt)&(CO.C,H,.NO),),. This compound crystallise2 64 ABSTRACTS OF CI-IEMICAL PAPERS.in plates melting at 93", and is the same substance previouslydescribed by Bischoff-who did not then obtain it pure-as ethylnitrobenzoylmalonate (Abstr., 1883, 912).The yield of this com-pound was small, half the quantity of sodomalonate used being recon-verted into ethyl malonate; small quantities of an oil were alsoformed, which exploded when heated above 179". When treatedwith sodium ethylate, ethyl dinitrobenzoylmalonate yields ethyl sodo-nitrobenzoylmalonate and ethyl orthonitrobenzoate, according to theequation-(COOEt),C(cO.C,H,.NO,), + NaOEt =(COOEt),CNa.CO.C,H,No~ + NO,.C,H,.COOEt.When an aqueous solution of this sodium-derivative is treated withhydrochloric acid, it yields ethyl inononitrobeiizoy lnzalonate~ which crys-tallises in colourless needles melting a t 54". I t s alcoholic solution gives$n intense bluish-red coloration with ferric chloride, and water thenprecipitates a bright red powder.Attempts to produce a substitutedethyl acetylenetetracarboxylate from this ether were unsuccessful.When treated with bromine-vapour, the sodium compound just de-scribed yields ethgZ mono?iit7obenzoyZbro711 oinalonate, which forms longprisms melting a t 72". When heated with excess of alcoholic ammo-nia in closed tubes a t loo", the dinitro-compound yields orthonitro-benzamide and ethyl malonate, together with a small quantity ofmalonamide. By the action of orthonitrobenzoic chloride on ethyldisodomalonate, the fiame dinitrobenzojl-derivative is obtained a swhen the monosodo-compound is employed. If, however, equalmolecular proportions of the chloride and of the ethyl disodomalonateare used, ethyl sodonitrobenzoylmalonat e described above is formed.When ethyl disodacetylenetetracarboxylate i n alcoholic solution istreated with orthonitjrobenzoic chloi-ide, ethyl orthonitrobenzoate m dethyl acetylenetetracnrboxylate are formed.I f t,he dry disodo-corn-pound is suspended in ether and then treated witth the chloride, ethyldicarbontetracarboxylate is formed, together with traces of a sub-stance crystallising in needles melting a t 150-158", of ethyl acetyl-enetetracarboxylate, and of a colourless oil volatile in a current ofsteam. When silver orthonitrobenzoate is added to acetic chloride,nitrobenzoic and acetic acids are formed. L. T. T.Paramethoxyphenoxycinnamic Acid. Ry A. VALENTIXI(Gazzetta, 14, 147--150).-Oglialoro, by the action of benzaldehydeand acetic anhydride on sodium pheny1glycollate, has obtained phen-oxycinnamic acid together with cinnamic acid (Abstr., 1881, 676).I n the present paper, the analogous reaction with anisaldehyde isstudied, and it is shown that there are obtained parcrmethoqj-cinnamic acid and pai,amethoz!jphenoxycinnariiic acid ; the former hasbeen prepared synthetically by Perkin by heating anisaldehyde withsodium acetate and acetic anhydride (Trans., 1877, i, 408).Thetwo acids may be separated from the crude crystalline product of thereaction by fractional crystallisation from aqueous alcohol, in whichthe paramethoxycinnamic acid is the less soluble. Paramethoxy-phenoxycinnsmic acid, C,H,( OMe) .CH : C(OPh).COOH, crystallises iOROhNlC CHEMISTRY. 265yellowish-white rectangular tablets, which melt a t 200" ; its methylsalt, obtained by saturating a warm mixture of the acid and methylalcohol with hydrogen chloride, crystallises in white, rectangularlamine melting a t 100".Thus the transformations of benzaldehydeand anisaldehyde are perfectly analogous.Derivatives of Salicylic Acid. By E. IIELLNIANN and R.GROTHMANN (Bey., 17, 2724--2i31).-~~oiiioiiitrosali~~l~c acid,C6H2Br(N0,)(OH).COOH [COOH : OH : Br : NO, = 1 : 2 : 3 : 51,may be obtained from nitramidosalicylic acid as follows : hydrobromicacid is added in four times the theoretical quantity to the nitramido-acid, the hydrobromide obtained dissolved in glacial acetic acid,nitrous anhydride passed through the solution, which is then warmeduntil no more nitrogen is giren off, the product diluted with waterand cautiously evaporated.It may also be obtained by the addition ofbromine to a solution of nitrosalicylic acid i n hot glacial acetic acid.Bromonitrosalicylic acid is readily soluble in hot, less so in coldwater, very readily in alcohol and ether ; it crystallises in needles orin nodules, and melts a t 222"; the bal-ium salt, (C,H,BrNO,),Ba +4Hz0, and caleiuin salt, \C,H,BrNO,),Ca + 6H20, are described.The hydrochloride of bromamidosnlicylic acid, obtained by the action oftin and hydrochloric acid on bromonitrosalicylic acid, forms colourlessneedles readily soluble in water and alcohol, almost insoluble inether ; neither the free acid nor the platinochloride could be prepared.A diazo-derivative may be obtained crystallising in yellowish-brownlustrous scales and yielding OH.C,H3Hr.COOH [COOH : OH : Br =1 : 2 : 31, on boiling with alcohol.This is sparingly soluble in cold,more readily in hot water and very readily in alcohol ; it crystallisesin needles melting at 1840, whilst the bromosslioylic acid obtainedby Hiibner and Heinzerling (Zeit. f. Chern., 1871, 309) from brom-amidobenzoic acid, [COOH : NH, : Br = 1 : 2 : 31, melts at219-230". The authors confirm the constitution of their acid byheating it with water a t 180", by which means it yields carbonicanhydride and orthobromophenol. The barium and calcium salts,(C7H4Br03),Ba + 3H20 and (C,H,BrO&Ca + 13H20, are described,and also t'he Zead salt, C7H3Br.O3Pb.OH.C,H,Br,.COOH [COOH : OH : Br = 1 : 2 : 3 : 51,may be obtained either by the action of hydrobromic acid on theabove-mentioned diazo-derivative, or better by the addition of bromineto a cold dilute solution of salicylic acid in glacial acetic acid.Itforms long colourless needles, melts a t 220°, is almost insoluble in coldand only sparingly soluble in boiling water. The barium salt has theformiila (C7H3Br203),Ba + 4H,O ; the Zead salt, C7H2Br,0,Pb, isinsoluble. When the monobromosalicylic acid (m p. 165") obtainedby brominating salicylic acid (see Hiibner and Heinzerling, Zoc. cit.)is nitrated, a bromonitrosalicylic acid, of the constitutionOH.C6H2Br(ONz).COOH [COOH : OH : NO, : Rr = 1 : 2 : 3 : 51is obtained. This melts a t 175", dissolves readily in hot, sparingly incold water, and crystallises in clusters of short yellowish needlescontaining 1 mol. H20 ; the following salts have been prepared:V.H. V.D~ibromosalicyZic acid266 ABSTRACTS OF CHEMICAL PAPERS.