ORGANIC CHEMISTRY. 210 r g a n i c C h e m i s t r y.Specific Gravities of Solid Organic Compounds. By H.SCHRODER (Ber., 12, 1611--1618).--The* author has determined thespecific gravity and molecular volumes of the following compounds :-Sp. gr.1.5591.281Malic acid . . . . . . . . . . . . . . . . . .Dimethyloxarnide .. .. .. ......Die thyloxamide . . . . . . . . . . . . . .Salicylic acid . . . . . . . . . . . . . . . .Metahydroxybenzoic acid. . . . . .Parahydroxybenzoic acid,. . . . .Phthalic anhydride . . . . . , . . . .1.4731-2471.2311.542 Protocatechuic acid1.7031.6851-3551.236Gallic acid . . . . . . . . . . . . . . . . . .Mandelic acid.. . . . . . . . . . . . . . . { 1.3671.385Methylparahydroxybenzoic acid 1.376 i' 1,364Phenylacetic acid .. . . . . . . . . . .1.2491.246 Cinnamic acidCumi * 'Benzoic anhydride, . . . . . . . . . . ,. . . . . . . . . .i 1.169. . . . . . . . . . . . , .Volume.85.990.5123.7122.892-993.193.793.594.556.956.7181.3183.2183.699.9-10O~c;99%100.9112.2111.2110.0111.5109.8110.5111.5118.6118.8140.3141.22 ABSTRACTS OF CHEMICAL PAPERS.sp. tT-1.296 { 1.2883 Orcinol . . . . . . . . . . . . . . . . . . . .Benzamide . . . . . . . . . . . . . . . . . . { ;:EAmidobenzoic acid . . . . . . . . . . { ;:;gOrthonitrobenzoic acid. . . . . . . .Metanitrobenzoic acid . . . . . . . . / ;:;;;1.216 { 1.205 Ace t anilide . . . . . . . . . . . . . . . . . .Benzanilide. . . . . . . . .. .. . . . ... . .1.2271.216 Aniline hydrochloride . . . , . . . .Thiocarbanilide . . . . . . . . . . . . . .Aniline nitrate . .. . . . . . . . . . . . .Aniline sulphate. . . . . . . . . . . . . .Naphthalene . . . . . . . . . . . . . . . .il": 1.201{ ;:;2Nitronaphthalene . . . . . . . . . . . . { ::;;;Ammonium benzoate. . . . . . . . . . { ?;;*1.3771.145a-Xaphthol . . . . . . . . . . . . . . . . . .&Naphthol. . . . . . . . ... . . . . . . . .1.2941.217Calcium benzoate . . , . . . . . . . . .Volume.109.7110.790.091.290-591.2106.0106.1111:6112.0111.0112.0149.2150.8171.5173-9105%106.5107.8114.8115.0206.311 1.9129.0131.0117.8118.2110.0110.3230.6234.1The molecular volumes of the majority of the above compounds aremultiples of 5.91, which in a former communication ( B e y ., 12, 566)was shown to be true for some benzene derivatives.I n the case of some isomerides, the " stere " appears to v a q a littlefrom 5.91, as shown by the following :-Volume. " Stere." __ .. .. .. . . .. .. .. . . 82.6-43.1 5-91 { Pyrocatechol Qainol .. .. .. .. .. 81.6-82.1 5.83* {4.{5. {Parahydroxgbenzoic acid 93.5-94.5 57153-5T Metahydroxybenzoic acid 93.7 -Orthohydroxybenzoic acid 93.9-93.1 5.8Orthonitrophenol.. .. .... 135.8-96.3 - G.0---?3%5Paranitrophenol . . . . . . . . 94.5-94.7Mandelic acid . , . . . . . . . . 111.2-112*2Anisic acid . . . , . . . . . . . . 109*8-110.5Isonaphthol . . . . . . . . . . . . 118.2a-Naphthol .. . . . . , . . . . . 11 7.85.915T1 's2*ORGANIC CHEMISTRY. 23The members of the following six groups are isosteric : (1.) Malicand tartaric acids. (2.) Benzoic and paraoxybenzoic acids. (3.) Re-sorcinol and pyrogallol. (4.) Phenylacetic and anisic acids. (5.)Protocatechuic and gallic acids. (6.) Benzamide and benzamic acids.In former communications, the author has shown that the element’scarbon, hydrogen, oxygen, and nitrogen occupy in the solid state thespace of one “ stere.”The determinations given above offer further support of this state-ment, thus : oxamide, dimethyloxnmide, and diethyloxarriide haverrloiecular volumes differing by CiH:, or 6 steres. I n naphthalene andisonaphthol we have difference of 0: = 1 stere, and in benzoic andorthonitrobenzoic acids we have the difference N:Oi - Hi = 2 steres.Some other examples are given.Prom this rule, i t follows that the benzene nucleus possesses onestere more than the sum of those of the elementary atoms containedin it. Thus : benzoic acid, C6H,.C00H = 16 x x1.Paranitro-phenol, C,H,.NO,O = 16 x 5.91, phthalic anhydride, C,HL03 = 16 x m. Orthonitroberizoic acid, C,H,.NO,.CO, = 18 X m. Phenyl-acetic acid = 19 x 5.8. lso-naphthol, C6H,.C4H,0 = 20 x 5- Cinnamic acid, C,H5.C,H2.COOH= 20 x 5-91. P. P. B.Naphthalene, C,H,.C,H, = 19 x m.-Formation of Hydrocyanic Acid in the Electric Arc. Bg J.DEWAR (Chem. News, 39, %3’L).-From the statements made by Plucker,ingstr6m, and Thalhn, that the so-called carbon lines are invariablyassociated with the formation of acetylene, the author made experi-ments with a view to extract this substance from the electric arc,which shows this spectrum a t the positive pole when the electric cnr-rent is powerful and occasionally intermittent. The carbons wereused in the form of tubes so that air could be drawn through them,and so that any gas might be passed up one tube and drawn downthe other and then examined.A Siemens and a De IRlkritens magneto-machine were employed.I n the first experiment a current of air was drawn down the nega-tive pole and passed through solutions of potash and potassiumiodide arid starch.No nitrates were indicated, but the potash solutioncontained sulphides.I n the second experiment in which hydrogen was led in by theposi-tive pole and withdrawn by the negative, acetylene was found by theammoniacal sub-chloride of copper-test, whilst water through which thegases were passed gave distinct evidence of hydrocyanic acid.Thehydrogen flame burning alone gave no evideiice of these substances.Air drawn through the negative pole gave considerable quantitiesof hydrocyanic acid, but when drawn through the positive pole alarger proportion was found, whilst the same carbons used with DeMhritens’ magneto-machine gave no result.I f the carbons are not purified, hydrogen sulphide is always foundalong with the other compound.The author concludes that the high temperature of the positive poleis required t o produce the hydrocjanic acid, which is in all probabilit24 ABSTRACTS O F CHEMICAL PAPERS.formed by the free nitrogen reacting on the acetylene thus : C,H, +2N = 2HCN, and that the hydrogen to form the acetylene is obtainedfrom the decomposition of aqueous vapour and from the combinedhydrogen in the carbons.Oxidation of Alcohols by Electrolysis.By A. RENARD (Ann.Chiw~. Phys. [ 51, 16, 289-33$).-I. Electrolysis of Alcohols in pwsenceof W a t e r A c i d d a t e d hj Sulphuric Acid. Methyl Alcolw1.-The purestmethyl alcohol of commerce, after being carefully freed from traces ofacetone and methyl ethers, was acidified with about 5 per cent. ofdilute sulphuric acid (1 : 4), placed in a flask holding from 100-200c.c., and submitted to the action of a current from 4 Bunsen cells ofabout a litre and a half capacity.Hydrogen was evolved at the nega-tive pole, and at the positive pole a gas was very slowly given off( a t the rate of 25-30 C.C. in 24 hours) : it contained CO,, 23.9 ; CO,SO.0; 0, 26.1. At the end of 48 hours the yellowish liquid was dis-tilled. The distillate was found to contain methyl formnte and methylaZ.Methyl aldehyde was never found as a product of the electrolysis,being no doubt oxidised to formic acid as soon as formed, or reactingwith the methyl alcohol to form methylal. The methylal is one of thechief products of the reaction, and may be prepared quite easily bythis method. The residue of the distillation of the electrolysed liquidcontained hydrogen methyl sulphnte. To show that this was pro-duced by the electrolysis, a mixture of the alcohol with dilute sul-phuric acid was prepared and divided into two parts, one beingallowed to rest, and the other submitted to electrolysis.The latterwas found to contain hydrogen methyl sulphate, whilst the former wasquite free from it.Ethyl AZcohol.-The electzolysis of ethyl alcohol has already beenattempted by various chemists, amongst others by tliche, D'Almeidaand Bontan, and Jaillard. The only products hitherto recognised,besides chloracetic acid and compound ammonias resulting from thehydrochloric and nitric acids employed for acidification, are aldehydeand acetic acid.The author's experiments were conducted in the same manner asthose with methyl alcohol. An abundant evolution of hydrogenoccurred at the negative pole; but a t the positive pole no gas wasdisengaged, all the oxygen being absorbed by the oxidation of thealcohol. The process was arrested at the end of 48 hours, and theliquid on being distilled yielded (besides alcohol) ethyZ fomzate, a littlealdehyde, and a large proportion of ethyl acetate ; small quantities ofm e t a l were likewise obtained, and a new substance which the authorconsiders to be ethylidewe monethylate, CH,.CH(HO).EtO, i.e., acetal,in which C2H5 is replaced by H. This substance when separated,and purified by fractional distillation, boiled a t 88-90" C., and onanalysis gave numbers corresponding with the formula C,H,,O,.Theresidue from the distillation of the electrolysed mixture containedhydrogen ethyl sulphate, the formation of which was proved, as in theprevious case, to be really due to the electrolysis.Under certain con-ditions, more than 60 per cent. of the sulphuric acid employed foracidification is transformed into the sulphate.W. TORGANIC CHEMISTRY. 25If the electrolysis of methyl or ethyl alcohol be continued for severaldays, a point is reached at which the liquid appears to containnothingbut formic or acet]ic acid; on still prolonging the operation, almostpure oxygen is disengaged a t the positive pole, in volume almostexactly half that of the hydrogen, and the liquid is found still tocontain a little hydrogen methyl or ethyl sulphate, the decompositionof which is very slow.Electrolysis of Hydrogen X r t l y Z XuIphate.-lOO C.C.of a solutioncontaining 20 grams of this ethereal salt, prepared by decomposingbarium methyl sulphate with sulphuric acid, was submitted to theaction of the current from 4 Bunsen cells. Hydrogen was disengageda t the negative pole, aiid oxygen containing 5 or 6 per cent. of theoxides of carbon a t the positive pole, about 23 volumes of oxygenbeing evolved for every 100 volumes hydrogen. After 48 hours theliquid was distilled, and the distillate was found to contain formicacid and a solid polymeride of methaldehyde, ti-ioxy methyleyhe, C3H603,which was obtained as a white, amorphous, insoluble residue byevaporation of the solution over sulphuric acid in a bell-jar. Similarrcsults were obtained by the electrolysis of a more dilute (5 per cent).)solution of hydrogen methyl sulphate, and also of a similar solutioncontaining a, little free sulphuric acid.From this, it would seem thatmethaldehyde is first produced, a part being a t once transformed intothe polymeric modification, whilst the other is oxidised to formic acid.No trioxymethylene is produced by electrolysis of methyl alcohol,because the methaldehyde as fast as it is formed, reacts on the methylalcohol to produce niethylal.Electrolysis of Hydmgen Ethyl Xu@hate.--This compound was sub-mitted to electrolysis in a manner similar to the corresponding methylcompound, and gave acetic acid and a little formic acid. No aldehydewas found in the distillate, but the odour of aldehyde was perceptibleduring the progress OE the electrolysis.Electrolysis of G7ycerol.-Glycerol diluted with two-thirds of itsvolume of water, acidulated with one-tenth of sulphuric acid, was sub-mitted to the action of the current from 5 Bunsen cells.Hydrogen wasdisengaged a t the negative pole, and at the positive pole a gaseous mix-ture containing CO,, 2.9 ; CO, 32.8 ; 0,64.3 volumes. After 48 hoursthe process mas arrested, the liquid saturated with calcium carbonate,filtered, and submitted t o distillation without boiling at a low pressurei n an atmosphere of carbonic anhydride. On spontaneous evaporationover sulphuric acid, the distillate left a white amorphous residue,which gave on analysis numbers agreeing with the formula CzH2xOx,and which proved to be identical with triozymethyZene, C,H,03. Theyield o€ this substance is very small, 130 C.C.of the distillate givingabout half a gram of the dry substance. Submitted to electrolysis,trioxymethylene gives rise to formic acid, and a gaseous mixture corl-baining, in 100 volumes, C02, 5 ; CO, 15 ; and 0 , W . By treating a solu-tion of trioxymetliylene with sulphuretted hydrogen, a white precipitateis obtained, of the formula, (C3H6S20)2H20. It differs therefore fromthe body C3H6S3, which Hoffmann obtained by acting on trioxy-methylene with a mixture of hydrochloric and hydrosulphuric acids.The oxysulphide obtained by the author melts at 80--82O, and solidifie26 ABSTRACTS OF CHEMICAL PAPERS.on cooling to a hard, white, opaque mass, like wax. It is soluble inhot water, insoluble in alcohol and ether, and boils a t 180-185" C.By treating the trioxymethylene with ammonia, the author obtainedthe hezamethyZenanzine of Butlerow, CsH12KT4, but was unable to obtainfrom it the hydrochloride C6Hl3NICI, described by that chemist.The residue from the distillation of the electrolysed glycerol containedcalcium format'e, acetate, and glycerate.Besides these substances thereis formed by electrolysis of glycerol a small quantity of a glucose isomericwith ordinary glucose, and which is probably a polymeride of trioxy-methylene. It is found in the alcohol used to precipitate the limesalts from the distillation residue of the electrol-ysed liquid. This alco-holic solution also contains the lime salt of a new acid, identical wit,hthat formed in the electrolysis of mnnnitol.The pure glucose isobtained in the form of a yellow-brown syrup, which may be dried a tGO" in a current of hydrogen. At 80-100" it blackens, loses water,and gives out, the odour of caramel. Its alcoholic solution yields aprecipitate with barium hydrate, the composition of which agrees withthe formuh (CsHI20,),( BaO),. The glucose reduces silver uitrate,with formation of a mirror, and precipitates cuprous oxide fromFehling's solution on heating. It is oxidised to oxalic acid when heatedwith dilute nitric acid. Slightly heated with soda its solution darkensstrongly. It is very soluble in water and alcohol, is not precipitatedby lead subacetate, but forms an abundant precipitate with ammoniacnllead acetate.It appears to be incapable of fermentation by beer yeast.When the electrolysid of glycerol is prolonged f o r several days, thetrioxymethylene and glucose disappear., the liquid becomes stronglycharged with oxalic acid, and this, as well as the formic and acdticacids, is finally resolved into carbonic anhydride and carbonic oxide,so that the solution a t last contains nothing but sulphuric acid.E'lectrolysis of Glycol.