126 ABSTRACTS OF OHEMICAL PAPERS.0 r g a n i c C h e m i s t r y .Preparation of Brcrmofomn from Acetone and Sodium Hypo-bromite. By G. DENIG~S (J. Pharm. [5] 24 243-247).-A litreflask is charged with 100 C.C. of soda lye 200 C.C. of water and then20 C.C. of bromine. After gentle shaking from time t o time theliqxid becomes uniformly yellow when sufficient acetone (about 10 c.c.)is added to decolorise the solution. There is quickly formed analmost colourless layer o€ bromoform. The product is washedrepeatedly with water from which it can be easily separated by filtra-tion and the compound is usually pure enouph for immediate em-ployment. The reaction takes place in two stages eodium hypo-bromite and sodium bromide are fiist formed ; then the hypobromiteand acetone react forming bromoform sodium acetate and sodiumhydroxide. The yield is 60-70 per cent.of that theoreticallypossible. The bromoform should be removed from contact withhypobromite as soon as possible otherwise carbon tetrabromide iORQANIC CHEMISTRY. 127produced. A pure sample of bromoform boiling at 150 (768 mm,)had a density of 2.906 a t 12" and 3.897 at 18" or say 2.90 at about15" confirming Cahonrs' previous determination of 2.90 at 12".Monobromobutylenes. By E. REBOUL (Compt. rend. 113,589-592) .-When the bromide CHMeBrCHMeBr boiling at 150°,and obtained by the action of bromine on symmetrical dimethylene,CHMeXHMe is treated with alcoholic potash it yields a mixture ofthe two bromobutylenes CHMe:CMeBr and CHnlleBr*CH:CH2.A new brombuhylene CH2Me*CBr:CH2 is obtained by the removalof HBr from ethylethylene bromide.Normal bromobutane is mixedwith one-third the theoretical quantity of bromine together withwater and the mixture exposed to sunlight i n a small closed flasknntil it is colourless. The product is then distilled and the fractionboiling below 160" is treat'ed again with bromine i n a similar manner.The successive products boiling above 160" are mixed and frac-tionated when they yield ethylethylene bromide boiling a t 166' andfree from isomerides.When ethylethylene bromide is treated with alcoholic potash in theordinary manner it yields monobromobutylene boiling a t 88" under apressure of 759 mm.; it is a colourless liquid with an alliaceousodour ; sp.gr. 1.28% at 21". Since the boiling point is 3" below thatof Bontlerow's bromisobutylene CMe2:CHBr. it is almost certain thati t has the bromine a t the end of the chain that is removed from theethylethylene bromide. If the compound is heated at 10U" in Rsealed tube with alcoholic potash it yields a light mobile liquid whichhas a strong alliaceous odour and boils at 14-14.5" under a pressureof 761 mm. With ammoniacal cuprous chloride it forms a deepsulphur-yellow cornpound and with ammoniacal silver nitrate awhite compound both of which yield the hydrocarbon when treatedwith dilute acids. The hydrocarbon is probably identical with theethylacetylene obtained by Bruylants from methyl ethyl ketonechloride.In view of this decomposition the monobromobutylene may be calledethylacetylene a-hy drobromide.It combines with bromine with greatenergy yielding a tribromobutane CH2Me*CBr2.CH2Br which boilsat 112-115' under a pressure of 40 mm. and with partial decomposi-tion at 214-218" under the ordinary pressure ; it is a colourless liquidof sp. gr. 2.136 at 17". It is not identical with the product ofstheaction of bromine on normal butyl bromide i n presence of sunlight ;the latter boils a t 117-122" under 40 mm. and its sp. gr. at 17" ic32.171.Eihylacetylene a-hydrobromide combines slowly with aqueoushydrobromic acid in the cold but more rapidly at lOO" yielding amixture of the bromide boiling a t 166" and a lower bromide probablyCH2&le*CMeBr2. Boutlerow's bromisobutylene behaves differentlyunder similar conditions.J.T.C. H. B.Penterythritol a Tetrahydric Alcohol obtained fromFormaldehyde and Acetaldehyde. By B. TOLLENS and P. WIGAND(Armalen 265 316-340) .