(C,H,BrNO,),Ba ; ( C7H3BrN05j2Ca + eH,O ; (C7H,BrN0,),Pb ;C7H2BrN05Ra + 2H,O ; C7H,BrN06Pb.CeH,Br2(N02).0H [OH : Br : NO, : Br = 1 : 2 : 4 : 61,is obtained as a secondary product in the preparation of the firstdescribed bromonitrosalicylic acid. It is sparingly solnble in water,more readily in alcohol, and crystallises in slender needles meltingat 142" ; the hu~ium derivative, (C6H2BraNO9),Ba + 10H20, formsgreen needles. Dibrornumido~72e.1zoZ, C,H,Br,(NH,) .OH, obtained bythe reduction of the nitro-compound, forms reddish-coloured needlesmelting at 1!10"; it is sparingly soluble in cold, more readily i n hotwater, and still more so in alcohol.It 'does not yield salts.Ethyleneamidobenzoic Acids. By H. SCEIFF and C. PARENTID~bromon.itl.o~herLol,A. K. M.(Annalen, 2 26, 243-248 ).--E'tlzylenediben zurnic acid,is prepared by boiling ethylene bromide with a saturated alcoholicsolution of metamidobenzoic acid for one day in a reflux apparatus. Itforms a crystalline powder, melts a t 222-225", is very sparinglysoluble in water, readily soluble in boiling alcohol or in cold alkalis,and is also soluble in moderately concentrated hydrochloric acid.A neutral solution of the ammonium salt gives with cupric acetate agreenis h-blue pnlverulent precipitate of the cwpric salt, C,sH,4N204Cu + H,O, and with nickel chloride a pale green precipitate of the nickelsalt.DiethyZ efI~yZensdietliyld.iben~amate, C,H,(NEt.C,H,.COOEt),,prepared by heating ethylenedibenzamic acid with ethyl iodide andalcoholic potash, crystallises in colourIess needles or prisms, melts at98-100", and is insoluble in water.I n the preparation of ethylenedibenzamic acid there is formed a t thesame time another acid distinguished by its more sparing solubility inall solvents. It forms a yellow powder, does not melt when heatedat300", and is probably a more condensed ethyleneamidobenzoic acid.By the action of ethylene bromide on amidobenzamide a t least twoamides of ethyleneamidobenzoic acid are formed ; beyond a statementas to their ready b u t unequal solubility in alcohol and in glacial aceticacid, no account is given of their properties.Ditolylphthalide.By P. D E BERCHEM (BUZZ. XOC. Chim., 42,lSS-169).-100 grams of phthalyl chloride are heated at 100" with450 grams of toluene, and 40 grams of aluminium chloride is addedgradually. When the theoretical amount of hydrogen chloride hasbeen given off, the reaction is stopped and the product thrown intowater. The toluene containing the phthalide in solution is separatedfrom the water, the toluene distilled off, the residue dissolved inalcohol, and purified by filtration through animal charcoal. Di-tolylphthalide, CfiH,<C(C6H'A'e)~> ---co--- 0, thus obtained forms prismswhich seem t o be monoclinic, with an angle of 63.15".These crystalsmelt at 116", and are soluble in alcohol, ether, benzene, and toluene,but insoluble in water or aqueous potash. The yield is only 4-5 percent., but six isomerides can exist, and possibly only one of them is acrptallisable compound. C. H. B.C2H4 (NH. CGH,. COOH) 2,A. J. GORGAKIC CHENISTRY. 267Diphthalyl. By C. GRAEBE and P. GUYE (Bw., 17, 2851-2852).-When a mixture of phthalic anhydride and phthalide is boiled for6-7 hours, water is set free and diphthalyl produced : C6H,<C0>0-+ C,H4<$F>0 = CO<,g4>C: C<,$&>CO + H20. The pro-duct is extracted with alcohol or chloroform, when nearly purediphthalyl remains behind. The reaction takes place more readilywith thiophthalic acid in the place of phthalic anhydride.coA.K. M.Phthalyl-derivatives. Parts T I and 111. By W. ROSER (Ber.,17, 2770-2775 and 2775--2778).-When preparing ethinediphthalylaccording to Gabriel's instructions, by heating together phthalic anhy-dride, succinic acid, and sodium acetate, the author succeeded inisolating two other compounds. When the melt is digested with boil-ing water, a double lactone, CllH8O4, is extracted, and crystallises outon cooling. The residue is then boiled with alcohol, to get rid of abrown bye-product, and the pale yellow residue dissolved in boilingnitrobenzene. On cooling this solution, the yellow needles of ethine-diphthalyl crystallise out first, but after a little time are acc-om-panied by red needles of an isomeric compound, which the authornames isot.thinedi~hthaly1.This compound may be purified by crys-tallisation from aniline, Aniline dissolves both the yellow and redcompound, but deposits the red needles again on cooling, whereas theFellow comDound combines witb the aniline and remains in solution. i LThe double lactone, CO<-,-> C6H4 C < CH2. CH, > C 0, crystallises inneedles.properties.conrerted into P-benzoyl~ropionorth~ear~~~y lie acid,COOH.C,H,.CO.CH,.CH,.COOH.It melts a t 120" and is decomposed a t 240". It has no acidWhen boiled with wat,er, carbonates, or alkalis, it isThis acid crystallises in hexagonal prisms, which melt a t 137", andare very soluble in water. When