-Hydrogen was evolved at the negative pole,and a t the positive pole a gaseous mixture containing CO,, 5.00;C0, 57.15; 0, 37.85. The current was interrupted a t the end of36 hours. The liquid, saturated wiLh calcium carbonate and distilled,gave a distillate containing trioxymethylene, whilst the residue i n theretort contained calcium formate and calcium glycollate, some unalteredglycol, and a glucose identical with that obtained by the electrolysisof glycerol.3Lectrolysis of MunnitoZ.-Hydrogen was evolved a t the negative pole,and a t the positive pole a gaseous mixture contaiuing CO,, 22.1;CO, 55.0 ; 0,22*9.The liquid treated as in the glycol experiment, gavetrioxymethylene, calcium formate, and the calcium salt of a new acid.This calcium salt, when separated from fhe accompanying calciumformate, purified, and analysed, gave numbers corresporldixlg with theformula C6H6Ca08 + 2H20. It is very soluble in water, and itis not precipitated either by lime water, or by lead acetate or sub-acetate. It reduces silver nitrate almost instantaneously, withoutheating, and in the dark ; if the mixture be heated slightly a metallicmirror is obtained.At 120" C., the wlcium salt loses 6-7 per centl.cf water, and at 150" it swells up, and begins to decompose. Theacid, obtained from the calcium salt by decomposition with oxalic acid,is a syrupy product, forming very soluble, gummy salts, with bariunlORGANIC CHEMISTRY. 27lead, and magnesium. The author assigns the formula C6H808 tothis acid, and suggests that it may be an aldehyde of saccharic acid,C6HI0O8, bearing the same relation to the latter that glyoxylic (01- gly-oxalic) acid, C2H2O3, does $0 glycollic acid, CLH403. A glucose iden-tical with that obtained from glycerol, and probably also with themannitose of Gorup-Besanez, was also formed during the electrolysis,togetLer with a considerable quantity of oxalic acid, but no saccharicacid or msnnitic acid could be detected.Electrolysis of Glucose.-Hydrogen was evolved a t the negative pole,and at the positive pole EL gaseous mixture containing C 0 2 , 22 8 ;CO, 18.2 ; 0, 59.0.The electrolysed liquid contained trioxymethylene,formic acid, and saccharic acid.Electroh~sis of Alcohols when the Electrodes are sepamted by n PorousPartition.-In these experiments, the liquids to be electrolped werecontained in a porous cell, into which the positive electrode was intro-duced, the porous cell being surrounded with acidulated water, intowhich the negative electrode was plunged. The alcohols experimentedwith were methyl alcohol, ethyl alcohol, and glycerol.The productswere the same as in the experiment in wbich no porous partition wasemployed.Electrolysis of Acetic Acid.-25 C.C. of glacial acetic acid was mixedwith 40 C.C. of water, acidulated with one-tenth of sulphuvic acid, andsubmitted to the action of the ciirrent from 4 Bunsen cells. At theend of three hours the gaseous mixture evolved a t the positive polecontained CO,, 41 3 ; CO, 11.4; 0, 47.3. After 24 hours the gasevolved consisted of COz, 45.4 ; CO, 9.2 ; 0, 45.4. The proportion ofcarbonic anhydride was still greater a t the end of 36 hours. After48 hours the liquid was examined, and found to contain formic acid,but no oxalic acid.Electrolysis of Oxalic Acid.-The sole products in this case were car-bonic anhydride and carbonic oxide.The gaseous mixture evolved a tthe positive pole contained about 50 per cent. C 0 2 , and 10 per cent. CO,the rest being oxygen. At the ecd of 48 hours all the oxalic acid haddisappeared.Electrolysu of Forinic Acid.-The sole products were carbonic anhy-dride and carbonic oxide. If concenkrated formic acid is used, car-bonic anhydride is the only product.E’lectrol!isis of Alcohols in presence of Phosphoric Acid.-Experimentswere made with solutions of methyl alcohol, ethyl alcohol, glycerol,and glycol, acidulated with phosphoric instead of sulphuric acid. Alarger proportion of phosphoric acid than of sulphuric acid was foundnecessary, in order to secure the decomposition of the alcohols, but theproducts were exactly the same, and in about the same proportions aswhen sulphuric acid was used, except that in the case of methyl andethyl alcohols no hydrogen methyl or ethyl phosphate was formed.Action of Ozune o n the Alcohols.-The action of ozonised oxygen onthe alcohols is very slow ; for example, when a stream of this gas ispassed through solutions of glycerol, glucose, or mannitol, the escapinggas is still strongly odorous, and the liquid contains only very smallquantities of acetic or formic acid, even after many days’ action.Carbon dioxide and carbon monoxide are also formed.Contrary t28 ABSTRACTS OF CHEMICAL PAPERS.expectation, ozone was found to act much more quickly on the alcoholsof low atomicity, such as methyl and et,hyl alcohols, than on the poly-atomic alcohols, glycol, .glycerol, mannitol, and glucose.The action ofelectrolytic oxygen i s similar to that of ozone in this respect.Action qf Hydrogen Peroxide on t h e AZcoho1s.-Hydrogen peroxideappears to have no actioa on the alcohols, whether in acid, neutral, oralkaline solutions, dilute or concentrated, even after the lapse ofseveral days.The author concludes that the products obtained in the electrolyticexperiments above described are riot due to direct electrolysis of thealcohols, but are simply due to the action on the alcohols of the oxygen,resulting from the electrolysis of the acidnlated water. He suggestst,he electrolytic method as a convenient one for effecting the oxidationof organic bodies at a low temperature, and in a manner permitt'ingthe examination of intermediate products.J. M. H. M.Two New Hydrofluoboric Acids and Ethylene FluoboricAcid. By F. LANDOLPH (Bey., 12,1583-1586).-When boric fluorideact's on amylene, the latter is polymerised, and a fluoboric acid,Bo20iH43HYl, is obtained. It is a clear yellow liquid boiling a t 160",is easily decomposed by water, forming boric acid. A second fluoboricacid, Bo209H1(LHF1, is obtained when boric fluoride acts on anethol a thigh temperatures. It is a heavy, transparent liquid, boiling at 130".Like the above it fumes in contact with air, and is decomposed bywater.Ethylene fluoboric acid, C2H~HF1.Bo02, is formed by the action ofboric fluoride on ethylene at 25-30" in sunlight. It is a clear, mobile,fuming liquid (b.p. 124-125"), of sp. gr. 1.0478 at 23". It burnswith a green flame. Water decomposes this compound, forming boricacid, and a volatile compound (b. p. 10-15'), which does not burnwith a green flame, and is supposed to be ethyl fluoride.Sulphates of Mono- and Poly-hydric Alcohols and Carbo-hydrates. By P. CLAESSOX (Bey., 12, 1719--1721).-Mefhyl sulphateis best prepared by the decomposition a t 130-140" of hydrogenmethyl sulphate obtained by the action of' sulphuric monochlorideon methyl alcohol.P. P. B.Ethyl s u l p h f e is an oily liquid insoluble in water (b. p. 208").The polyhydric alcohols when treated with sulphuric monochlorideyield the corresponding hydrogen sulphates.Dextrose, dextrin, starch, and cellulose, form with sulphuric mono-chloride cZezt~-osechZorz'd e-tet ram@ honk acid, C4H5 ( S 0,OH) 4.C HC 1. C HO ,which cryst allises in large prisms. Corresponding compounds couldnot be obtained with levulose and galactose. w. c. w.Changes of Ammonium Isethionate at High Temperatures.By 3'. CARL (Bey., 12, 1604-1607) .-Ammonium isethionate heateda t 210-220" loses 12 per cent. of its weight, forming a body whichcrystallises from alcohol in leaflets, having a pearly lustre (m. p.196--198).-Seyberth (Bey., 7, 391) has observed the same change,but gives 190-193" as the melting point of the compound producedORGANIC CHEMISTRY. 29which he describes as an amide of the formula C,H7KSOs. Theauthor finds this compound has the formula C4H16S2N207, and explainsSeyberth's results by the suppositiori that his product contained smallquantities of another substance, which is formed simultaneously.Byboiling with baryta-water, this compound does not form barium ise-thionate as it. would if it mere an amide, but a barium salt is formedcrystallising in prismatic tables united to globular masses, having thecomposition C,U1,S2BaO7 + H,O. This salt differs from barium ise-thionate in its action on polarised light, as also i n its solubility i nalcohol. The author regards the new product as ammonium di-isethionate, NH,SO,.( CH,),.O. (CH,).,SO,NH.+Besides ammonium di-isethionate another bod7 is produced, which ismore soluble in alcohol, and has the composition C4H,,S,NO7. Itowes its existence to the evolution of ammonia observed whenammonium isethionate is heated.That it is not anacid salt is shownby the fact that when treated with alcoholic ammonia, and the solutionevaporated on the water-bath, the solution has still an acid reaction.For this reason the author attributes to this compound the formulaNH4SO,.(CH2),.S03.(CHz),.OH. P. P. B.By M. BEES LAUER ( J . pr. Chenz.[ S ] , 20, 188--193).--Von Richter (Ber., 10, 677) observed that drysodium acetate has no action on epichlorhydrin, but that in presenceof absolute alcohol, ethyl acetate and epihydrin alcohol (glycide) areformed. The author confirms von Gegerfelt's statement (BuZl. Xoc.Chim., 23, l60), that epihydrin acetate, C3H50Ac, is produced by theaction of potassium acetate on epichlorhydrin.The best mode ofpreparing this acetate is to heat equivalent proportions of epichlor-hydrin and potassium acetate in a flask provided with an uprightcondenser at 110-115° for several hours, and then raise the tem-perature slowly to 150". By extracting the product with ether,epihydriiz acetate (To. p. 164-168") is obtained, and also a liquid boilingatl 258-261 O , which Gegerfelt regarded as glycerol- triacetin, butwhich is really a polymeride of epihydrin acetate,Epihydrin acetate is a mobile liquid (sp. gr. 1,129 a t 20°), soluble inalcohol and ether. It precipitates metallic silver from an ammoniacnlsolution of silver nitrate. By the action of potash on epihydrin acetatediluted with ethyl acetate, glycerol is produced, but if soda is usedinstead of potash e p i l z y d h atcohol, C3H50.0H, is obtained.Thealcohol boils a t 160°, and is soluble in water, alcohol, and ether.When heated with water glycerol is formed.Diglycid, ( C,H,O.@H),, results from the saponification of the poly-Sugar from Populin. By E. 0. v. LIPPMANN (Bey., 12, 1648-1649). When the glucoside populin, CJ&208 + 2H20, is decom-posed by dilute acids, it splits up into benzoic acid, saliretin, ClaH,,O,,Partial Synthesis of Milk-sugar, and a Contribution to theSynthesis of Cane-sugar. By X. UEMOLE (Compt. rend., 89, 481).Epichlorhydrin-Derivatives.meric modification of epihydrin acetate. w. c. w.and grape sugar. w. c. w30 ABSTRACTS OF CHEMICAL PAPERS.-Schutzenberger (Ann. Chim. Phys., 21, 235), by the action of aceticanhydride on glucose, obtained an acetyl-derivative of a body formedby the union of 2 mols.of glucose with elimination of water, for whichthe author proposes the name of diylucose. Schutzcnberpr consideredthis body identical with octacetyl-saccharose. The solnhili ties cf thesetwo ethers in alcohol are, however, different ; and octacet~yl-saccharosehas a specific rotatory power [a],, = 38.36, whilst that of octacetyl-diglucose is [a]= = 54.62 ; moreover, the saccharose-derivative yieldssacchsrose by saponification, whereas the diglucose-compound yieldsdiglucose.When milk-sugar is heated with a dilute acid, it is converted byassimilation of water into galactose and lactoglucose. When themixture of these bodies, obtained in the-above manner, is dried andheated with acetic anhydride, it is converted into a pitch-like ether,having all the properties of octacteyl-lactose, and giving milk-sugar bytreatment with alkalis.When 2 mols. of glucose, like OF unlike, are in presence of a dehy-drating agent, they are converted into their anhydrides ; and by theaction of these anhydrides on acetic anhydride, an ether of a diglucoseis formed, just as ethylene oxide takes up acetic anhydride to form anReaction of Tungstates in presence of Mannitol. By KLRIN(Compt.Tend., 89, 484).