-A crystalline compound which th128 ABSTRACTS OF OHEMICAL PAPERS.authors name penterythritol is formed together with volatile fattyacids amorphous syrupy substances aldehydes and small quantitiesof a crystalline substance the nature of which has not yet beendetermined when a mixture of formaldehyde (194 grams) acetalde-hyde (60 grams) water (9 litres) and calcium hydroxide (160 grams)is kept for one to two nionths or longer a t the ordinary temperaturewith frequent shaking. The boiling filtered solution is treated withR quantity of oxalic acid exactly sufficient to precipitate the calciumi n solution then filtered and evaporated t o a syrup ; on keeping forsome time the residue solidifies to a mass of yellowish crystals andis purified by recrystallisation from water with the addition of auimalcharcoal. The yield of the crude crystalline product dried on porousearthenware is about 115 grams.Penterythritol C,H,(OH) crystallises from hot water in large,well-defined prisms melts at 2.50-255" and is soluble in about18 parts of water a t 15"; its molecular weight was determined i nglacial acetic acid solution with results in a8ccordance with themolecular formula ascribed to it above.I t s aqueous solution isoptically inactive even in presence of borax ; when a neutral aqueoussolution of pent.erytjhritol is added to a small quantity of a solutionof borax the latter acquires a distinctly acid reaction. When pent-erythritol is heated quickly it gives off an odour recalling that ofdecomposing glycerol ; i t does not give the iodofo~m reaction.Thetetracetyz derivative C5H8( OA?) prepared by heating the alcoholwith acetic anhydride and sodium acetate is a crystalline substancemelting at 84" ; molecular weight determinations in acetic acid solu-tion gave results agreeing with those required by a compound of themolecular formula given above.The di-iodhydrin C5H812( OH) is formed when penterythritol isheated with concentrated hjdriodic acid and amorphous phosphorusat 170-180"; it forms colourless crystals melts a t 1W" and isreadily soluble in alcohol but only sparingly in water.The tri-iod-hydrin C,H,I,*OH is produced together with the tetriodide describedbelow when penterythritol is heated with concentrated hydriodicacid and amorphous phosphorus at 190" in sealed tubes; when theproduct is boiled with water the residue dissolved in alcohol and thecold solution evaporated large rhombic plates melting at 70" aredeposited ; if these crystals of t,he tri-iodhydrin are dissolved in hotalcohol and the solution then allowed to cool the compound isobtained in lustrous needles melting a t 62'. The tetriodide C,H,I,,is isolated by extracting that portion of the product which is insolublein alcohol with boiling benzene from which it is deposited on coolingin colourIess plstes melting at 225".When penterythritol is oxidised with nitric acid it gives oxalicacid and an amorphous product the nature of which has not been de-termined ; when treated with chromic acid it yields formic acid andcarbonic anhydride.The constitution of the alcohol is most probablyfixpressed by the formula C(CH,.OH),.A Sugar from Quince-juice. By R. W. BAUER (Landw. Versuchs-Stat. 469-470).-When quince-juice is boiled with 5 per cent.F. S. KORGANIC CHEMISTRY. 129sulpburic acid it yields a sweet syrup which bas approximately thesame rotatory power as dextrose and from which a yellow osazonemelting at 204” can be obtained. F. S . K.Cellulose Gum. By W. HOFFMF:ISTER (Landw. Vemuchs-Stat. 39,461-468 ; compare Abstr. 1890 581).-When cellulose prepared inthe usual manner by extracting certain vegetable products with ethey,alcohol water and cold dilute ammonia successively is treated with5 per cent.soda a considerable but variable quantity of wood gumpasses into. solution ; this gum is completely soluble in an ammoniacalsolution of copper oxide znd is not destroyed by the “chlorinemixture ” previously referred to. If after extracting with soda thecellulose is dissolved in an ammoniacal solution of copper oxide andrepi-ecipitated with hydrochloric acid in the cold 01- if it is treatedwith the chlorine mixture glacial acetic acid or dilute ammonia tofree i t from incrusting substances i t again yields a considerablequantity of soluble carbohydrates on extraction with 5 per cent.soda;when the portion insoluble in soda is again treated with any of theabove-named reagents a fiirther quantity is rendered soluble and,by repeating the treatment many times the whole of the cellulose isobtained in a form which is soluble in 5 per cent. soda.The quantity which is rendered soluble by any single treatmentdepends on the source of the cellulose ; it would seem therefore thatcellulose is not a homogeneous substance. For the soluble productobtained in the manner described Tollens proposes the name cellulosegum ; this substance also exists in various forms. F. S. K.Constitution of the Ligno-celluloses. By C. F. CROSS and E. J.BEVAN (Chem. News 64,63-64).