heated on the water-bath for sometime, this acid is reconverted into the double lactone.The lactonedissolves in ammonia to a violet solution, which on the addition ofacids deposits a compound crystallising in needles and containingnitrogen ; this is probably phthalimidylscetic acid. The metallicsalts of the carboxylic acid are insoluble or sparingly soluble in water.The author explains the formation of the lactone by the followingequations :-CO C6H,<CO>O + C,H,(COOH), =On reduction with sodium amalgam in the cold, the dibasic acidyields phthaZido-P-pr~p;or~~~ ucz'd, CllHloOl, which crystallises in mica-C ~ O U S scales melting at 121". It is easilr soluble in boiling water2 68 ABSTRACTS OF CHEMICAL PAPERS.alcohol, and ether. The metallic salts are easily soluble in water.When t'his acid is boiled with excess of barium hydroxide, the solutionallowed to cool, the excess of barium removed by carbonic acid, andthe solution evaporated in a vacuum over sulphuric acid, the buriuwa,and from that the siZver salt of the bibasic acid,COOH.CsH4.C)H(OH).CH2.CH~.COOH,may be obtained.These salts are very unstable, and if the evapora-tion of the barium salt is carried out on the water-bath the phthalido-acid is reformed. This behavionr very closely resembles that of thealkali salts of diaterebic and diaterebilenic acids. Further reductionof the above acid yields phthalidobutyric-orthocarboxglic acid.Isoethinedipl~thaZyZ is insoluble in water and alcohol, easily solublein boiling nitrobenzene or aniline. It does not melt a t '280", and hasthe properties of a feeble acid. When boiled with alkalis, it formsviolet solutions which deposit violet salts, but these salts are decom-posed even by water..Neither acetic chloride nor anhydride norphenylhydrazinc have any action on this compound. From its beha-viour, the author believes that it must have the constitutionc H /cO.cH*cO )C6H4 or C,H,<~~>CH.CH<CC~>C6H*.PART 111.-When phthalic anhydride, pyrotartaric acid, and sodiumacetate are heated together at 240-250", yi-o~iibedi~htht-clyl, CI9HE,,O4,is formed. This compound is soluble in alcohol and nitrobenzene,crystallises in yellow needles, is still solid a t 280", and is analogous inproperties to ethinediphthnlyl. If, however, during the reaction thetemperature is allowed to rise to 290°, a considerable quantity ofphthalylisopropylidene, CO<Ffj>C C(Me)2, already described b7Gabriel, is formed.The author believes this compound to be pro-duced by the decomposition of a double lactone analogous in consti-tution to that described above. When boiled with alkalis, it yieldsb enzo y lisoprop y loi*t/zocarboxy 1 ic acid, C 0 0 H . C,H,. C 0. C €Me2. Bythe reduction of this acid with sodium a,malgam, phthalidoisopropyl,CO<-, ->CH.CHMe2, is formed, which is easily volatile in steam.L. T. T.4\C0.AH.C0C s KDecomposition of Sulphonic Acids. By C. FRIEDEL and J. 31.CRAFTS (RNZZ. Xoc. Ghim., 42, 66-69, and Amer. Chem. J,, 6, 182).-The authors, without questioning the priority of Armstrong andMiller's method for the regeneration of an aromatic hydrocarbon bythe decomposition of its sulphonic acid (Trans., 1884, 148), showthat they have applied it to the separation of naphthalene tetrahy-dride from naphthalene.The sulphonic acid of the latter is themore readily decomposed, and when the mixed acids are mixed withsulphuric acid, heated to 160°, and a current of steam passed in, thegreater part of the naphthalene distils over. The formation of oxida-tion products is t h u s completely avoided. The authors have appliedthis reaction to benzenesulphonic acid and its homologues, but havenot, as they hoped, been able to ext'end it to the purification oORGANIC CHEMISTRT. 269pentamethylbenzene, owing to difficulties in the preparation of thesulphonic acid.V. H. V.By BEYE R andKEGEL (Dingl. polyt. J., 254, 356).-On boiling potassium mono-nitrophenolparasulphonate, obtained from potassium phenolparauul-phonate, with dilute nitric acid until all evolution of gas ceases, ztyellow colouring matter is produced : OH.C6H3(N02).S03K + HNO,= OH.C6H2(NO2),.SO3K + H20. The same dye is obtained on boilingpotassium phenolparasulphonate with an excess of dilute nitric acidBy treating phenolort hosulphonic acid or potassium mononitrophenol-orthosulphoriate in a similar manner, an isomeric colouring matter isobtained, which gives the same shade when dyed, but dissolves morereadily in water. This dye is produced also by heating potassiumphenoldisulphonate with moderately dilute nitric acid. Diazoben-zeneparasulphonic acid being converted into phenolparasulphonic acidwhen boiled with water, yields the same dye as phenolparasulphonicacid, whilst diazobeneenedisulphonic acid gives the same dye as phenol-disulphonic acid.D. B.Action of Aluminium Chloride. By R. ANSCH~TZ and H.IMNENDORFF (Bey., 17, 2816-2817).-1t has been shown that alumi-nium chloride reacts with benzene and acetylene tetrabromide, withproduction of anthracene. The authors have repeated this reactionwith toluene, the three xylenes, and with ethylbenzene in the place ofbenzene. Toluene, acetylene tetrabromide, and aluminium chlorideyield a dimethylanthracene, but it is obtained in much smaller quantitythan anthracene is from benzene ; the xylenes also yield methylatedanthracenes, but in extremely small quantity, whilst no homologue ofaiitlhracene could be obtained from ethylbenzene.I n all these re-actions homologues of benzene are also produced, the formation ofwhich appears to be independent of the acetylene tetrabromide. Bythe action of aluminium chloride on toluene, benzene and xylenes areobtained ; metaxylene when similarly treated yields benzene, toluene,niesitylene, and pseudocumene, whilst et hylbenzene yields benzene anddiethyl benzene. Dimethylanthracene is also formed in small quan-tity by the action of aluminium chloride on boiling tolnene.By T.ZINCKE and A. BREUER (Annalen, 226, 23--60).