-The action of tungstates on mannitolresembles that of borax. A solution of 12 grams mannitol and4 grams sodium tungstate, made up to 100 c.c., gives %deviation of + 40’. The solution has an alkaline reaction; boiling effects nochange.A solution of 10 grams of mannitol and 4 grams of sodium paratung-state, 5Na,0.12W0,.25H20, made LIP to 100 c.c,, has no rotatory powerin the cold,.but after boiling produces a deviation of + 36’.Thesolution, which is originally neutral, becomes strongly acid onboiling.Barium metatungstate, BaW40,5.9H,0, added to a solution ofmannitol, produces no deviation, even after boiling. The barium saltis not decomposed by the solution of mannitol, although it is by wateralone.If baryta-water be added t o the above solution when boiling, theliquid, after filtering, has a; rotatory power of + 25’; this effect is notether of diglycol. c. w. w.produced in the cold. c. w. w.Decomposition of Ethylamine Hydrochloride by Heat.ByM. FILETI and A. RICCINI (RPT., 12, 1508).-When this salt is beatedto a temperature somewhat lower than that a t which lead melts, amixture of ammonia and mono- and di-ethplamine (separated in neutralsolution by means of potassium nitrite), ethyl chloride and ethylene isevolved, whilst the residue consists of ammonium chloride, diethyl-amine hydrochloride, and some undecomposed ethylairline hydrochlo-ride. The reaction is thus analogous to the decomposition of phenyl-ethylamine by heat, except that a further decomposition into ammoniaanti ethyl chloride takes place. W. RORGANIC CHEMISTRY. 31Cyanethine. By E. v. METER (J. pr. Chem. [2], 19, 484-485).-Cyanethine appears to be a tertiary base. When heated with mode-rateIy dilute sulphuric or hydrochloric acid a t 180-200", it is trans-form€ d into a crystalline base, C9H14N20, which forms easily solubleand Enely crystallising salts.The investigation is being continued.A. J. C.A Double Function of the Monobasic Acids. By LOIR (Apm.Chirn. Phzp. [5], 18, 125-1 38).-In reference to Gerhardt's paper onthe anhydrides (illid. [3], 37, 333), the author considers that if theanhydrides are classed as ethers, that under certain circumstances theacids may act as alcohols, and if such be the case they must also havethe properties of aldehydes. This becomes evident on examination ofthe formula for acetic acid, which may be written thus : OH.CH,.COH.Considered as an alcohol it, is CJ&O(HO), the Ct,H,0 containing analdehyde grouping ClH2.COH.The fbllowing experiments are adducedin support of this vieF.By the action of reducing agents on aldehydes, atcohols are obtained,and when acids are treated with hydriodic acid, Berthelot has shownthat the hydrides of the alcohol radicles are formed.Bntyric acid (b. p. 155-160') when heated with a concentratedsolution of sodium hydrogen sulphite a t O", yields long transparentneedles ; these melt a t 20" without the evolution of sulphurous anhy-dride, whilst butyric acid floats on the top of the solution. On col-lecting the crystals, dissolving in water, and distilling with sulphuricacid, sulphnrc>us anhydride is evolved, and biityric acid distils over.R n tyric acid decolorises potassium permanganate, and reduces ammo-niated silver solutions.That acetic anhydride possesses the functions of an aldehyde as wellas an ether has been shown by the author (this Journal, Abst., 1879,621).Acetobenzoic anhydride, however, exists in two isomeric modifica-tions, according as it is prepared from sodium benzoate and aceticchloride, in which case the author calls it acetyb henzoic tcnhydride, orfrom sodium acetate, and benzoic chloride, when it is called benzoyl-acetic nrrhydr-ide.The two bodies have the same chemical properties,except in their reaction with hydrochloric acid.Beizzoy Z- acetic cilzhydride when heated in hydrochloric acid gas boils atISO", and acetic chloride comes over, leaving benzoicacid as a crystal-line rpsidue.AcetyZ-benzoic anhydride when treated in a similar manner boils at160', and benzoic chloride distils over.With chlorine similar results are obtained, the residue in the firstcase being chlorobenzoic acid, and in the second chzoracetic acid.These two isomeric bodies may be considered as ethereal salts;benzoyl acetic anhydride being the acetic salt of benzoic acid whichacts as an alcohol, whilst acetyl benzoic anhydride is the benzoic saltof acetic acid acting as an alcohol.Renzoic chloride at 0" forms a crystalline compound with sodinlnhydrogen sulphite.Since glyoxal and glyoxyli: acid are obtained from alcohol by theValeric acid has similar properties.The same holds good for butyric anhydride32 ABSTRACTS OF CHEMICAL PAPERS.action of nitric acid, they may be considered as derivatives of aldehydeand acetic acid.As glyoxal, COH.COH, contains the aldehyde-grouptwice, its mode of formation depends on the previous formation of analcohol aldehyde ; arid as me have acetic acid (alcohol), OH.CH,.COH,yielding glyoxylic acid, 0H.CO. COH, containing the acid and aldehydegroups, i t requires the same conditions.A table showing the relations of the derivatives of alcohol and aceticacids is given. L. T. 0's.Existence of Double Salts in Solution. By P. H. B. INGEF-HOES (Ber., 12, 1678--1684).--Bariurn formio?citrats, Ba.NO,.CHO, +2Hz0, is prepared by dissolving barium nitrate i n an almost satu-rated warm solution of barium formate. Crystals of barium nitrateare first deposited, and then the double salt separates out.Solutlionsof barium formio-nitrate and aceto-nitrate and calcium acetochloridewhen dialysed, diffuse like mixtures of simple salts ; this shows thatthese salts dissociate in dilute solutions. w. c. w.Oxidising Action of Cupric Oxide ; Transformation of AceticAcid into Glycollic Acid. By P. CASENEUVE (Compt. rend., 89,525).-It is known that formic acid is oxidised by cupric oxide tocarbonic acid, and similarly, if carbonic acid be regarded as the acidof methylene glycol, it might he expected that acetic acid, the homo-logue of formic acid, would be oxidised to glycollic acid.Cupric acetate was heated in a sealed tube with water a t 200" foran hour. The tube contained crystallised cuprous oxide, and a liquidwhich deposited crystals o i glycollate of copper.A small quantityof carbonic anhydride was also formed. The reaction is probablyexpressed by the equation, 2Cu(C2H302), + 2H,O = C2H403 +The carbonic anhydride is due to a secondary reaction by whichpropionic acid is also formed: 2Cu(CaH30,), + H,O = CO? 1-C,H,O, + CuzO + 2CzH402 : this reaction takes place to a very limitedand variable extent.CUZO + 3CzHi02.c. w. w.Action of Nitric Acid on Epichlorhydrin. By V. V. RICHTER( J . yr. Chem. [2], 20, 193-195) .-When epichlorhydrin is treatedwith 3 or 4 parts of warm nitric acid (sp. gr. 1.38) an energetic reac-tion takes place. On pouring the acid liquid into water and extractingwith ether, monochZoroZactic acid is obtsined. To r2move the chloro-nitrohydrin and oxalic acid with which it is mixed, it is dissolved inwater, again extracted with ether and converted into the calcium salt.The acid crystallises in flat prisms (m.p. 77"), which are deliquescentEthyl Nitracetate. By FORCRAND (J. pr. Chem. [el, 19, 487-488).-This is obtained by the action of silver nitrite on ethyl bromacetate.The product is distilled, and the portion which pawes over at 130"(with slight decomposition) is essentially ethyZ rzitranetate, a liquid ofsp. gr. 1.133 at 0' (b. p. 151-153"). By the action of zinc and hydro-and dissolve readily in alcohol, ether, and water. w. c. wORGANIC CHEMISTRY. 33chloric acid it was converted into amido-acetic hydrochloride, whencethe silver salt was obt(ained in iridescent crystals which blacken onexposure t o the light.Preparation of Nitrated Fatty Acids.By J. LBIWKOWITSCH (J. pr.Chem. [2], 20, 159-173).-Nitro-products could not be obtained bythe action of the strongest nitric acid (sp. gr. 1-53) o r of a mixture ofiiitric and sulphuric acids on caproic and stearic acids.EthyZ nityoacetate, CH,(NO,).COOEt, is formed by digesting ethyliodacetate with silver nitrite at 100' ; towards the end of the processthe mixture is heated up to 130". On treating the product with abso-lute ether, a pale-yellow liquid, insoluble in water, is obtained, whichboils between 150" and 160" with decomposition.E t h y l nitropropionate, prepared by the action of silver nitrite onethyl 6-iodopropionate (which is most readily obtained by heating analcoholic solution of 6-iodopropionic acid with a small quantity of sul-phuric acid), is a colourless mobile liquid (b.p. 161-165"). Theethyl salt dissolves in a dilute solution of potash ; by acidifying theliquid with sulphuric acid and extracting with ether, crystals of nitro-propionic acid were in one instanoe obtained, but the operation gene-i d l y yields a thick liquid which dries up to a hard glassy mass whenexposed over sulphuric acid.P-Nitropropionic acid is easily obtained by adding about 2 equivalentsof silver nitrite to 1 of P-iodopropionic acid dissolved in water. (Thebest results are gained bg working with not more than 5 grams ofiodopropionic acid for each operation.) The solution of silver nitro-propionate which is formed is decomposed by hydrochloric acid andextracted with ether.After evapora'ting the ethereal soltition, a thickliquid remains which solidifies forming a white deliquescent crystallinemass. By recrystallisation from chloroform, the nitro-acid is obtainedin pearly-white scales which melt a t G6" and decompose a t 160". Theacid is soluble in water, alcohol, and ether ; its salts are also soluble inwater, but undergo decomposition. By reduction with tin and hydro-chloric acid, /3-nitropropionic acid is converted into /3-alrcizine 1zydro-chloride. w. c . w.A. J. C.Derivatives of Thiacetic Acid. By S. GABRIEL (Ber., 12, 1639-1641).-Phe~z2/Zene-dithiacetic acid, C,H,(S.CH,.COOH),, is preparedby the action of chloracetic acid (2 mols.) on a warm alkaline solutionof thioresorcinol (1 mol.).On acidifying t'he mixture with hydro-chloric acid, the acid separat'es out as an oily liquid, which soonsolidifies to a crystalline mass. The crystals melt a t 127", forming aturbid liquid which becomes clear at 1.50".Toluene-dithiacetic acid, C6H,Me(S.CH,.COOH),, obtained by asimilar reaction, crystallises in needles (m. p. 151*5"), soluble in hotwater.PhenyZene-dioxyacetic acid, C,H4(0.CH2.COO€I)2, produced b, theaction of chloracetic acid on an alkaline solution of resorcinol, fornispale-yellow crystals (m. p- 193"). Dibro.lno~lL~n~le.1Le-dioxllacetic acid,separates out as a white powder when bromine vapour is passed intothe aqueous solution of this acid. It is deposited from a hot alcoholicVOL.YXXVIII. 34 ABSTRACTS OF CHEMICAL PAPERS.solution in white, silky needles (m. p. 250"). Benzyl-thiacetic acid,C6H,.CH,.S.CH2.COOH, crystallises in flat plates (m. p. 59"). Theantide, C6H3.CH2.S.CH2.CONH2, is obtained in rectangular plates(m. p. 97"), by the action of ammonia a t 100" on ethyl benzyl-thi-acetate (b. p. 275-290"). w. c. w.Lauric Acid and its Conversion into Undecylic Acid. By F.KRAFFT (Bey., 12, 1664-166€) .-Lauric acid is best prepared fromcommercial bay oil (01. Zaurin w~girinos). For this purpuse the oil issaponified by boiling with a solution of potash for several hours ; thepotash soap is decomposed by warm hydrochloric acid, and the mixtureof acids thus set free is distilled under greatly diminished pressure.The first portion of the distillate subjected to repeated redistillationunder diminished pressure yields pure lauric acid (m.p, 435", b.p.222-5" under 100 mm. pressure).The ketone, C,,H2,0, obtained by the dry distillation of a mixtureof barium laurate and acetate under diminished pressure, melts a t 28"and boils a t 263". On oxidation with chromic mixture this substanceyields acetic acid and an oily liquid consisting of a mixture of unde-cylic acid and unaltered ketone. The undecylic acid is converted intoits barium salt, which is treated with ether to remove the ketone.This acid crystallises in scales, which melt a t 28.5" and boil at 213'under 100 mm. pressure. w. c. w.Tridecylic, Pentadecoic, and Margaric Acids. By F. KRAFFT(Ber., 12, 1668-1 675) .