-Cold dilute aqueous chromic acid€orms a compound with the substance of jute fibre which by treatmentwith mineral acids is converted into a brittle soft substance lustrousand greenish in appearance containing from 2 to ’2.5 per cent.ofchromic oxide and convertible into an oxycellulose the alkalinesolution of which reduces Fehling’s solution on boiling. The yield ofthe chromium compound from a fibre which gave 74 per cent. ofcellulose by the chlorination method was 85-90 per cent. so that aportion of the jute convertible ir,to soluble derivatives by chlorination,here appears t o yield product,s rno1.e intimateiy connected with cel-lulose. The soluble products of the oxidation are brown gummysubstances which when chlorinated yield substitution productshaving characteristic colour reactions. The formation of the chromiumcompound may be regarded as a step in the process of lignification.The authors draw attention to the substance which Lindsey andTollens (Inaug.Diss. GSttinpn 1891) have isolated from the gummyresidue left cin evaporation of the waste liquors from the Mitscherlich(bisulphite) fir-wood paper-pulp process ; it has the compositionand appears to be related to the ketonic substance lignone previouslyobtained from jute (Trans. 1889 55 213). JN. W130 ABSTRACTS OF CHEMICAL PAPERS.Thio-derivatives of Ethylamine. By S. GABRIEL (Ber. 24,3098-3104 ; compare Abstr. 1891 815).-The action of varioussubstances on ethylmercaptophthalimide CJ34O2:N.CH,*CHZ*SH hasbeen studied.A warm solution of ethylmercaptophthalimide (11 grams) inabsolute alcohol (25 c.c.) is treated with sodium ethoxide (2.3 grams ofsodium in 25 C.C.of alcohol) and bromethylphthalimide (14 grams) andboiled for half an hour in a reflux apparatus. The solution is cooled,and the crystals washed with alcohol and hot water ; diphthaZimido-ethyZ suzpphide (C,H,O,:N*C,H,),S melting at 128-129' is thus ob-tained the yield being two-thirds of the theoretical.When a solution of ethylmercaptophthalimide (20 grams) in alcohol(50 c.c.) is gradually heated with sodium ethoxide ('2.3 grams ofsodium in 50 C.C. of alcohol) and then with ethylene chlorhydrin (10grams) boiled for half an hour in a reflux apparatus the alcoholdriven off and the residue treated with water a colourless syrup(20 grams) which will not cyystallise separates; it is doubtless/3- hy droxy -P-pht ha:im idoet hy Z sulphid e OH.C,H,*S *C,H4*N C,H402.When warmed with double the volume of phosphorus oxychloride ityields p-chZoro-~-phthnZimidoethyi suZphide C2H,C1*S*C2HI.N:CBH102,which separates out when the mass is poured into water as an oilthat gradually crystallises.Recrystnllised from acetic acid andalcohol it forms colourless needles melts a t 76-77" and dissolveseasily in ether benzene caybon bisulphide chloroform and boilinglight pe trole um.C2II4Br*S*C,H4*N C8H402,is obtained in a similar manner by using the pentabroinide instead ofthe oxychloride of phosphorus. It crystallises from hot light petr-oleum in long needles melts at 89-90' and dissolves readily i nethyl acetate warm carbon bisulphide and ethyl and methylalcohol.The oxidation of diphthalimidoethyl sulphide has also been studied.When a slight excess of bromine w-ater is added to a solution of thesulphide ( 3 grams) in hot acetic acid (15 c.c.) diphthalimidoethylsulphoxide ( C,H,02:N*C2H4),S0 is formed and separates whenthe solution is cooled in long needles melting at 191".When thissubstance (18 grams) is boiled with 20 per cent. hydrochloric acid(250 c.c.) for three hours in a reflux apparatus a complex decomposi-tion takes place resulting in the formation of diamidoethyl sulphoxide,taurine ammonia and thioethylamine ; f o r details as to the sepallationof these reference must be made t o the original paper. UiarnidoethyEsdphoxide picrate SO (C2H,.NH?),,SC,H,N30 forms a yellow crystal-line powder which softens at 190° and melts with decomposition a t200".Thioethy Zninine picrate S ( C,H,.NII,>,,2C,H,N3O forms long,broad prisms softening at 190" and melting with decomposition at213". The platinochloride S (C2H,*NH,),,H2Pt CIS forms orange-yellow needles. The benzoyl derivative S ( C2H4*NHBz) crystallisesfrom ethyl acetate in scales which soften at 106" and melt a t109-1 10".When diphthalimidoethyl sulphide (G grams) is dissolved in a/3- Bromo- /3-pl~thalimidoethzyt sulphideOROANIC CHEMISTRY. 