-The preparation ofthe hydrocarbon UIsH,, from styrolene alcohol, arid the preparation ofthe qninhydrone amd quinol derived from it, have been already de-scribed (Abstr., 1878,885, 889 ; 1879, 327 ; 1880,665 ; and 1882,207).Aqueous sulphurous acid, stannous chloride, o r hydriodic acid re-duce the quinone to 8 quinhydrone and a quinol.The latter crys-tallises in colourless needles or plates which melt a t 92". In presenceof moisture, it rapidly oxidises. The acetate, C,,H,,,O&, formsneedle-shaped crystals melting a t 152".The calcium and barium salts of the quinol, (C,,H,O,),Ba, formdark-coloured needles soluble in alcohol. The silver salt is a brownamorphous body insoluble in alcohol.Preparation of Dinitrophenolsulphonic Acid.thus : OH.CsH4.SO3K + 2HNO3 = OH.CsH,(NO,)?.SO,K + 2HZO.A. K. &I.The Hydrocarbon C,,H,, from Styrolene Alcohol2 70 ABSTRACTS OF CHEJIICAL PAPERS.On oxidation with potassium perruanganate, both the hydrocarbonand the quinone are converted into benzoic acid.The quinol uiidersimilar treatlment yields benzoic and phthalic acids, but if the oxida-tion is conducted in an alkaline solution, an acid of the compositionC,H,O, is obtained instead of phthalic acid.The constitution of the hydrocarbon may be represented by theformula PhC,H,Ph ; the constitutions of the quinone and the quinoIJapanese Camphor Oil. By H. OISHI (Chew. News, 50, 275-277).-When the woody parts of the Laurzis camphora, growing on thesouthern coasts of the islands of Shikoku and Kiushiu, are distilledwith water, the distillate contains solid camphor and an oil. Thequantities obtained vary with the season; more of the former andless of the latter are obtained in winter than in summer, and vicevers6.The crude oil when redistilled yields from 20 to 26 per cent,of camphor. The rectified oil is a colourless liquid, and burns withsmoky flame; its sp. gr. a t 15" is 0.895 (crude oil, sp, gr. = 0.9513) ;rotatory power by Soleil saccharimeter = tjS.96O. Treated with hydro-gen chloride, it separates into two layers: the upper one transparent,the lower turbid. Nitric acid in the cold produces a similar effect,the upper layer being yeliow, the lower colourless. When heated, theoil becomes red and oxidises, producing camphor and other oxidiseclproducts. Sulphuric acid dehydrates it, leaving a liquid with anodour resembling that of terpene ; large quantities of this acid charthe oil.Chlorine is absorbed by the oil with elevation of tempera-ture and evolution of hydrogen chloride, the liquid becoming yellowand viscid. Bromine behaves in a similar manner, producing an amor-phous red substance. Heated with iodine, which dissolves yeadily init, the oil becomes red, and on cooling below 0" semi-solid. Thesereactions, coupled with analytical and physical data, lead the authortr, conclude that the oil is ft mixtiire of terpenes, camphors, and someother oxidised hydrocarbons. The oil dissolves many resins, asphalt,sulphur, &c., and has been successfully applied as a solvent f o rYarnishes. I). A. L.Bromonitro-camphor. By P. CAZ ENEWE (BUZZ. XOC. Chim.. 42,69-70) .-The author has shown that dextrorotatory monochloro-caniphor, C,oH15C10, yields a laevorotatory mononitro-derivative,CloH,,(NO,)C1O ; he now ascertains whether a similar, thoughinverse phenomenon, occurs on nitrification of monobromo-camphoi..The substance, C,,H,,(NOf)BrO, prepared according to the methodindicated by Schiff (Abstr., 1882, 526), crgstallises in large prismsmelting at 103".For a 1 per cent. solution (temperature not given)the author found [a$ = - 27"; the nitrobromo- and nitrochloro-camphor (so-called %-derivative) thus belong to the same series.The so-called Oxycamphor of Kachler and Spitzer. ByH. Gor,DscHMiDT (Ber., 17,2717-2718).--In reply to the above-namedchemists, as to the identity of the " oxycamphor " with campholenicacid (this vol., p.17S), the aixt'hor points out a difference of 10" in theboiling points and the strongly acid character of the latter substance-have not yet been definitely ascertained. w. c. w.V. H. VORQAXIC CHE3lISTRY. 271The existence of camphoroxirne (Bey., 16, 494) is against Kachlerand Spitzer's formula, whilst the formation of an amide by the actionof heat on the amnionium salt, indicates the presence of a carboxyl-group in campholenic acid.Convallaria Majalis (Lily of the Valley). By A. LANGLEBERL'(Jour. Pharm. [ 51, 10, 26-N).-T wo glucosides, convallamarin andconvallarin, occur in Cowualluria majrxlis. The author prepares con-vallanzrxrin by extsacting the whole plant with water, convallarin, notbeing soluble, is thus left behind.The extract is precipitated withlead acetate, and from this, by the action of a solution of tannin, atannate of conrallnmarin is formed. The tannate dissolved in alcoholis precipitated by milk of lime, and the filtrate when evaporatedgives the convallamarin as an amoyphous powder. This substance issoluble in water, concentrated sulphuric acid, alcohol, ordinary, andmethylic ether, chloroform, and amyl alcohol. Dissolved in mono-hydrated sulphiiric acid, its colour is yellow, then reddish-brown,becoming violet on contact with water and moist air. The abovemethod of treatment applied to an alcoholic extract of the whole plantgave a residue of convallarin, which differs from conrallamarin onlyin its insolubility in water. Under the influence of dilute acids, con-vallamarin is resolved into glucose and convallarnaretin, whilst con-vallarin gives glucose and convallare tin.Substances obtained from Turmeric.By C. L. JACKSON and A.E. MENKE (Arner. Chenz. J., 66, 77-89) (compare Abstr., 1881, 611 ;1S82, 1107 ; 1883, 480) .