-Myristic acid, prepared by the saponificationof Muscata butter and purified by distillation under diminished pres-sure, melts a t 53.5" and boils at 248" under 100 mm.pressure.The ketone, CI,Hl,O, obtained by the dry distillation under dimi-nished pressure of a mixture of barium acetate and myristate, meltsak 39", boils at 294", and on oxidation yields acetic and tridecoicacids.The latter acid, purified by redistillation and conversion into itsbarium salt, melts at 40.5" and boils a t 2Z6" under 100 mm. pressure.By a similar process pentndecoic acid, C15H3002, can be obtainedfrom palmitic acid (m.p. 62" and b. p. 268.5" under 100 mm. pressure).The ketone melts a t 48" and boils a t 320". Pentadecoic acid meltsat 51", and boils a t 257" under 100 mm.pressure.Mnrywic a,cid, prepared synthetically from stearic acid (b. p. 387"under 100 mm. pressure), is identical with the margaric acid obtainedby Heintz (Pogg. Ann., 102, 257) by the saponification of cetylcyanide. The acid melts a t 59.8" (uncorr.), and boils at 277" under100 mm. pressure.The discovery of tridecoic and pentadecoic acids makes the list offatty acids complete as far as stearic acid. w. c. w.Hydroxethylrnethylacetic Acid. By W. v. MILLER (Bey., 12,1544).-To show that Neubauer's angelic acid resulted from ethyl-methylacetic acid, which, together with isobutylformic acid, is a productof the oxidation of amyl alcohol obtained by fermentation, the autlioORGANIC CHEMISTRY. 35prepared ethylmethylacetic acid by Sauer's process, and oxidised itwith potassium permanganate.The product was 'a-hydroxethyl-methylacetic acid, CEtMe(OH).COOH (m. p. 68'). On didilling thisacid with sulphuric acid no methylcrotonic acid was formed.W. R.Hydraxisobutylformic Acid. By W. V. h'lraLEin (Ber, 12, 1542-1543).--From a careful comparison of the copper salts, the authorconcludes that the dimethacrylic acid, prepared by him by oxidising6-hydroxisobutylformic acid, CMe,( OH).CH,.COOH, is identicalwith an acid obtained by A. and M. Sajtzeff, by oxidising syntheti-cally prepared ally1 dimethyl carbinol. The P-hydroxisobutylformicacid, of which the formula is given above, is an intermediate productbetween isobutplformic acid and its ultimate product of oxidationwith potassium permanganate, viz., dimethacrylic acid.W. R.Synthesis of Ketonic Acids. By P. HOFFERTCHTER ( J . pr. Chem.[a], 2Q, 195--20O).-FrichZoru,cetic cyanide, prepared by the action ofsilver cyanide on trichloracetic bromide, is a colourless liquid (b. p.117-119"), soluble in ether. It refracts light powerfully, and has asp. gr. 1.559 a t 15". It is decomposed by water with formation ofhydrocyanic and trichloracetic acids. On exposure to moist air, adeliquescent white crystalline substance is formed. A solid poly-meride, which is produced in small quantities in the preparation of theliquid trichloracetic cyanide, crystallises in rhombic plates (m. p. 140"),soluble in alcohol and in ether. It is decomposed on boiling withwater.Trichloracety Zcarboxy Zic acid is formed when the liquid cyanide istreated with dilute hydrochloric acid (sp.gr. 1.16) a t 50". It isseparated from trichloracetic acid by recrystallisation of the sodiumsalts. Sodium trichloracetylcarboxy late cry stsllises in prisms contain-ing 2 mols. HzO, which are less soluble than the tabular crystals ofsodium trichloracetate. The acid forms small prisms (m. p. 89O),soluble in water. By the action of fuming hydrochloric acid on tri-chloracetic cyanide, a white cr,ystalline amide is produced, whichappears t o have the composition C,C1,05H8N2. w. c. w.Maleic Acid from Dichloracetic Acid. By S. TANATAR (Ber.,12, 1563-1566) .-Ethyl dichloracetate dissolved in alcohol is notacted on by molecular silver a t the boiling point of alcohol ; if, how-ever, ethyl dichloracetate is heated with molecular silver a t 210" insealed tubes, silver chloride is formed, and a small quantity of anethereal salt boiling about 210", which on saponification with baryta-water yields barium mnleate.Sodium acts energetically on dry ethyl dichloracetate ; if the reactionis modified by use of anhydrous ether, there is found amongst the pro-ducts of decomposition, an ethereal sait distilling between 100-120",which is more soluble in water than the ethyl dichloracetate; it issoluble in warm baryta-water.On standing, this solution decomposeswith formation of barium carbonate. The nature of this product isas yet unexplained. P. P. B.d 36 ABSTRACTS O F CHEMICAL PAPERS.Occurrence of Tricarballylic and Aconitic Acidk in Beet-Juice.By E. 0. VON. LIPPMANN (Ber., 12,1649-1651) .-Tricarbally-lic acid is not found in fresh beetroot, but the author confirms hisprevious observation (Ber., 11, 707, this Journal, 1878, Abst., 662) as tothe occurrence of 6he calcium salt of this acid in the vacuum pans ofthe beet-sugar manufactory. Aconitic acid, detected by Behr in thejuice of the sugar-cane (Ber., 10, 351, this Journai, 1877, 2, 182) isBy G. STEIN (Ber., 12,1603) .-According to Lucas and Trommsdorf (Annct7en, 8, 237) theacid contained in this plant is malic, whilst Reess and Will (Centyal-blirtt f . AgricuZticrchei~zie, 10, 230) suppose it t o contain formic, pro-pionic, and butjric acids, and finally Hager asserts that it containscitric and malic acids.The author has extracted some of this acid,and from the characters of its salts concludes that i t is citric acid.The acid has also been cjhtained crystallising in rhombic prisms, andthe analysis of its lead salt shows it to be citric acid.Derivatives of Triethyl citrate. B y J. CONEX ( B e y . , 12, 1653-1655).-T~-lethyZ citpate, C,H,OH( COOEt),, prepared by the action ofhydrochloric acid on a mixture of citric acid and alcohol, is a thickcolourless liquid, sp. gr. 1.1369 at 20° compared with water a t 4",b. p. 261" under 300 rnm. pressure.Tetrethyl c i t m f e , C,I-I,OEt(COOEt),, is formed when the product ofthe action of sodium on triethyI citrate (diluted with dry ether) isheated with ethyl iodide atl 100".This citrate is a pale-yellow oil,sp. gr: 1.1022 a t 20", boiling a t 290" with decomposition.A liquid having the composition C,H,(COOEt),, and of sp. gr.1.1064, is produced by hesting a mixture of phosphorons chloride andethyl citrate a t 100".also present in beet-j uice. w c. w.The Acid of Drosera Intermedia.P. P. 13.This substance decomposes on dist3illation. w. c. w.Action of Phosphorus PentachIoride and Hydriodic Acid onSaccharic Acid. By H. m LA MOTTE ( B e y . , 12, 1571--1573).-Theresults published by C. J. Bell (t.his Journal, Abst., 1879, 917) arethe same as those published by the author in his Dissertation (Halle,1878). The author also points out that chlorornucic acid obtainedfrom saccharic or mucic acid always crystallises with 2 mols.of waterof crystallisation, C6H4C1,O~2H,O.Saccharic acid when heated with hydriodic acid and amorphousphosphorus in sealed tubes a t 140-150", yields a small quantity of anacid, m. p. 148-149", the analysis of whkh, and its properties, as alsothose of its salts, show it to be adipic acid. P. P. B.Ccmstitution of Deoxalic Acid. By J. K L E r x (J. pr. Chem. [2],20, 146-159).-By acting on ethyl oxalato with sodium-amalgam,Liiwig, in 1861, obtained a substance of the formula C1lHlsOs, whichhe regarded as the triethyl salt of deoxalic acid, C5H,0e, and by heat-i n g this with dilute sulphuric acid, he converted it into ethyl racemate,with evohtion of carbonic anhydridc. Brunner, in 1870, contendeORGANlC CHEMISTRY.37that the original reduction-product of ethyl oxalate has the formulaClrH200g, and is the triethyl salt of an acid of the formula CeH60g,which, however, he could not isolate, owing to its decomposition intoracemic and glyoxylic acids. The author has confirmed Lowig's resultsin the following manner :-Et"nyl deoxalate prepared by the action ofsodium-amalgam on ethyl oxalate melts a t 85", and has all the pro-perties attributed to it by Lowig. The barium salt was prepared bytitrating the ethyl salt with standard baryta-water. Bot'h the titra-tion and the ai~alysis of the barium salt point to the correctness ofLowig's formula. The calcium salt has the formula ( C5H308)2Ca3.The free acid, prepared from the barium salt by means of sulphuricacid, forms very deliquescent crystals, and from several analysesappears to have the formula C,H,O,.HI,Q.Treated with acetic or with benzoic chloride, it farms monacetyl-and benzoyl-deoxalic acid, and with acetic anhydride, or with benzoicchloride, a t a higher temperature, a diacetyl or dibenzoyl acid.Itlappears therefore to contain two alcoholic hydroxyls. The amount ofcarbonic anhydride erolved on bailing the acid with dilute; sulphuricacid was estimated, and agreed with the equation C,H,O,.Et, =C,H,O,.Et, + CO,, ethyl racemat'e being formed a t the same time.The ethyl raceniate gave an acid agreeing with the ordinary racemicacid in all its properties.On heating deoxalic acid with hydriodic acid no reduction tookplace, but it was converted into racemic acid, and a t a still highertemperature, succinic acid .was produced.The tricarboxylic acid,of which debxalic acid is a hydroxylic derivatire, was not isolated inthis reaction. W. R.Synthesis of the Closed Benzene Ring. By V. v. RICHTER( J . p. Chena. [el, 19, 205--208.-In order to accomplish the synthesisof benzene by means of diethylene-diketone the author subjected thesuccinates of potassium, sodium, magnesium, calcium, and lead to drydistillation. The distillate contained quinol, and benzene was obtainedby the action of zinc dust on the distillate, but diethylene-diketane hasnot yet been isolated.Xo benzene derivatives were formed by distilling ethylene succinatewith zinc dust. w. c. w.Derivatives of Isodurene. By M.BBTECEFELDT (AnnaZen, 198,380--388).--The isodurene used in .these experiments was prepared bythe method described by Jannasch (Ber., 8, 355), viz., by the actionof sodium on a mixture of monobromomesitylene and methyl iodidediluted with a small quantity of benzene. Tsodurene boils at 195-19 7". Isodz~renesu~~~iorLic acid obtained by treating the hydrocarbonwith fuming sulphuric acid crystallises in plates which meltin their water of crystallisation at 100". Lead isodurenesulpl~ate,(CGHMe4S03),Pb + 3H20, forms needle-shaped crystals, so also dothe salts of barium (anhydrous), cdciuin (3H20), and potassium(lH,O). The copper s d t crystallises in pale bluish-green needles,which are anhydrous. The siZuer suZt forms trandparent rhombicplates ; the strontium salt is deposited in lustrous plates containin38 ABSTRACTS OF CHEMICAL PAPERS.9 mols.HzO. The sodium sa7t crystallises in shining rhombic platescontaining 6 mol. H,O. The cohalt snlt crystallises in pale red four-sided plates which contain 74 mols. HzO.When isodurene is boiled with dilute nitric acid (1 : 4) for two days,a mixture of a- and 6-isoduric acids (CloH1202) is formed, togetherwith a polybasic acid, which does not melt a t 300", and also severalnitro-products. The a- and @-acids can be separated by recrystallisa-tion from hot water, or by fractional crystallisation of their calciumsalts.a-Isoduric acid melts a t 215" and at a higher temperature sublimes,forming long glistening needles. It is very sparingly soluble inwater, but dissolves in alcohol, ether, and hot benzene. Prom a diluteethereal solution, the acid is deposited in clear monoclinic crystalswhich refract light powerfully.The a-acid can be distilled in acurrent of steam. Ibs salts are crystalline and are soluble i n water.( CI0H110&Ca + 5E20, ( CloHllOz)~Sr + 5H@, and ( CloHl102)2Ba + 4H2Oform needle-shaped crystals.P-lsoduric acid is much more soluble in water, ether, chloroform,benzene, alcohol, and light petroleum than the a-acid. It crystallisesin needles which melt at liL0-123°, The oaZciurn salt forms glisten-ing needle-shaped crysbals containing 2 mols. H.0.Monobromisodurene boils at 252-254", and crystallises in nacreousBehaviour of Cymene in the Animal Organism. By JACOBSEB( B e y ., 12, 1512--1518).-As cImene has been prepared from normalpropyl iodide and parahromotJoluene, and as the author has shown thatthe hydrocarbon produced from parabromocumene and methyl iodide isnot cymene, but an isomeride,.no doubt would remain regarding thecoristitution of cymene were it not for two reactiions. The first of these,noticed by Kraut and aonfirmed by the author, is that cymene is pro-duced by the action of zinc dust on cymyl alcohol, and the second isthe oxidation of cymerie in the organism to cuminic acid, observed byNencki and Zieglen. Bobh of hhese results are unfavourable to thetheory that cymene contains a normal props1 group. In the present,paper, the author gives an aocount of a repetibion of Kencki aiidZiegler's experiments.The cymene was administered to a.dog, and its urine, after evapo-ration, was acidified and shaken with ether. After distillating off theether, the residue gal-e a copious precipitate with hydrochloric acid,which was found to consist for the most part of cuminuric acid,CI,Hl,NO,. The filtrate from this precipitate gave a, distillate contain-in; a little paraxylylic acid, showing that the cymene administered tothe dog had contained a little pseudocumene.Cuminuric acid melts a t 168", and volatilisea without decomposi-tion. It is almost insoluble in cold, but comparatively easily solublein warm water ; it dissolves with the greatest readiness in alcohol ;ether, however, dissolves it with difficulty. From water it crystal-lises-(l), on addition of an acid, in nacreous scales; and (2), onslow evaporation, in large iridescent rhombic plates, without water ofcrystallisation ; and from alcohol, on evaporation, in radiated crystals.plates.TV. c. wORGANIC CHEMISTRY. 