131mixture of acetic acid (60 c.c.) and water (6 C.P.) on the water-bath and chromic acid ( 5 grams) added transparent colourlesscrystals of diwhthalt ~~aidoethyl~ulpl~one SO1 ( C2H4-N:C,H,0,) separate(6 grams).This sof ens at 250" melts at 255-256" and dissolves verysparingly in most solvents slightly in hot acetic acid and can becrystallised from hob nitrobenzene. The same compound may beobtained although 1 ctss conveniently by oxidising an acetic acidsolution of the sulph ide with potassium permanganate. When thesulphone (3 grams) is heated with alcohol (20 c.c.) and 33 per cent.aqueous potash (3 c. :.) it dissolves and ethyZsul~honed~hthala?72icacid crystallises out wiien the solution is diluted with water acidifiedwith hydrochloric acid and cooled. I t forms broad colourless needles,readily soluble in ammonia and boiling water. The silver saZt,S0,(C,H4*NH.CO*C6H COOAg) forms an amorphous precipitatewhich changes to a crystalline powder.When t,he acid is boiled withhydrochloric acid it is decomposed into phthalic acid and diamido-ethylsulphone the hydrochloride of which SO,( C2H,*NH,)2,2HCI isobtained by filtering and concentrating the solution. The platino-chzoride SO,(C,H,.NH,),,H,PtCI~ forms sparingly soluble orange-red,hexagonal tables. The picrate SO,( C,H,*NH,),,2C,H,N,O crystallisesin long needles softening above 170" and melting at 185".8-Chlcrrobutylamine and a Synthesis of Pyrrolidine. By S.GABRIEL (Ber. 24 3231-3235) .-a- C hlorobutylamine may be pre-pared from y-chlorobutyronitrile in the following manner :-35 gramsof y-chloyobutyronitrjle is mixed with 32 grams of phenol and addedto a sollition of 8 gi-ams of sodium in 100 grams of alcohol. Afterboiling for an hour the alcohol is distilled off water added and theoily layer which separates taken up with ether and fractionated ; thefraction boiling at 285-290" consists of y-phenoxybutlJronitriZe,OPh*CH2*CH,*CH2*CN and solidifies on cooling t o crystals melting at4 5 4 6 " . The same compound has been obtained by Lohmann fromy-bromopropyl phenyl ether (Abstr.1891 1467). On reduction withsodium in alcoholic solution this compound yields 6-phenozybutyl-amine OPh*CH,*CH:,*CH,*CH,.N~ a colourless alkaline oil boilingat 254-257" which is converted by hydrochloric acid a t 180-185"into phenol and 2-chlorobutylamine hydrochloride,C. I?. B.CH,Cl*CH2*CH2.CH2*NH,,HCl.The former is extracted with ether and the acid aqueous solutionevaporated ; the oily residue solidifies after some time to a crystaI-line mass which deliquesces in the air and may be purified by dis-fiolving i t in hot amyl alcohol and adding ethyl acetate.The picrate,CaHloNCI,CsH3N30 forms amber-yellow .oblique prisms or plates,and melts at 120-121" ; and the platinochloride (C4H,oNCl),,H,PtCl,,crystallises in orange scales.When 8-chlorobutylamine hydrochloride is treated with more than2 mols. alkali in aqueous solution and steam passed through theliquid a base distils over having an odour closely allied to t h a t ofpiperidine; i t boils a t 87.5-88.5" has the sp. gr. 0.8520 at 22*5",mixes with water forming a strongly alkaline solution and fuiiies i132 ABSTRACTS OF CHEMICAL PAPERS.the air. Its platimchlo?.ide (C4NH9),,H2PtC16 crystnllises in compact,yellowish-red prisms which become dark at 190" and melt at about200' ; the aurochloride C4NH9,HAuC14 becomes plastic at 200" andmelts a t 205-206" with decomposition ; the picrate C4NHB,C6H3N307,becomes plastic at 105" and melts at 111-112"; and the cadmioiodide,(CaNHg),,H,CdI forms long silky needles which become plastic at210° and melt at 217-219".These properties agree except in thecase of the cadmioiodide with those ascribed by Ladenburg (Abstr.,1886 528; 1887 499 1052) and by Petersen (Abstr. 