-~loi~acetoc~rcumir?Y, C,,H,,ZO, is it viscousbrown mass ; the acetyl-gronp replaces hydrogen in the phenolichydroxyl. Diacetocu~cumin, CllH12Ac203, forms bright yellow cq-stals,melting a t 154" ; it is probably an anhydride of the formulawith alkalis a red colour is produced only slowly.Curcumin treated with phosphoric oxychloride yields a reddish-purple product, difficult of examination. Its reactions and analyseswould show it to be an acid anhydride.The action of hot potassium permanganate solution in excess onturmerol has been already studied (Abstr., 1883, 482) ; terephthalicacid is formed.Using cold solutions, the whole of the oil was oxidisedin about three days, some acetic and carbonic acids being formed ; thefiltered solution was acidified and extracted with ether, and the pro-duct distilled with steam. The distillate contains an acid, turmericacid, forming a crystalline calcium salt, Ca(C,IH,30,) + 3H20, whichis used for the isolation of the acid ; water dissolves 1-27 per cent. ofthe salt at 16". Free turmeric acid, Cl1HI4O2, is liberated by theaction of hydrochloric acid on the calcium salt, it forms oily dropswhich slowly crystallise. It melts a t 34-35", has a faint odour likethat of cocoa-nut, is sparingly soluble in water, freely in other ordinarysolvents.The silver, barium, and zinc salts were examined,From the non-volatile residue, containing tarry products, a whitecrystalline acid separated ; it was recrystallised from water. Apotur-meric acid, C10H120+ melts at 221", aud is easily soluble in hot water ;A. I(. If.J. T.C6H,(OMe) (O&).C,H,.COOZ 272 ABSTRACTS OF CHEMICAL PAPERS.it forms the salts CaCl,H,0,.2H,0 and Ba.CloH804.2H,0 (?), Theproducts of its oxid ation could not be determined, but terephthalicacid is not formed. H. B.Catalpic Acid. By SARDO (Gaznetta, 14, 134--139).-Decoctionsof the siliquaceous capsule of the Bignonirc catalpa, a member of theBignonia family, naturalised in Italy from America, me given in casesof asthma.By a prolonged extraction of these decoctions with ether,there is obtained an acid substance, together with a resin, which maybe separated by frequent treatment with alcohol. The acid substancethus purified forms large, white crystals, melting a t 2Otj0, and re-sembling resorcinol in appearance ; also very slightly soluble in water,but imparts to it a decided acid reaction : it is also soluble in alcoholand ether. Its barium salt forms white, glistening laminse, its silversalt is a, white precipitate, which rapidly turns brown, owing to somereducing action. The analpes of the acid and its barium and siIversalts point to the formula C14H1406 ; i t is proposed t o call the substancecatalpic acid. It may be isomeric with hgdrocardenic and akin toipecuanic acid, which differs from it by 1 mol.of water and 1 ofhydrogen, although both acids are bibasic.Decomposition of Pyridine Methiodides and Ethiodides bythe Action of Alkalis. By 0. DE CONTNCK (BUZZ. SOC. Chivb., 42,1 77--18O).-When the methiodides and ethiodides of t.he pyridinesderived from brucine and cinchonine are distilled with a slightlexcess of potassium hydroxide, in presence of a small quantity ofwater, decomposition takes place in three stages. I n the first theproducts are neutral compounds with tinctorial properties ; in thesecond, the products are pyridic, hydrides, whilst a t a high tempera-ture inflammable gases are given off.In order to obtaiii the colouring matters, the methiodide or ethiodide,washed with ether and dried a t a low temperature, is mixed withpotash in lumps, water is added until t'he mixture becomes fluid,and the liquid is distilled on a sand-bath over a Bunsen flame.Thedistillate is exhausted with ether, the ethereal solution evaporated,aiid the residue taken up with methyl or ethyl alcohol. The colonrof the products is intensified in a very marked manner by the additionof acids, especially acetic acid, whilst soda and potash change theeolour to a dirty red. Ammonia, as a rule, produces no effect.Sometimes the addition of acids intensifies or produces fluorescenceor modifies its character. These colourinq matters are perfectlyneutral. Those deriwd from brucine and cinchonine (in acetic acidsolutions) dye silk various shades from straw colonr to orange andlight brown.Those derived from the bases from coal-tar producethe same shades, but, as a rule, have less tinctorial power.Products of this kind were obtained from a-picoline, f3-lutidine,y-lutidine, a-collidine, and @-collidine. T bey give ethereal andalcoholic solutions of various shades of orange and red, with usuallya well-marked fluorescence, both the colour and the fluorescence beingfrequently altered on addition of acetic acid. No analyses of thesecompounds are given. When the ethereal solutions are allowed toV. H. VORQANIC CHEMISTRY. 273evaporate spontaneously with exposure to air, a black resinous solidsubstance is deposited, which gradually becomes less soluble in alcoholand ether. Probably the oxygen liberated during the distilIationwith potash plays the same part as the oxygen of the air.C.H. B,Constitution of Pyridine-derivatives from Brucine. By0. DE CONINCK (BUZZ. SOC. Chim., 42, 100--104).