39The barium saZt, ( C,,H,4N03)2.H,0, dissolves wiih some difficulty,and crystallises from its hot solution in long right-angled plates orin flat needles, arranged in a fan-shaped form. The caZczuwz srclt,( C,2H2,N0,)2.3H20, crystallises in thin needles, and is also solublewith difficulty. The unmmiurn and potassium salts are very easilysoluble, and crystallise in needles. The two latter salts give pre-cipitates with salts of zinc, manganese, cadmium, magnesinm, ferrousand ferric salts, copper, lead, and silver ; with mercuric chloride, itgives no precipitate, and with mercuric nitrate, a flocculent insolubleprecipitate.This cuminuric acid probably differs from that which Cahours pre-pared from cuminic chloride and glycolyl silver.I n order further t o confirm the relations of this acid, it was decom-posed by heating with liydrochloric acid ; it split up into glycocine andcuminic acid, melting a t 116-117", and agreeing in all its propertieswith that described by others.It thus appears that cuminic acid isreally a product of oxidation of cymene in the animal organism, butto remove all doubt, and further to connect cumiiiic and cuminuricacids, the latter acid was synthetically prepared from cymyl alcoholand glycocol silver. The product was identical in all respects withthat separated from the uriue.If, then, there is conclusive proof that cumene contains normalpropyl and that cuminic acid contains isopropyl, then the preparationof cumene from cymyl alcohol with zinc dust involves the trans-iormation of isopropyl into normal propyl, and, on the other hand, theformation of cuminic acid from cymene implies the opposite change.In conclusion, the author draws attention to the fact that in hisexperiments, the chief product was cuminuric acid, whilst in those ofNencki and Ziegler, cuminic acid was formed.He also found thelatter acid, but in very small amount. W. R.Products of Distillation of Gum-ammoniac Resin withZinc-dust.. By G. .L. CIAMICIA4N (Bey., 12, 1658--1664).--The oilyliquid which is obtained by the distillation of gum-ammoninc resinwith zinc-dust consists of a mixture of para- and metaxylenes (b.p.136-138"), meta-ethyltoluene (b. p. 160"), methyl ortho-ethylphenate(G. p. 180-200"~, and a hydrocarbon having the composition C,3H,n0,which yields on oxidation henzoic, acetic, and perhaps propionic acids.No naphthalene derivatives are formed. Ortho-ethylphenol obtaiuedby the saponification of the methyl ether is a thick, colourless oil(b. p. 220"), which remains liquid when cooled down in a freezingmixture. On fusion with potash, it is decomposed with production ofCondensation-products of Aldehydes with Primary AromaticBases. By 0. PISCHER (Bey., 12, L693-1694),-Although the authorwas unable to obtain dia?)iidotri~henyZmethane by decomposing tetra-inethyldiamidotriphenylmethane with concentrated hydrochloric acid,he has succeeded in preparing it by the action of zinc chloride on amixture of aniline and benzaldebyde.This base is a crystalline sub-stance and is soluble in light petroleum. By the action of methylsalicylic acid. w. c. w40 ABSTRACTS OF CHEMICAL PAPERS.iodide, at 130", on the solution of the base in methyl alcohol, Letra-methyldiamidotriphenylmethane methiodide is produced. w. c. w.Condensation-products of Tertiary Aromatic Bases. By0. FISCHER (Ber., 12, 1685-.1693).-A good mode of preparingtetrn7neth~ldinmic7otr~?tenylmetliaite consists in digesting on a water-bath a mixture of benzaldehyde (I mol.) and dimethylaniline (2 mols.)m ith a quantity of solid zinc cliloride, equal in weight to the dimethyl-aniline taken, until scarcely any dimethylaniline separates out on theaddition of an alkali to a small quantity of the product.If the massgrows very thick during the operation, sufficient water should beadded to reduce it to a pasty consistency. The solution obtained bytreating the crude product with boiling water deposits the base in astate of comparative purity. The IydrochZoride, Cz3H,,N22HC1, crys-talliges out in colourless hygroscopic needles, when ether is added t o asolution of the base tiissolved in strong hydrochloric acid mixed withalcohol. The methiodide, C,,H2JY22MeI, is deposited from concentratedaqueous solutions in plates, and from dilute solutions in needles,which melt a t 218-222" with decomposition izto methiodide andthe original base.T e t rai72ethyldiai7aidotri23T2 en y lcarbinol, C,,H,,N,.H,O, the base con-tained in benzaldehyde green, is obtained in colourless needles byrecrjstallising from light petroleum the precipitate formed by theaction of an alkali on the salts produced by the oxidation of the leuco-base.The crystals melt at 120°, and form ethers when recrystallisedfrom alcohol. The etlryZ ether, best prepared by heating the carbinolwith alcohol at llO', melts a t 162".The zimochloride, C,3H24N, + ZnC1, + HzO, crystallises in dark-green glistening needles or scales freely soluble in water. Thesulyhate, CZsHz4N2 + HzS04, forms beetle-green needles, containing1 mol. of water.The metliiodide, C23H2,0C&N2(MeI)2 + 2H20, crys-tallises in colourless needles, which begin to decompose a t 100".The constitution of benzaldehyde green (Ber., 12, 796 ; and thisJournal, 1879, Abst., 787) is represented by one of the followingformids :-C6H4NMe CH,.Ph( CsH,.NiWe2)C<&:>NMe, or Ph(C,H,.NMe,)C( 1Tet rcnmeth y Idinmidoprop y Ztr+ 1~ eny 1 me€hane, obtained from cumic alde -hjde and dimethylaniline, crystallises in long colourless needles (m. p.118"). It bears close resemblance to the leuco-base of benzaldehydegreen, yielding on oxidation 8 bluish-green colouring matter.Dimethylaniline and methylal yield tetramethyldiamidodiphenyl-methane (m. p. 91"), which has been previously described by Han-hart (Bey., 12, 681 ; this Joarnal, 1879, Ahst., 714.Doebner (Ber.,12, SlO), and by Michler arid Moro (ibid., 12, 1170). The compoundwhich Pauly ( A n n a l e n , 187, 198) obtained by the action of benzoORGANIC CHEMISTRY. 41phenone chloride on dimethylaniline has the composition C21H21N, andnot. C2,H,,N as given by the discoverer.Dimethylaniline-phthale'in, C2.1HllN202, is prepared by the action ofzinc chloride on a mixture of phthalic chloride and dimethylaniline.The excess of dimethylaniline is removed from the resulting productby treatment wit<h hot water, apd the residue is dissolved in diluteacetic acid. The precipitate which is thrown down on the additionof an alkali to this acid liquid is dried and dissolved in a small quantityof benzene.When light petroleum is poured into this solution, theimpurities separate out, together with a portion of the phthalein. Onevaporating the filtrate, the phthale'in slowly crystallises out, and ispurified by recrystallisation from benzene. The pure substance formscolourless rhombohedrons, which melt, at 188". A green colonringmatter is produced as a bye-product in the preparation of dimethyl-aniline-phthalejin ; its formation increases with the temperature a tSome New Colouring Matters. By P. GREIFF (Bey., 12,which the process is conducted. w. c. w.1610-1611) .-By the action of chloranil on dimethylaniline, a deepbluish-violet colouring matter is obtained ; it is insoluble in water, butdissolves in alcohol and acetic acid. Methyldiphenylamine gives acolouring matter of a deeper blue.These reactions take place a t theordinary temperature, and give good yields. Quinone gives similarproducts. Chloranilic acid and the s-ulpho-acids of chloranil reactdifferently. Phenanthraquinone gives under similar circumstancesbluish-violet bodies, having strongly marked dichroism. The additionof zinc chloride in all these reactions is advantageous. P. P. B.Action of Hydrocyanic Acid on Diazo-compounds. ByS. GABRIEL (Bey., 12, 1637--1639).-A substance, having the com-position C8&N4, separates out in orange-colonred crystals when a coldaqueous solution of diazobenzenesulphate or nitrate is allowed to dropslowly into a well-cooled solution of potassium cyanide. The crystalsare dissolved in a small quantity of warm alcohol, and warm water isadded to the solution.When .the mixture cools, large prisms (m. p.69") are deposited, which decompose, forming a brown resin, if left incontact with the mother-liquor for several hours. The compound isalso decomposed by boiling in water, hy drocyanic acid being evolved,and a resinous bodyformed.By the action of potassium cyanide on bromodiazobenzene nitrate(from bromaniline, m. p. 61) an unstable crystalline product (m. p.127.5") is obtained, which appears to have the composition C8H,BrN4.By a similar reaction, the compound CgH8N4 may be prepared fromtoluene. It is deposited from an alcoholic solution in reddish-yellowplates or needles, which melt at 77-5", but decompose if heated a t 60"for some time.w-. c. w.Formula of Quinhydrone. By H. WICHELHAUS (Bey., 12,1500-1505).-The question considered in this paper is which one of the fol-lowing formulae for qninbydrone is the correct one :-HO.CJ&. O .O. C6H4. OH = C,?H,,O42 ABSTRACTS OF CHEMICAL PAPERS.proposed by Graebe, or H0.C6H,0.0C6H,0.0C,H~.oH = C20H1006,siiggested by the author.Nietzki's argument in favour of the former formula is, that asquinone is reduced to quinol in theoretical proportion by sulphurousacid, quinhydrone should also be acted on in the same manner. I nsupport of this view, he has adduced a series of experiments, in whichquinhydrone was reduced by such a qnantitg of sulphurous acid as tolead to the formula C,,H,,,Oa.The author has repeated these experiments, and has fonnd that theyare untrustworthy, owing to the fugitive blue colour produced by iodinein pyesence of quinhydrone during titration of excess of sulphurousavid.He next brings forward in support of his own views, the factthat ~nethylquinhydrone, prepared by melting ab 100" a mixture ofmethylquinol with quinone, gives numbers which, though differingliut slightly from those required for Graebe's formula, still agreebetter with the formula proposed by him; also, t!liat during the re-action between methylquinol and qninone, hydrogen i s set free, whichreduces the latter, giving rise to a considerable formation of quinol ;and, lastly, that on decomposing methylquinhydrone with sulphurousacid, the resulting quinol bears to the methylquinol the.proportion of1 : 2.5. This agrees closely with the proportion calculated forC20Hl,06, viz., 1 : 2-26, but not with that for C,,H,,OA, viz., 1 : 1-13.In further support of his views, the author calls attention t o thefact that dimethyl- and diethyl-quinone have no action c?n quinol, forhydroxyl is not present in their molecules. When substituted quinolsact on quinone, unsubstituted quinhydrone is invariably focmed, whilsta reduction takes place owing to the liberated hydrogen.I n a similar manner the formation of chloroquinol by treatment ofquinone with hydrochloric acid is explicable by the followingequations :-C&02 + 2HC1 = C~HGOZ -k GI,; and c12 -k c6&02 =An analogous reaction takes place with hydrobromic acid.C*HSG102 + HC1.Theresulting monobromoquinol has the formula C6H5Br02; it may besublimed in small quantities, melts at 110-112", and is soluble inchloroform, benzene, and hot water: During its purification by crys-tallisation from light petroleum, a product, agreeing fairly with theformula CGH4Br20, is obtained less soluble Ghan the former ; it crys-tallises in white needles grouped in stars, and melts a t 185-186".W.R.Constitution of. Phenylhalogenpropionic Acids. By E. ERLEN-NEYEIR (Bsr., 12, 1607-1610). The author criticises the views heldby Glaser (Annalen, 154, 167) and Fittig (ibid., 195, 170) on theconstitution of the phenylhalogenpropionic acids and phenyllacticacids prepared by them, and concludes that these acids have the fol-lowing constitutions :-C6H,.CHX. CH,.COOH ; C6H5. CH (OH). CH,. CO OH, andCGHs.CH(OH) .CHX.COOH. P. P. BORGANIC CHEMISTRY. 43Monobromocinnamic Acids and Phenylfumaric Acid. ByF. BAKISCH ( J . p. Chenz. [23, 20, 173-188).-By the action ofalcoholic potash on dibromohy drocinnamic acid, Glaser (AnmZei-L, 143,330) obtained two isomeric monobromocinnamic acids, which wereseparated by recrystallising their ammonium salts. /?-Bromostjrene,PhCBr : CH, (b. p. 117"), is former1 as a bye-product in this opera-tion from the decomposition of a portion of the monobromocinnamicacid (m. p. 131"), PhCBr : CH.COOH.Glaser prefixes a to the acid crystallising in needles (m. p. 131"),and calls the isonleride which forms crystalline plates (m.p. 120°)the &acid.The author proposes to reverse this nomenclature. sincea-derivatives have a lower melting point, and enter inore readily intoreactions than PLcompounds. Both a- and 13-monobrornocinnamic acidwhen treated with alcoholic potash yield the same phenylpropionic acid,PhC i C.CO0H. When hydrochloric acid is passed through theiralcoholic solutions, they both yicld the same ethyl 6-bromocinnamate(13. p. 290"). The a-acid during the act of etherification is transformedinto the 6-acid.P'henyIfuinaYic acid, CloH804, or COOH.CPh : CH.COOH, is ob-tained by heating at 150" a mixture of potassium c-janide, alcohol, andethyl-P-bromocinnamate, and builing the product with alcoholicpotash. On the addition of hydrochloric acid, a resinous substanceseparates out, the supernatant liquid is concentrated by evaporationand extracted with ether, whrn the new acid is obtained in whitecrystals (m.p. 161"), freely soluble in alcohol, ether, and hot water.The potassium, sodium, ammonium, calcium, and barium salts of thisacid dissolve readily in water. TV. c. w.Formation of Para-hydroxybenzoic Acid from Sodium Phe-nate. BJ- H. OST (J. p ~ . Cl~em. [2] 20, 208).