1888 498) t opyrrolidine with which i t must therefore be identical. That it isnot the isomeric butallylamine CH2:CH*CH2*CH2.NH2 is shown bythe fact that it does not decolorise bromine-water in acid solution.H. G.C.Action of Nitrous Acid on Nonylarnke. By M. FKEUSDand F. SCHOIYFELI) (Bey. 24 3350-3366).-Methylhexylcarbinoiis prepared by heating castor oil (100 parts) with 15 per cent.potash (150 parts) for half an hour; water (200 parts) is thenadded gradually and after remaining for some time the productcrystallises. These crjstals (500 grams) are mixed wit>h finelypowdered potassiiim hydroxide (170 grams) and tlhe whole rapidlydistilled ; the distillate is finally dried over potassium hydroxide andfractionated. The pure alcohol boils at 176.5-177". The iodide isobtained by treating the alcohol with hydrogen iodide at 60" ; theyield is almost quantitative. The cyanide CN*CHMe*CsHI3 is formedfrom the iodide by the action of potassium cranide ; the actual yieldis 14-15 per cent.of the theoretical. It is suggested by the authorsthat methyl cyanide should be termed carbin cyanide and that thenames of the higher hornologues should be derived from this in asimilar manner to that prevailing in the ca'se of the alcohols; theabove compound would therefore be termed methy lhexylcarbincyanide.iVon enylamidoxime NH,*C(:NOH)*C,H, is prepared by the action ofhydroxylamine hydrochloride and sodium ethoxide on the precediiigcompound ; it crystallises from light petroleum in short squareprisms and melts at 84".Nony Zamine NH2*CH2*CH&fe*C6HI3 is obtained by the reductionof the cyanide with sodium in alcoholic solution and is purified bymeans of the hydrochloride ; it is n colourless liquid with a fishyodour and boils at 185-1.86".The hydrochloride crystallises fromlight petroleum and melts at about l:3Uo; the pZatinochZorn.de isdeposited from its alcoholic solution in yellow needles.Nonyldithiocurbamic acid is deposited in crystals on mixing nonyl-amine with carbon bisulphide.Nonylcarbanzide NHz.CO*NH*CBHIg crystdises from water incolourless lustrous square prisms which melt a t 92". Dinonyloxmnide,prepared by the action of nonylamine on ethyl oxalate in etherealsolution crystallises from alcohol in small colourless needles andmelts at 92".PltenylnorLyZcarbaiizide NHPh*CO-NH*C,HIg is deposited fromdilute alcohol in groups of long prismatic crystals and melts a t 63OORGANIC CHEMISTRY. 133P~nylnonylfhiocarbamide NHPh*CS*NH*C9Hlo crystallises fromdilute alcohol in small plates and melts at 58-60'.Nonglaniine hydrochloride i n aqueous solution is digested withargentic nitrite in excess at temperatures below 50" and the clearsolution distilled ; nitrogen is evolved and on drying and fraction-ating the distillate two portions are obtained the one boiling a t135-1550" the other at 170-192".The lower fraction consist<s of(3-methyZhexyZeth?yZene CH,:CMe*C6H ; it boils a t 141.5-143" has thesp. gr. = 0.7318 at llo/llo and readily absorbs bromine a t ordinarytemperatures. Thr constitution of the compound is shown by themode of its formation. The higher boiling portion of the distillateproved to be di?,zethzJEhex~ZcarcrhinoZ C6H,3*CMe,*OH ; this boils at183-184' has R sp.gi-. of 0.8211 a t 12"/12" and combines with bariumoxide. The yield of alcohol is increased by allowing the mixture ofnonylamine hydrochloride and argentic nitrite to remain for threedays at the ordinary temperature the reaction being then completedby gently warming.On oxidation with dilute sulpliuric acid and potassium dichromnte,dimethylhexylcarbinol yields carbonic anhydride acetic acid andcaproic a5d thus proving its constitution ; with hydrogen iodide,the corresponding iodide C,,H13*CMe21 is formed and yields OII heat-ing with alcoholic potash a hydrocarbon which boils a t 140-144r" ;whether t!he latter is identical with the one described above (b. p.141~5-143") or whether it is a-din~ethlllhe~tylethyle~~e CMe,:C H:C,,H,,,could not be determined. J.B. T.Formation of Tetralkylarnmonium Iodides. By H. MALBOTand A. MALL%OZ (Coin@. rend. 113 554-556).