-In order to deter-mine the constitution of the two lutidines present in the crude quino-line from brucine, the author has submitted them to oxidation bypotassium permsnganate, added cupric acetate to the product, andsepamted the copper salts formed, by fractional crystallisation. Fromthe fraction melting between 155-170", there were obtained nicoticand pyridine-monocarboxylic acids, together with formic and aceticacids. The oxidation of the P-lutidine contained in the original sub-stance can be represented by the following equation :-C5H4EtN +0, = C,H,N.COOH + H.COOH + HzO.From the fraction meltingbetween 185-200", there were obtained on oxidation a methyl-pyridinecarboxylic acid and pyridinedicarboxylic or cinchomeronicacid, the former of which melts a t 211". The oxidation of the collidinecontained in the mixture can thus be represented as taking place in twosuccessive stages ; a t the first, the ethyl- and then the methyl-group isoxidised thus :-(1.) C,H,NMeEt + O5 = C,H,NMe.COOH + HCOOH + HzO, and (2.) C5H,NMe.COOH + 0 3 = HzO + C5H3N(COOH,,.It is proposed to carry on further researches regarding the constitu-tion of these acids. V. H. V.Constitution of Quinoline. By L. HNORR and 0. ANTRICK(Ber., 17, 2870-2880) .--This research was undertaken in the hopesof being able to decide between the older formula assigned to,CH.CHquinoline and that more recently suggested, namely, C6H/ I 11 .\N-CHKnorr's synthesis of quinoline from aniline and ethyl acetoacetate(Abstr., 1884, 1198) can be explained by either formula, thus :-I. NH2Ph + COMe.CH2.COOH - H20 = PhN CMe.CH2.COOH11. NH2Ph + COMe.CH2.COOH - H20 = NHPh.CMe : CH.COOHN- CMe= C,H,/ I 11 + HZO.'C(Ol3). CHIt is shown that at least the first stage of the synthesis takes placeas in equation 11, for when anilacetoacetic acid is dissolved inchloroform, and bromine added, two atoms of t'he latter are taken up,and on warming the solution, hydrobromic acid is evolved with form-ation of monobromanilucetoacetic acid (a-bromoyl2eiLyE-P-amidocrotonicacid), NHPh.CMe : CBr.COOH, which is converted by snlphuric acidVOL.XLVIII. 22 74 ABSTRACTS OF CHEMICAL PAPERS.N---CMe NH.CMe4"C0. CBrinto bromoxyquinaZdine, I, C6H/ 1 11 , or 11, C6H / 1) ;this crystallises in silky needles melting a t about 258", is insoluble inwater, soluble in alkalis and in acids, sparingly also in alcohol, ether,and chloroform. From its behaviour with nitrous acid, aceticanhydride, acetic chloride a t 130", methyl iodide at 180", boilingphenylhydrazine, and hydroxylamine in alkaline and acid solutions,rpoxyquinaldine appears to contain neither an imido- nor a carbonyl-group, and therefore to have the constitntion indicated by formula I ;its resemblance to carbostyril, solubility in alkalis, its quantitativeconversion (by fusion with phosphorus pentachloride) into mono-chloroquinaldine, and the production of quinaldine by distilling i t withzinc-dust, likewise indicate the presence of a hydroxyl-group.When,however, y-oxyquinoline is boiled with an excess of methyl iodide andan equivalent of sodium methylate in methyl alcohol, 1' : 2' dimethyl-pSeudoquinoxyZ, C6H/ 11 , is obtained; this compound mayalso be prepared by heating ethyl acetoacetate with aniline at 150",and digesting the product with concentrated sulphuric acid ; thesolution is then poured upon ice and supersaturated with alkali. I tcrystallises in slender needles melting a t 132", is readily soluble inalcohol, chloroform, and in acids, soluble in ether and water, butinsoluble in alkalis ; the platinochloride, ( CllH,,NO) z,H2Pt CIS, formsslender needles melting a t 215".Dimethylpseudoquinoxyl remainsunaltered when heated with 20 per cent. hydrochloric acid at 180-200" ; with bromine-water, it yields a bromine-derivative crys tallisingin white needles. It bears a strong resemblance to Hantzsch's methyl-pseudolutidostyril (Abstr., 1884,1043), and to Lieben and Haitinger'smethylhydroxypyridine (Abstr., I 884, 1196).2' : 3' Methy Ichloroquinoline, CIoH8NCl, prepared by heating y-oxy-qiiinaldine with phosphorus pentachloride and a little oxychloride a t135-140°, crystallises in slender needles, is almost insoluble in water,readily soluble in alcohol, chloroform, and ether, melts a t 59" andboils a t about 290'.It dissolves readily in acids, and yields a platiuo-chloride crystallising i n cubes. Its chlorine may be displaced byboiling chloroquirialdine with alcoholic potash.From the above, it is concluded that yoxyquinaldine is mostprobably 2' methylquinoxyl, [N : Me : 0 = 1' : 2' : 4'1, but furtherexperiments are being made with the view of deciding the qiiestion.A. K. M.Dimethylquinoline 11. By L. BEREND (Ber., 17, 2716-2717).A dimethy ZquinoZine may be obtained from ordinary metaxylidine[l : 3 : 41, in the same way as from orthoxylidine (Abstr., 1884,1197).It is a colourless, refracting, oily liquid, boiling at 268-269" (corr.) ;its sp. gr. a t 4" is 1.0665. The pZatinochZoride, (CllH,,N)z,HzPtC16,forms yellow needles sparingly soluble in hot water, the acid sulphate,CllH,,N ,H2SOa, is a white crystalline powder ; the dichromate crystal-lises from hot water in long needles. A sulphonic acid, Cl1H1,,N.SO3H,is obtained by the action of fuming sulphuric acid on the base at'C( 0 H) .C B rNMe. CMe'CO-CORGANIC CHEMISTRY. 275160-170"; it is very readily soluble in water and hot alcohol, andcrystallises in pale-yellow microscopic needles melting at 165-166'.The above described dimethylquinoline is perhaps identical with thebase obtained by Leeds by distilling acralxylidine (Abstr., 1883, 669).A. K. If.Diquinoline from Benzidine. By W. ROSER (Ber., 17, 2767-2769).