--Very small quantitiesof para-hydroxybenzoic acid and traces of a-phenol-dicarboxylic acidare formed by the action of carbonic anhydride on sodium phenate.The presence of these acids can be detected in the filtrate after theConstitution of Ellagic Acid. By H. SCEIFF (Ber., 12, 1533-1537) .-Gallic acid, when boiled with, arsenic anhydride, forms digallicacid by union of twosmolecules.If the mass is dried and heated tolC;O", the arsenic acid is reduced and ellagic acid is formed :-The question is, are the two benzene-groups in ellagic acid uniteddirectly, o r by means of oxygen ? The ease with which that acid isformed from gallic acid seems to point to a~ negative answer ; but, onthe other hand, no attempt to convert ellagic into gallic acid has beensuccessful. Assuming that direct union subsists, the author suggeststhe following formulax-precipitation of the salicylic acid. IT. c. w.2C14H1009 + As205 = 2C,4H,O, + 4HzO + AS~O~.2C6H,( OH),.COOH = C6H( OH),(COOH) .CsH (o'H),.COOH.2 mols. of ellagic acid. EIlagic acid dried in air.Ellagic anhydride cannot be etherified, does not combine with hydro-gen, and cannot be reconverted into gallic or tannic acids; it forms 44 ABSTRACTS OF CHEMICAL PAPERS.tetracetyl derivative.The author supposes it to have one of the fallow-ing formule : - - coo-\c,H(oH), /o\/o\ I I O \ ICO-C,H(OH), orCO-C6H(OII), CO--CGH(OH)2.The two molecules of water are not expelled a t the same temperature,but it has recently been shown that the temperature a t which thesecond is expelled is much lower than was formerly supposed. Theseformuh sufficiently represent the neutral and basic salts formed byellagic acid. W. R.New Organic Acid occurring in Agaricus Integer. By W.THORNEX (Ber., 12, 163,%1637).--Prom 19 to 20 per cent. of mannitolcan be extracted from Agaricus integer by treatment with boilingalcohol.An acid having the composition C,,HsoO, is contained in thealcoholic mother-liquors. I n order to isolate it, the alcoholic solutionis evaporated to dryness on a water-bath, the residue is exhausted firstwith water to remove any mannitol which may be present, and thenwith hydrochloric acid. It is finally dissolved in a solution of soda towhich one-third of its volume of alcohol has been added. After eva-porating off the alcohol, the acid is precipitated by boiling with dilutehydrochloric acid. The pure acid is deposited from an alcoholic solu-tion in white needles (m. p. 70') soluble in ether, benzene, toluene,carbon bisulphide, chloroform, boiling alcohol, a d 'boiling glacial aceticacid. The potassium, sodium, and ammonium salts are sparingly solublein cold water, but dissolve in warm dilute alcohol.Ba(C15H2,0,)2 andPb( C,,H2,0,)2, and also \the calcium, magnesium, and silver salts arewhite insoluble compounds. The lead salt melts a t 114". w. c. w.Kynuric Acid. By M. KRETSCHY (Ber., 12, 1673-167.5).-Kynuric acid is completely r-olved into its elements by fusion withpotash. Chinoline is formed when this acid is heated at 240" withstrong hydrochloric acid, and also when it is distilled with zinc-dust. w. c. w.Aromatic Thiocarbamides. By C. FEUERLEIN (Ber., 12,1602-1603) .-The preparation of phenylcyanamide from monophenyl thio-carbamide has been described in a, former communication (this Journal,Abst., 1879, 804). NPh), +3H20 ; when placed over sulphuric acid, it forms a syrupy mass, whichon standing becomes crystalline, forming phenylcyanamide.Theplatinum, (NH : C : NPhHCl),PtCI,, and the silver compounds,(NH : C : N(Phj),Ag, have been obtained. Monophenyl thiocarb-amide is converted into monophenylguanidine, NH,.C (NH),Ph, by theaction of alcoholic ammonia. This compound when heated burns with-out previously melting, and is decomposed by exposure to the air o rover sulphuric acid into phenylcyansmide.By C. LIEBERMANN and A. L.~x'GE(Ber., 12, 1588--1595).-0ne of the authors has already describedFrom analysis, its formula, is (NH : CI'. P. B.Formulze of ThiohydantoinsORGANIC CHEMlSTRY. 45the preparation of diphenylthiohgdanto’in (this Journal, Abst., 1879,651), which when decomposed with alcoholic potash mas supposed toyield diphenyl thiocarbarnide, potassium sulphide, and potassium glg-collate.Further investigation has shown that this decompositionyields thioglycollic acid, a reaction also observed by Andreasch ( B e y . ,12, 1385). This decomposition is expressed thus : C,,H,?N,SO +KOH + H20 = C,,H,,N20 + C2H,KS02. Diphenyl-bhiohydanto‘inis similarly decomposed by alcoholic ammonia a t 150”, forming anilineand thioglycollic acid, thus: C,,HI2N2SO + 3NH, + 4HzO =The supposition that thioglycollic acid owes its formation to asecondary reaction, is found t o be untenable, since glycollic acid cannotbe converted into this thio-acid either by boiling with potassium hydro-gen sulphide or with diphenylthiocarbamide and alcoholic potash.Further, the product C,HiNSO, obtained from diphenylthiocarbamide(Zoc.cit.) is also resolved by alcoholic potash and baryta-water intocarbanilide, carbonic anhydride, and thioglycollic acid. These resultsshow that the formula, CS 1 , attributed to diphenylthio-hydanto’in is incorrect. Rather must it be regarded as analogous toJager’s phenjlcarbodiimido-thiacetj c acid,2C,H,N + CzHSSO2NHA + C03(NH4)2.,B Ph-CH,‘flPh-CO,COOH.CH,S.C(NHPh) N H(J. pr. Chem. [2], 16, 17), and therefore its formula isS.K,C\NPh.&OPhN : C’Its formation may then be explained as follows :-(1.) CS(NHPh), + C1C2H302 = CIC(NHPh),.S.CHz.COOH.(2.) ClC(NHPh),S.CH.zCOOH - IECl - HZO =S.H,CPhN : c/‘NPh .This view of the constitution of the tjhiohydantoin is supported bythe investigations of Wallach (this Journal, 36, 312), Wallach andBleibtreu (Ber., 12, 1061), Bernthsen (AnsaaZen, 197, 341), and theinvestigation on thiocarbamide of Claus (Ber., 7, 236 and 841).In this light thiohydantoin will have the formnla-NH,.C S < ;%> C 0,and the product obtained by Lange from diphenylthiohydantoin (Zoc.cit.) is a derivative of monothiocarbaniIic acid, having the formula0 : CS<,,~>CO. This is analogous to Volhard’s C,H,NS02(J.yy. Chem., 9, 8 ) , which may be written 0 : CS<:%>CO. . InC46 ABSTRACTS OF CHEMICAL PAPERS.an analogous manner Nencki's compounds (J. pr. Chern. [el, 16,l) hasthe constitution S : CS<NH >CO, and to the carbaminethiaceticacid of the same aut,hor, the formula 0 : C(NH,)S.CH,COOH maybe attributed.These new formulae also explain why it is so difficult to remove thesulphur from thiohydant(iins, a fact which has been point,ed out byVolharci (Anwalen, 166, 384), Mulder (Ber., 8, l264), Maly (A.n.nalen,168, 133), and noticed by the aut'hors in the case of diphenylthiohy-dantoin. P.P. B.CH,Action of Potassium Pyrosulphate son Indigo-white. ByA. BAEYER (Ber., 12,1600-1609) .-According to Baumann, the intli-can contained in urine is riot a glucoside, but the potassium salt of asulphonic acid of indoxyl (Zeit. .f. Physiol. Chem., 1, 60 ; Die Synthe-1isclze.n Processe <w ThierIcorpe~-, Berlin, 1878, 6 ; R. Baumann and L.Brieger, Zeit. f. Physiol. CJzem., 3, 254 ; and Baumann and Tiemann,this Journal, Abst., 1879, 936).A body possessing the same proper-ties as the above-mentioned indican is obtained by heating 1 part ofindigo, 1 of ferrous sulphate, 2 of potagh, 2 of water, and 3- 4 of potas-sium pyrosizlphate'in sealed tubes for 12 hours a t 60". From this, theauthor concludes that the indican froni urine is potassium hydrin-cligotin-sulphonate, 4216HloN2( O.SO,K),. Baumann's analyses confirmthis observation. P. P. B.Action of Chlorine on Dibenzyl. By R. 'KADE ( J . p. Cliern. [g],19, 461-467) .-Pa~adiclaZorodibeizzyl, CsH,C1.CH2.CHz.C,H,C1 (m. p.112'), is formed by passing chlorine over the crystalline productobtained by melting together iodine and dibenayl, and continuing theaction until hydrochloric acid begins to be evolved.The resultingthick cherry-coloured oil is ,distilled, and the crystals of para,dicliloro-dibenzyl deposited from the oily djstiIlate are purified by crystallisationfrom alcohol. It forms &in fine laminae, closely resembling naph-thalene, and is casily soluble in alcohol, ether, and chloroform.It can be sublimed, giving an odour of bitter almonds when heated,and be distilled without decomposition. It yields parachlorobenzoicacid by oxidation with chromic mixture.The oily body which is formed a t the same time is probably mono-chlorodibenzyl .Quite a different reaction takes place when chlorine is passed into amixture of pzdreimised dibenayl with iodine. In this case toluylenewith unaltered dibenzyl is produced.Toluylene is also formed t,o someextent by the action of chlorine on the vapour of dibenzyl, and bypassing chlorine into melted dibenzyl until it hegins to turn brown,and then . distilling, the whole is transformed into toluylene. Con-tinuing the action until hydrochloric acid is again given off, dichloro-toluylene, CliHl0Cl2 (m. p. 170") is obtained. It crystallises in silkywhite needles or laminae, and easily dissolves in alcohol and ether.'I'olu-ylene is also formed from dibenzyl by the action of potassiumchlarate and hydrochloric acid. It can be distilled and sublimed likORGANIC CHEMISTRY. 47benzoic acid.chloride. A. J. C.Its alcoholic solution gives a red coloration with ferricDerivatives of 7-Dichloronaphthalene, &Nitronaphthalene-sulphonic Acid.By P. T. CLEVE (Ber., 12, 1714).--~-Trichloro-naphthalene (m. p. 65') was prepared by the action of phosphoruspentachloride on 7-dichloronaphthalene (m. p. 48"). The salts of8-nitronaphthnlenesnlphonic acid are crystalline. The chloride of thisacid melts a t 169", the smide a t 216", and the ethyl salt at 108". vv. c. w.Action of Chlorine on C hloronaphthalene : Nitro-derivativesof a- and p-Dichloronaphthalene. By 0. WIDMARN (Ber., 12,1714-1715) .-a-Monochloronaplithalene combines with chlorine toform C,,H,CI, (m. p. 67"), and CI,H,Cl.C1, (m. p. 131*5"), whilst13-monochloronaphthalene forms a liquid trichloronaphthalene, and atetrachloride, C,oH,Cl.Cl~ (m. p. 81°), which when treated with potashgives a t8richloronaphthaleiie, melting a t 140".By the action of chlo-rine on an acetic acid solution of a-monochloronaphthalene, an aceto-chloride, C,,H,C12. C1,Ohc (m. p. 195") is produced. a-Dichloronaph-thalene yields only one nitro-derivative, viz., the trinitro (m. p. 178"),but the P-componnd forms a mono- and a dinitro-derivative, which melta t 92" and 158' respectively. w. c. w.On the Quinone occurring in Agaricus Atrotomentosus.By W. THORNER (Bcr., 12, 1630--1635).--The spectrum of the redalcoholic solution of the quinone extracted from Agnl-lcus LEtrotomen-toszu by means of ether is chsracterised by a deep red band betweenB and D.A crpt,alline ammonium salt separates out as a dirty green-colouredpowder, when strong ammonia is added to a hot alcoholic solution ofthe quinone.It, dissolves in dilute alcohol and in water, forming aviolet solution, which produces coloured precipitates with manymetallic salts, viz., a flesh-coloured crystalline precipitate with bariumchloride ; dirty pink flocculent precipitate with calcium chloride ;brownish-green with lead acetate ; black with ferric chloride ; darkgreen with mercuric chloride ; brownish-black with alum ; reddish-brown with copper sulphate ; brown with platinum chloride ; dirtygreen with silver nitrate ; and a beautiful green crystalline precipitatewith magnesium sulphete.The conipound obtained by the action of benzoic anhydride on theyuiiione forms yellow needle-shaped ci-ystttls, which melt a t 285" withdecomposition. By heating the quinone with dilute nitric acid, oxalicand nitric acids and also a nitro-product are formed.The latter bodyis a yellow powder (m. p. 255-260") soluble in alcohol and chloro-form.By the reduction of the quinone with hydriodic acid, or by zinc andhydrochloric acid, two bodies are produced, viz., a yellow powder,insoluble in the usual solvents, but easily converted into qninone byalkalis, arid a white crystalline compound (m. p. 162-164'), solublein alcohol and ether48 ABSTRACTS OF CHEMICAL PAPERS.When heated with zinc-dust,, a large volume of gas is evolved, hutno solid hydrocarbons were formed in appreciable quantity. Fromthese results, the author concludes that this substance is ruethyldihy-droxynaphtlioquinone, CloH,Me( 0,) (OH),.The mother-liquor from the quinone contains an acid (m.p. 54"),which dissolves in benzene, toluene, ether, chloroform, carbon bisul-phide, glacial acetic a,cid, and petroleum ether. I t s barium, calcium,lead, and silver salts are insoluble in water. w. c. w.Action of Ammonia and Amines on Quinones. By T. ZINCKEBey., 12, 1641--1647).