-The author gives the following proofs of the non-identity ofthe diquinoline obtained by him from benzidine (Abstr., 1884, 1371)with the a-diquinoline of Weidel (Abstr., 1882, 69).The measure-ment of the crystals of the two compounds show decided differences ;the axial ratio, for instance, is 1.33 : 1 : 1.05 in the author's cornpound,but 1.37 : 1 : 1.32 in Weidel's. Roser's comp0un.d gives additivecompounds with 1 and with 2 mols. of methyl or ethyl iodide;Weidel's a-diquinoline gives a mono-additive product, but no di-additive product could be obtained even when a large excess of iodidewas employed. L. T. T.New Method for the Synthesis of Nitrogenous OrganicCompounds : Synthesis of Xanthine and Methyl-xanthine. ByA. GAUTIEB (Bull. SOC. Cl~irn., 42, 141--146).-A mixture of hydro-cyanic acid and water is heated in sealed tubes with a quantity ofacetic acid suficient to keep the liquid acid.The products have amaroon or reddish-brown colour, and can be separated by takingadvantage of the difference in their solubilities. One part of the con-tents of the tube is soluble in cold water, and consists of aldehydic acidswhich the author is investigating, and a yellow snbstance soluble inalcohol and oxidising in presence of air to a deep slaty-blue compound.If the alcoholic solution, made in the cold, is mixed with excessof hydrochloric acid and allowed to remain exposed to the air, itdeposits purple microscopic crystals with the lustre of cantharides.It appears to be a weak bibasic acid, and yields a potassium salt, thecolour of which is wine-red or rose, according to the proportion of alkali.That portion of the crude product which is insoluble in cold wateris exhausted repeatedly with boiling dilute acetic acid, and the pre-cipitate which separates from the solution on cooling, is washed,redissolved in hydrochloric acid, neutralised with ammonia, filtered,mixed with copper acetate, and heated to boiling.Copper xanthateand methyl xanthate are precipitated, and are then decomposed byhydrogen sulphide, the resulting magma boiled with dilute hydro-chloric acid, filtered, the filtrate neutralised with ammonia and con-centrated until t,he xanthine and methyl-xanthine crystallise out oncooling. The two substances can be partially separated by fractionalcrystallisation. The xanthine thus obtained gives all the reactions ofordinary xanthine, and forms salts which are identical with ordinaryxanthine compounds.The synthesis of xanthine and methyl-xanthinemay be represented by the equation llHCN + 4H20 = C,H,N,O, +C6&N,O, + 3NH3, but this does not take into account the compoundsdescribed above, or the aznlmin which is formed in large quantity.If the water is replaced by various alcohols, ketones, phenols, alde-hydes, &c., and the hrdrocyrtnic acid by carbylamines, an almostzL276 ABSTRACTS OF CHEMICAL PAPERS.infinite series of complex bases, acids, and indifferent bodies can beobtained.This synthesis of xanthine, together with results published in 1872and 1873, and recent investigations, not yet published, respecting therelation between xanthine and the alkaloids derived from animaltissues, indicate that xanthine has one of the following constitu-tions :-CO<NH- c(NH).C(NEA>~:~~ or HCO.N<~--- C(NH).C(NH) C=>CO,most probably the second.The constitution of sarcine will then be-C. H. B.Synthesis of Homoquinine. By 0. HESSE (Annulen, 226,240-242).-The author has shown (Abstr., 1884, 1385) that homoquinine,when treated with potash, yields quinine, and fancied that it was theonly product. Paul and Cownley, however, on repeating the experi-ment, found that besides quinine, another alkalo'id, cupreine, is formedin about equal amount; the author now confirms their statement.Cupreine crystallises from ether in concentrically grouped smallprisms, inelts at 191", dissokes without fluorescence in dilute snlph-uric acid (the solution gives a green colour with chlorine and ammonia,less intense than that given by quinine), and yields compounds withboth acids and bases.The normal sulphnte forms slender prismssparingly soluble in water ; the hydrochloride crystallises in smallneedles, the sodium salt forms satiny plates. Homoquinine can beprepared artificially by dissolving equal molecular proportions ofquinine and cupreine in excess of dilute sulphuric acid, precipitatingwith ammonia, and extracting the precipitate with ether ; homoqui-nine then crystallises from the ethereal solution. A. J. G.Brucine. By W. A. SHENSTONE (Bey., 17, 2740).-A question ofBy A. HANSSEN (Ber., 17, 2849--2850).--After obtain-ing nothing but oxalic acid by the action of potassium permanganateon brucine, the author tried boiling the latter with dilute chromicmixture. The product is poured into hot baryta-water, carbonicanhydride passed through the filtrate, which is then concentrated,the barium precipitated as sulphate, filtered, and the filtrate evapo-rated to a syrup ; on cooling a vitreous mass is obtained which is in-soluble in absolute alcohol, chloroform, and benzene.The product isan acid, C16H?ONz04, the platinochloride of which crystallises in magni-ficent golden-yellow scales containing 5 mols. H,O.By the action of phosphorus pentachloride on brucine, the authorhas also obtained a substance which yields a crystalline platinochlo-ride. He intends to continue the experiments. A. K. M.Crystalline Metahaemoglobin from the Dog. By G.H~FNERZeits. Physiol. Chem., 8, 366) .-Crystalline metahaemoglobin is a8priority.BrucineORGANIC CHEMISTRY. 277readily prepared from oxyhemoglobin from the dog, as from that fromthe pig. It closely resembles that from the latter source in all par-ticulars. A. J. G.Oxyhaemoglobin of the Horse. By G. H~~FXER and M. B~~CHELER(Beits. Ph,ysioZ. Ohm., 8, 358-365) .-The substance was prepared inthe usual manner from the separated corpuscles. The crystals ob-tained were usually large needles 2-3 mm. long and about 0.5 mm.thick ; on one occasion, however, well formed hexagonal tables wereobserved. T t contained about 3.94 per cent. of water. 100 C.C. of waterdissolved 2.614 grams at 1" and 14.375 grams at 20". Elementaryanalysis gave-0. H. N. 5. Fe. 0.54.40 7.2 17.61 0.65 0.47 19.67These numbers agree closely with those previously obtained byKossel (ibid., 2, 150) and Otto (PJEiiger's Archiv, 31, 240). Themean of the results of the three observers would correspond with theapproximate formula, C55,H,52N,4,S,Fe0149. On the assumption that1 mol. of hEmoglobin combines wit8h 1 mol. of carbonic oxide,1 gram of oxylmrnoglobin should absorb 1.41 C.C. (at 0" and 1 mm.pressure) of that gas. It was found that the amount of oxygen dis-placed by treatment with carbonic oxide was 1.31 c . ~ . (mean of fivedeterminations), and that the carbonic oxide compound on treat-ment with nitrogen gave up 1-39 C.C. of gas (mean of 14 determina-tions) per gram of oxyhEmoglobin. A. J. G.New Forms of Albumose. By W. K~HNE and R. CHITTENDEN(Amer. Chein. J., 6, lUl--120. Continued from Abstr., 1884, 1389 ;see also 849) .-The methods of purification of heterodbumose aredescribed ; it is well characterised by the appearances accompanyingits coagulation. When dissolved in dilute (0.1-0.2 per cent.) hydro-chloric acid the coagulum is in great part reconverted into hetero-albumose ; a portion of dpalbuniose is also formed. Heteroalbu-mose, unlike prot- and dys-albumose, is not precipitated by mercuricchloride ; when acetic acid is added to the mixture, a heavy precipi-tate is formed.Its mean composition is-C. H. N. S. 0.50-74 6.72 17.14 1-16 24-24Dysalbumose prepared from Witte's " pepton " gave on analysis-C. H. N. S. 0.50.88 6.89 17.08 1.23 23.92The specik rotary power could not be determined. The authorsregard dysalbumose as a form of heteroalbumose which has becomeinsolnble in neutral salt solution. Protalbumose and dysalbumosewere found in the precipitate formed by addition of alcohol to theurine from a case of osteomalacia.Its specific rotary power was [aID = -68.65"2 78 ABSTRACTS OF CHEMlCAL PAPERS,The authors consider that they have succeeded (1) in proving theexistence of a series of bodies intermediate between albumins andpeptones, the composition of which points to a gradual course ofhydrolytic decomposition, and that these forms of albumose are to beconsidered collectively as the first hydrates ; (2) in obtaining proofthat the different forms of albumose not only fall apart into the anti- andhemi-group, but that now the hemi-group by itself can he consideredas consisting of several members (namely, proto-, deu tero-, hetero-,and dys-albumose). " Insoluble '' hemialbumose consists of heteroalbu-mose, and " soluble " hemialbumose corresponds with both protalbu-mose and deuteroalburnose, or with a mixture of both these bodies.H. B.By. L.BRIEGER (Ber. 17,2741-2742) .-The internal organs of corpses whichhad been left for 24-48 hours in a cool cellar, were cut up, treatedwith water and enough dilute hydrochloric acid to give a faintly acidreaction, the whole heated nearly to boiling, filtered hot, and evapo-rated. The syrup obtained was repeatedly treated with alcohol,platinic chloride added to the alcoholic solution, the precipitate driedand extracted with water, when choline platinochloride was obtained.The amount of choline obtained from the organs of one corpse is verysmall, and no other basic substance appears to be formed during thefirst stages of the decomposition. By further putrefaction morepoisonous substances are formed ; in one experiment a substance wasobtained which resembles muscarine in its action on rabbits andBasic Products (Ptomaines) from Human Corpses.Guinc a pigs, and in the composition of its platinochloride.A. I(. M.Genesis of Ptomaines. By F. COPPOLA (Gazzettrc, 14, 124-130).-The author's recent researches on the genesis of ptomdines as pro-ducts of cadareric putrefaction, have tended to show on the one hand,that the arterial blood contains no such alkaloids, and on the other,that the processes, such as Dragendorff's, used for their extraction, arein themselves sufficient to produce them (Abstr., 1883,522,624). Theseresults have been confirmed by the experiments of Marino, who wasable to extract traces only of neurine and lecithine from various physio-logical products, and of Moss0 and Guareschi, who state that in theextraction of alkaloi'ds by sulphuric acid (Di~agendorffs process), thesubstances owe their formation for the most part to the decompoEingaction of the acid. Finally Mattei has demonstrated that death pro-duced by the injection of aqueous extracts of fresh organs, is not dueto a poisoning material within the organ, but to a purely infectiveprocess (Abstr., 1884, 199). As these views are in opposition to thoseof Selmi, Schwanert, and others, the author has made experimentswith blood, as a liquid which preserves its alkalinity in the process ofits putrescent decomposition, and thus can be extracted by varioussolvents, without resource to the use of free alkali for the purposes ofneutralisation. Blood taken from the carotid of a dog, and not defibrin-ated, was kept for two days a t 30" and afterwards allowed to putrefy a tthe ordinary temperature without direct contact with air. The residuewas then extracted with chloroform and benzene, and the extract testedwith the ordinary reagents for the alkalo'ids, but the results werPHYSIOLOGICAL CHEMISTRY. 2 79negative, even aftel. putrefaction bad lasted for two months. Theauthor calls particular attention to this fact, although he would notconclude therefrom that putrefaction is in no case sufficient of itselfto cause the formation of the alkaloids. V. H. V

ISSN:0368-1769    

DOI:10.1039/CA8854800232

出版商:RSC    

年代:1885

数据来源: RSC