--Phe,zantl~reneqz~ino~~i~7~ide, C14H80.NH (m. p.159') is obtained in yellow, needle-shaped crystals, by passing gaseousammonia into a warm alcoholic solution of the quinone, or by dissolv-ing the quinone in warm concentrated alcoholic ammonia, C,2HR02 +NH, = C14H8.0.NH + H,O. The b i d e is decQrnposed by boilingwith alcohol, the quinone being regenerated. It combines with acidsto produce red-coloured compounds, which are destroyed by water,with production of the quinone.When heated with acetic or benzoicanhydride, the imide loses a molecule of water, giving rise to a crystal-line compound (m. p. 247") which is sparingly soluble in hot benzene.By the prolonged action of alcoholic ammonia on phenanthrenequinone,the imide which is first formed disappears. and a mixture of a basicsubstance soluble in acetic acid, and a ceutral compound insoluble inacetic acid, is produced. The latter cornpound sublimes in lustrousyellow needles, which have the composition CZ,H,,N2. A second basicsubstance, very soluble in alcohol, is also formed. It is probably iden-tical with voii Sommaruga's base (IUer., 12, 982). A yellow crystallinecompound, probably CldH8.0.NMe, separates out, when phenanthrenequinone is treated with an alcoholic solution of methylamine.Thecrystals are insoluble in atlcohol, but dissolve in hot benzene. Theyform a blue compound with strong hydrochloric acid.The mother-liquor froin the yellow compound contnins a strongbase, c16Hl*Na which appears t o be formed according to the followingequation: CldH.,02 + 2MeNHz = C,J&(NMe)2 + 2H20. This sub-stance crystallises in colourless prisms (m. p. 186"), and formswell crystallised salts, viz., the hydrocldoride Cl&Il~N,HCl, colour-less prisms, soluble in water, insoluble in alcohol ; the nitrate, fineneedles, sparingly soluble in water and in alcohol ; the sulphate, needlessparingly soluble in alcohol ; the oanlate, transparent prisms, solublein hot dilute nlcohol. hTaylit7ioquii~o?ae forms with ammonia a brownarnorpbous product, but with primary amines it yields crystallineclerivatives, according to the equation :-2C,,H,02 + NHZR' = C,,H,(O),NR' 4- CmH,(OH),.Naphtho- Amine.New compound. Naphthoquinol,quinone.The compound C,,H,.O,.NPh is obtained by adding an excess ofaniline to a hot alcoholic solution of naphthoquinone. The precipitatewhich is thrown down on the addition of water to the mixture istreated with acetic acid to xemove excess of aniline, and is thenrccrjstallised from alcohol, when the pure substance separates oiit iORGANIC CHEMISTRY. 49lustrous red needles, which melt at 191", and sublime a t a higher tern-perature. The crystals dissolve in hot benzene, alcohol, and ether ;they yield with sulphuric acid a red solution, and with alcoholic potasha purple colour.By the action of zinc and hydrochloric acid, or of sulphurous acid,the compound is split up into naphthoquinol and aniline.With paratoluidine, naphthoquinone forms a beautiful red compound,crystallising in needles (m.p. 200"). The methylamine compoundcrystallises in bright red needles, which melt a t 225", and the ethyl-amine compound fornis orange-coloured needles (m. p. 140").A crystalline substance is also produced by the action of diphenyl-amine on naphthoquinone, in presence of hydrochloric acid.Benzoquinone differs from naph thoquinone in its behaviour toamines, e.y., 2C6H402 + 2Ph.NH2 = C6H402(??BPh)2 + CsH*(OH)2. w. c. w.Amidoanthraquinone from Anthraquinone-monosulphonicAcid. By H.It. v. PERGER (BET., 12, 1566--1571).-Anthraquinone-monosulphonic acid, or its ammonium salt, when heated with ammoniain sealed tubes a t 19@", yields a red crystalline product, which is solublein concentrated hydrochloric acid, and on addition of water is throwndown again as an oraiige or red flocculent precipitate. By repeatedsublimation in a current of carbonic anhydride, and crystallisationfrom alcohol and benzene, this compound is obtained pure. Analysisshows it to be monamidoant8hraquinone, C1,H702.NH2 (m. p. 302") ; andits formation may be expressed thus : C,IH,02S03NH, + (NH,), =C,,Hi02.NH2 + (NH4),SOs. Bourcart (Bey., 12, 1418) describes acompcmnd obtained in the same way, which melts a t 301", and to whichhe attributes the formula CI,H,02.NH2.0H; such an amidoanthraquinolshould be soluble in alkalis, which is not the case with this compound.The views of t,he author are further supported by the behaviour of thiscompound with nitrous acid ; first a yellow crystalline body is obtained(m.p. 23S0), which on boiling with alcohol yields authraquinone ; andon boiling with water, a-monoxyanthraquinone is obtained.Heated with acetic anhydride_ amidoanthraquinone yields the yellowacetoxy-derivative, C,,H,O,NHAc ; i t is soluble in alcohol and ether.It melts a t 257", the melting-point of Bourcart's (Zoc._cit.) acetoxy-derivative, to which he attributes the formula C14HS03NAc3.I n conclusion, the author states that attempts made to prepare mono-nitrosnthrayuinone according to Bottger and Petersen's method(Annaleib, 166, 147) have given negative results.Y. P. B.Decomposition of Hydroxyanthraquinone by Potash. By C.LIEBERMANN and J. DEHNST (Ber., 12, 1597).-Amongst the productsobtained by the fusion of anthraquinonemonosulphonic acid with potash,the authors found small quantities of paraoxybenzoic acid. Thisowes its existence to the decomposition of monhydroxyanthraquinone,which may, therefore, have the constitutional formula-P. P. B.e VOL. XXXVIIL 50 ABSTRACTS OF CHEMICAL PAPERS.Constitution of Camphor-compounds. By M. BALLO (Be?.., 12,1597-1600) .-In another communication (Awnaten, 197, 321) theauthor has given his reasons for regarding camphor as a tertiary alco-hol, having the constitution 1 1 .Thisview is sup-ported by the fact that when camphor is oxidised by boiling chromicmixture, acetic, carbonic, and adipie acids are formed, thus :H C : C(CH,)-CHZ(0H)C : C(C,H,)-CH,the central nucleus of the camphor forming adipic acid,the methyl group, carbonic acid, whilst the propyl group forms carbonicacid and acetic acid.The author regards camphrene, C9€€,IU, as a homologue of camphor,since it also yields adipic acid when oxidised (Kachler, Ann,aZen, 164,90), and has the properties of an alcohol.Essence of Marjoram. By BRUPLANTS (J. Pharm. [4], 30, 33-3?5).-Essence of marjoram, obtained by distilling the flowery tops of0rignlzzl.m Mncyjoyaaa in a current of steam, is a yellowish liquid, whenfreshly prepared (sp.gr. 0.911 a t 15"), but becomes brown on stand-ing. It has a pungent smell, and a hot, peppery, and slightIy bittertaste. It is dextrorotatory, and has an acid reaction. When distilled,it begins to boil a t 185", but the temperature rnpidlyrises to 200°, andremains constant between 215 to 220", a resinous mass being left inthe retort.By repeatedly fractioning the oil which passes over a t 185--190", aportion is obtained, boiling between 160-162", consisbing principallyof a terpene.The fraction boiling a t 215-2.20" yields no portion having a constantboiling point, nor does it deposit crystals when cooled to - 2.5". Itsvapour-density and analysis correspond with either laurel camphor orborneol. When distilled with phosphoric anhydride, it yields a mix-ture of cymene and a terpene (b.p. 160--170"). When treated withacetic anhydride, it forms a compound (b. p. 230-235'), which withalcoholic potash yields terpene and potassic acetate. Chi-omicmixture oxidises it with the formation of acetic and formic acids, andlaurel camphor.Essence of marjoram is therefore composed of a dextrorotary hydro-carbon, 5 per cent. ; a mixture of dextrorotatory camphor and borneol,85 per cent. ; resin, 10 per cent.(C H2) 4( coo H) 2,P. P. B.L. T. 0's.Essences of Lavender and Spike. By BRUYLANTS (J. P~Kw-H?.[ 4 ] , 30, 139--141).-Essence of lavender when freshly preparedis a colourless liquid, which becomes yellow on standing; i t smellsof lavender, and its taste is hot, camphorous, and slightly bitter.It is lEvorotatory, has an acid reaction, and sp.gr. 0.87.5 a t 1.5'. Itbegins to boil a t 185", the temperature quickly rises t o 190", and thegreater portion distils over between 195-215". The first portion ofthe distillate consists of a mixture of acetic and formic acids, but con-tains no vnleric acid. By repeated fractionation, a laevorotatory terORGANIC CHEMISTRY. 51perene (b. p. 162") is separated, capable of forming a crystallinehydrochloride. The essence also contains a mixture of camphor andborneol : this mixture Forms an acetate (b. p. 230°), which is decom-posed by potash, yielding a terpene and potassium acetate. When it isdistilled with phosphoric anhydride, a hydrocarbon is obtained, con-sisting for the most part of terpene, and containing also some cymeneEssence of lavender consists of terpene, 25 ; borneol (+), and cam-phor (+), 65 ; resin, 10 per cent.Essertce of Spike.-This essence obtained from Lavnndula aspicoZatyolia is a colourless liquid, which in time thickens and darkens incolour. It has an acid reaction, and sp.gr. 09081 a t 1 5 O . Itsodour resembles that of lavender. I t s composition is almost identicalwith that of essence of lavender, but as it contains more hydrocarbon,it begins to boil a t 170-175". Its composition isas follows:-Terpene, 35; borneol and camphor, 55; resin, 10 percent. L. T 0's.It is ltmorotatory.Limited Oxidation of the Essential Oils. Part V. TheAtmospheric Oxidation of Turpentine.By C. T. KINGZETT(Chew. News, 39, 279).-The author has shown in his previous papersthat when so-called essential oils are exposed to the atmosphere, per-oxide of hydrogen is indirectly produced. In turpentine oil, i t appearsas if a camphoric peroxide, CloHla04, is first formed, and that in con-tact with water t3his is decomposed, yielding hydrogen peroxide andcamphoric acid, thus : Cl0Hl4O4 + 2H,O = CloHl,Oa + H202.Similarly, berpene, CIoHl,, and menthene, CloHl, give rise to per-oxide of hydrogen, whilst hydrocarbons of the formula CI,H,, do not.As all terpenes and menthene yield cymene, CloHI4, and as cymeneitself yields hydrogen peroxide, the author believes that there is somerelation between Che formation of this body and that of hydrogen per-oxide, and this opinion is strengthened by the fact t,hat the hydro-carbon from oil of cloves, CI5H2p, yields neither cymene nor hydrogenperoxide.The product of oxidation which is formed by exposing turpentineto tlie action of the air, and which in contact with water forms hydro-gen peroxide, may be produced in such quantities that when the tur-pentine oil containing it is heated a little above the boiling point,decomposition occurs v1 ith almost explosive violence. The atmo-spheric oxidation of turpentine is now carried out, on the large scale, inthe manufacture of? the disinfectant called " sanitas."Different essential oils and varieties of turpentine absorb oxygenwith different degrees of rapidity, and when oxidation has once com-menced, the oil absorbs oxygen with increasing rapidity in proportionas the oxidation increases, up to a certain point.As to the differencesin this respect in different oils, the author gitres the following resultsdeduced from experiment by exposing the various oils under similarconditions to light and air. Assunling that the amount of oxygenabsorbed by Russian oil of turpentine (which absorbs the largestamount) be represented by 100, then Swedish oil of turpentine absorbs100.e 52 ABSTRACTS OF CHEMICAL PAPERS.An oil obtained from Switzerland. ................... 89.4American oil of turpentine.. ........................ 78-9Oil of eucalyptus.. ................................ 75.0Adulterated Swedish turpentine ....................52.6'' Scotch distilled American turpentine ". ............. 42.1The two last-mentioned oils were presumed to be adulterated with so-called pine-oil of commerce. When these oils are placed in cylinders,the mouths of which are covered with papers saturated with a mix-ture of potassic iodide and starch, the papers become coloured in theorder given above, owing to the formation of different quantities ofhjdrogen peroxide in the vicinity of each.When the aqueous solution obtained by blowing air through a mix-ture of turpentine and water (" snnitas "), is evaporated to drynesson a steam-bath, the hydrogen peroxide contained in i t is decomposed,the acetic acid is expelled, and there remains a dark coloured matter,which when hot is viscid, and has a sugar-like odour, b u t on coolingsets to an adhesive but firm mass; when treated with sulphuric:acid it gives a colour reaction somewhat resembling that bearingPettenkofer's name.This adhesive mass, which was slightly volatileat looo, after drying gave numbers corresponding with the formulaC10H1803. It has remarkable antiseptic properties, t'o which thesimilar properties of " sanitas " are largely due.About 95 per cent. of this adhesive matter is soluble ~JI water,forming a yellowish-brown solution, from which charcoal failed toremove the colour, although it absorbed a considerable proportion ofthe substance itself. This solution on evaporation to dryness left atransparent varnish-like substance, semi-fluid wlien hot, and volatile a t100".The 5 per cent.of the original adhesive substance which was in-soluble in water did not give the vivid reaction with sulphuric acidwhich the soluble poktion did; this insoluble matter is soluble inpresence of an oily substance which the original aqueous solutioncontained, and which was expelled on evaporation.On submitting the soluble portion to distillation, it melted, boiled,and a small quantity of an almost colourless oil passed over, which oncooling became a colourless, soft crystalline mass ; this was followedby a permanent oil, which became darker as the distillation pro-ceeded ; towards the end, the vapour in the retort had a green colour,~ i i d a pitch was left. None of these products have as yet been furtherexamined.On acidulating the solution of the soluble portion, CI0Hl8O3, withdilute sulphuric acid, it becomes milky, and on standing, a slightlycoloured oily body separates in considerable quantity.The authorhopes that a study of this substance will throw light not only on theconstitution of the soluble substance, but also on that of the terpenefias a class.The aqueous solution (" sanitas ") obtained by oxidising Russianturpentine, when neutralised with soda, darkens very much in colour,and on evaporation of the mixture a t loo", a dark soft resin-like residueis left. On treating this with dilute sulphuric acid, it yields it darkProm analysis, the formula ClOH1803 was calculatedORGANIC CHEMISTRY. 53oily mass : the clear acid solution is filtered and.subjected to distilla-tion ; as it becomes hot more oil separates out, and an acid distillatepasses over, together with 20 or 30 C.C. of a slightly yellow oil with anodour resembling that of mixed cymene and eucalyptus. At the endof the distillation a quantityof tarry-looking matter remains in theretort floating on the acid solution. The acidity of the distillate wasfound t o be due to acetic acid, which amounted to about 0.25 graniper litre of the aqueous solution (“sanit;tr~”), and no other volatileacid could be detected. The author anticipates that the further studyof those compounds will be attended with very important and interest-ing results, inasmuch as they have the advantage of having beenproduced by the mildest possible oxidation. W.T.Fusion of Rhamnetin with Potash. By L. SMORATVSRI. (Ber.,12, 1595-1596).-According to Stein ( 2 e i t . f . Chenz. [Z], 5, 183, 56S),rhamnetin when fused with potash yields phloroglucinol and querceticacid. The aubhor finds that by fusion with potash or soda, rham-netin is decomposed into phloroglucinol and protocatechuic acid ; a tthe same time, sniall quantities of a substance are formed which, likequercetic acid, gives a deep red coloration with alkalis. This last-named body could not, however, be obtained in quantities sufficient foranalysis. P. P. B.Chlorophyll.. By F. HOPPE-SEYLER (Ber., 12, 1555-1.556).-When grass-blades, after treatment with ether to remove wax, arecohobated with alcohol, two crpstalline cdouring matters are dissolved,one of which, named erythrophyll by Bougarel, ci*ystallises out first ingreenish-white quadratic tables, whilst the other is more soluble inhot alcohol, and may be purified by optallisation from ether, fromwhich i t is deposited in microscopic needles and scales, dark green byreflected, and brown by transmitted light.The crystals of the latterbody are of the consistence of soft wax ; it dissolves with difficnlty incold alcohol, easily in hot alcohol, and readily in ether and chloroform.The ethereal and alcoholic solutions of this substance have the knownred fluorescence of chlorophyll, and absorb the light between B and Cof the spectrum with such intensity, that 1 milligram dissolved in alitre of water gives distinct absorption-bands in a thickness of 3.5cm., with a Browning’s spectroscope.Several analyses show it tohave the composition: .C, 73.4 ; H, 9.7 ; N, 5.62 ; 0, 9.57 ; P, 1.37 ;Mg, 0.34 p.c. The presence of phosphorus and magnesium may be dueto impurities, and the author proposes to investigate this more closely,He has named this substance chZorophyZlan, and remarks in conclusion,th:rt i t is now possible to estimate the amount of chlorophyll in plantsapproximateIy by means of its power-of absorbing light.Characin. By T. L. PHIPSON (Chein. News, 40,86) .-Amongst theorganic substances present in fresh water IS a new and interesting pro-duct, to which algae in general owe their peculiar odour, and commu-nicate this odour to the water in which they abound. The author hasobtained this substance in minute quantities only at present from.Pnlnzella crue”lzta, Vauckeria terrestris, and from several OscillariE.ItW. R54 ABSTRACTS OF CHEMICAL PAPERS.is appazvently more developed in the genus Chnra, and C. fcetida millprobably yield it in larger quantity than the plants already mentioned.Characin is R kind of camphor, which is extracted from the aboveplants in the following manner.The PaZnLelZa or Oscillaria which is to be treated must be previouslydried by exposure to the air, a t a temperature not exceeding summerheat, for about 24 hours; it is then covered with cold water in acapsule, which must itself bc covered with a sheet of glass, and in thecourse of about 36 hours more (with PaZmeZZa cruenta) thin films ofcharacin will be observed floating on the water.The latter is thendecanted off into a long tube, together with the films, and shaken upwith ether. On evaporation a product is obtained which is quite white,devoid of crystnllisation, and more or less unctuous in appearance.Up to the present time, the author has not obtained this substancein sufficient quantity to ascertain more of its properties. D. B.Phthalei'n of Haematoxylin. By E. A. LETTS (Bey., 12, 1651-1653) .-H~matoiiyli?L-phthalei'n, CIOH30011, is prepared by heatinghacmatoxylin wioh rather more than half its equivalent of phthalicanhydride a t 150-170" for five hours. The alcoholic solution of thecrude product is poured into water, when a brown flocculent precipi-tate separates out, which is filtered, washed, and dried in a vacuum.The phthalein conld not be obtained in the crystalline state ; when thealcoholic solution is evaporated, it leaves a gummy residue insolublein water, but soluble in ammonia and soda, with a purple colonr.Hacmatoxylin fornis white crystalline potassium, sodium, and bariumcompounds. w.c. w.Collidine from Aldehyde. By A. WISCHNEGRADSKY (Ber., 12,1506--1508).-Thc object of this research was to ascertain by oxida-tion whether collidine, CsHIIN, is trimethyl-pyridine, C5H2NMeS,ethyl-methyl-pyridine, C,H,NMeEt, o r propyl-pyridine, C5H4NC3H7.The collidine was oxidised with chromic acid in presence of sulphuricacid, and yielded an acid crystallising in white slender prisms, solublewith difficult'y in cold, but easily soluble in hot water.Its formulawas C8H7NO4, and as it yielded picoline on distillation with lime, it isprobably methyl-dicarbopyridenic acid. From this research, theauthor believes that collidine may be viewed as trimethyl-pyridine.W. R.Piperidine Salts : Quinine Sulphate, hnd Selenate. By T.HJORTDAHL (Ber., 12, 1730-1731 j.-The hydrochlorides and golddouble salts of piperidine and methylpiperidine are isomorphous.Quinine sulphate and selenate are also isomorphous ; the relationbetween the axes of the latter substance is a : b : c = 0%04 : 1 : 0.3110. w. c. *w.Aspidospermine. By G. FRAUDE ( B e y . , l2,1560--1562).--Someaccount of this alkaloid has already been given by the author (thisJournal, 1879, Abst., 470).The bark containing it is that of Aspido-sperrna querbracho bZanco (Schlectendahl). Further analyses showaspidospermine to have the composition C22N30N202. Concerning itORGANIC CHEMISTRY. 55preparation, the author finds that the liquors obtained after a precipi-tatJion of the alkaloid by means of sodium carbonate yield a furtherquantity by treatment with phosphotungstic acid. This precipitate istreated with baryta-water, and the solution thus obtained with car-bonic acid to precipitate the barium ; the alkalo'id is then extracted bymeans of alcohol from the residue left on evaporation. One part ofaspidospermine is soluble in 600U parts of water a t 14" ; this solutionhas a bitter taste. It is also soluble in 48 parts of alcohol (99 percent.) at 14", and in 106 parts of pure ether a t the same tempera-ture.A small quantity of aspidospermine treated with a few drops ofconcentrated sulphuric acid, and then with a little lea,d peroxide, givesa cherry-red coloration, which has a violet shade if the alkalo'id is notquite pure.Iodic anhydride and sulphuric acid produce the same reaction,whilst pot,assium dichromate and sulphuric acid give a brown zoneslowly changing to an olive-green.Chlorine reacts on aspidosperminesuspended in water, producing a white flocculent mass, which is notdissolved by hydrochloric acid ; this compound begins to decompose at145". Bromine acts similariy.Aspidospernzii~e sulphate, ( C22H,~,0,),H4S04, is obtained byevaporation and drying a t 120" as a hard, transparent, resinous mass.The ?yhochZoride, 3( C2,H,,N202 + 4HC1, has similar properties to thesulphate. Bg treating solutions of the base with potassium chromatethe chi-onzate is obtained as a yellow precipitate, which on exposureto the air becomes green. The perchlorate is obtained by addingaqueous perchloric acid t o a not too dilute solution of the base.Hydrochloric acid solutions of the base are precipitated by potassiummercuric iodide in yellow flocks; by potassium sulphocyanide, as awhite flocculent precipitate ; by iodine dissolved in potassium iodide, asbrown flocks ; by picric acid, as a yellow precipitate; and by tannin,as a white precipitate. Further, these solutions reduce Fehling'ssolution when boiled with it.According to Penzoldt ( B e r l . Klilz. Tochenschrift, 1879, 14), thebark of Aspidospermu querbracho bZanco has important medicinal pro-perties. P. P. B.Oxidation of Cholic Acid. By H. TAPPEINER (Ber., 12, 1627-1629) .-The author obtained stearic acid as an oxidation-product ofcholic acid ( B e y . , 11, 2258), but, Latschinoff denies that this acid isformed (Ber., 10, 2059, and 12, 10%). The discrepancy between theseresults is explained by the fact that the author employed a mixture ofpotassium dichromate and sulphuric acid as the oxidising agent, wbiktLatschinoff used potassium permanganate.A weak solution of the oxidising mixture must be used when it isdesired to isolate the fatty acids obtained by the oxidation of a smaZZqzmi~tit!j of cholic acid.A crystalline barium saZt, (C12H13C7)2Ba3 + 6H20, is formed byheating a saturated solution of cholic acid in baryta-water in sealedtubes at 120". It crystallises in long white prisms, which are verysparingly soluble in water56 ABSTRACTS OF CHEMICAL PAPERS.To prepare pyrochoZesteric acid on the large scale, a solution ofcholesteric acid in glycerol is heated a t 198" for a week ; the glycerateis then saponified, and after removing the volatile prodiicts by distilla-tion, the pyrocholesteric acid is extracted from the residue by meansof ether. w. c. w.Oxidation-products of Cholic Acid. By P. LATSCHINOFF (Ber.,12, 1518-152S).-By oxidation of cholic acid, the author did notobtain cholesteric acid, nor fatty acids, as Tappeiner did, but an acidtermed choloidic acid, to which Redtenbacher gave the formulaC16H2407. This acid, which he prepared by oxidising cholic acid withnitric acid of sp. gr. 1-37, evaporating the oxidised product to dryness,and separating the acid first with alcohol, and then as soluble bariumsalt', after repeated crystallisation from alcohol, gave numbers agree-ing with the formula C1,H,,O4 ; it is thus isomeric with camphoricacid, and the author has therefore named it cholecany?m..ic acid.The properties of cholecamphoric acid are as follows :--It is solublein water and in ether with difficulty ; easily in alcohol, more easilywhen aqueous, also in acetone, and in acetic acid. From ft boilingaqueous solution, i t is deposited in such a thick mass of interlacedhair-like crystals, that it presents the appearance of a jelly. It has a,bitter, acid, somewhat astringent taste. when heated, it loses water,varying in quantity, but approximating to +H,O. It does not melt,but begins to blacken a t 270". Its solution is dextrorotatory. It is adibasic acid, forming soluble salts wit'h metals of the alkalis andalkaline earths, and insoluble salts with the heavy metals. The authoradduces numerous analyses of the salts to confirm the formula of theacid, and indicates the acid potassium salt, Cl0HI5KO4, as a proof of itsdi basic character.Cholecamphoric acid may be regarded as a product of hydration ofcholic acid, thus: C20H2806 + 2lLO = 2CloHl,O4.Such bodies, and many resembling them, for example cholesterinand cholic acid, may be regarded as compounds of condensed valery-lenes, and may be connected with the terpenes. Thus cholesterin mayprovisionally be given the formula (C,H,),H,O, and cholic acid(C,H,),O,.+H,O. This view is supported by the oxidation of cholicacid into cholecamphoric acid, and also by the results of oxidisingcholesterin, the product being trioxycholesterin, analogous to betu-lin. W. R