-'11he three types ofreaction between amines and ethereal salts pointed out by one of theauthors do not appear to depend on the nature of the alcohols fromwhich the salts and amines are derived. Trimethylamine reacts inthe cold with normal propyl iodide primary isobutyl iodide primaryisoamyl iodide primary ally1 iodide and secondary isopropyl iodide.The reaction proceeds comparat,ively rapidly but is favoured byheating t o 100".cipitated when added t o potash ; they are notl decomposed by boilingwith the latter. With silver oxide (not necessarily freshly prepared),they a,ll yield hydroxides. The platinochlorides are generally insolublein alcohol.Normal propyl iodide reacts with methylaminc more rapidly thanisoamyl iodide and still more rapidly than isobutyl iodide.Izopropyliodide ad though secondary reacts more rapidly than primary isobutyliodide. With ally1 iodide the reaction is very violent like its reactionwith bromine.The union between certain systems of amines and ethereal salts isaccompanied by elimination of hydrocarbons due not so much to thedecomposition of the ethereal salt by heat as to a new type of reactionoccurring which corresponds with a greater development of energyThe solutions of the tetralkylammonium iodides formed are pre- .(compare AYL~L. Chinz. Phys. [6] 13 451). w. 1'134 ABSTRACTS OF CHEXIOAL PAPERS.Benzoyl Derivatives of Glucosamine.By G. PUN (Monntsh.,12 435-440) .--The author confirms the statement of Kueny (Abstr.,1890 578) that glucosamine hydrochloride does not form benzoy1derivatives when it is heated for a long time with excess of benzoicanhydride.Pentabenxoy Z glucosamine C6HJ3z5NO5 is obtained when glucos-aminc hydrochloride (15 grams) is dissolved in water (60 parts) andthe solution shaken with 10 per cent. sodium hydroxide (420 c.c.)and benzoic chloride (60 c.c.). It crystallises in snow-white slenderneedles is insoluble in water dissolves in hot alcohol and acetic acid,and is reconverted int,o glucosamine hydrochloride and benzoic acidwhen treated with concentrated hydrochloric acid. The pure sub-stance melts at 203" ; but the author found that on recrystallisingfrom acetic acid the crude product obtained in one operation a meltingpoint of 215" was shoari. The substance of higher melting pointdoes not appear to differ i n composition from that which melts at alower temperature (compare Kueny loc.cic.).By R. SCHIFF (Gazzetta 21 490-497) .-Pinnerand Fuchs (Abstr. 1877 584) by t,he action of ammonium acetate onchloral hydrate obtained a substance of very indefinite melting pointwhich they supposed to be chloralimide CC13*CH:NH. The authorfinds this to be a mixture.Chloral hydrate ( 3 parts) and ammonium acetate (2 parts) arefused together on the water-bath the product cooled and then pouredinto water; about one-fifth of the mass remains undissolved as ayellow solid.On crystallising this from alcohol Pinner and Fuchs'chloralimide is obtained ; it begins to melt a t 80" and finally meltswith decomposition towards 200". On fractional crystallisation fromalcohol. it is split into three distinct compounds melting at 14Go Y7",and 225" respectively. If the heating on the water-bath in the pre-paration of the mixture be too prolonged the substance melting a t97" cannot be detected in the product.The compound melting at 146" on analysis and determination of itsmolecular weight by the ci-yoscopic method i n acehic acid solution isfound to be trimoZecuZai* chloralimide (CCl,.CH:NH),.The substance melting at 97" is in a similar manner found to bediinoZecular chloralirnide (CCl,*CH:NH) ; on heating to above 146",it is wholly converted into the trimolecular compound.When thetrimolecular compound is heated with acetic anhydride colourlessneedles sparingly soluble in the usual solvents and melting withdecomposition a t 235" are obtained. This is trimolecular diacetylchloral-ammonia [CC13*CH(OAc).NHAc]~ ; the mother liquors contain thesimple diacetylchloralammonia previously described by the author(Abstr. 1877 308). When dimolecular chloralimide is etuployed inplace of the trimolecular compound the same products are obtained.The compound melting with decomposition at 225" has the com-position C6HGC15N30 and seems to be formed by the mutual action oftrimolecular chloralimide and ammonium acetate.G. T. M.Chloralimide.W. J. PORGANIC CHEMISTRY. 135Amidoxirnes and Azoximes.By I?. T~EMANN (Ber. 24,3420-:3426).-This paper is an introduction to the following papers.The author has observed t,hat the reaction between orthocyanobenzylcyanide and hydroxylamine is not normal. Under varying conditions,only 1 niol. of hydroxylamine reacts with 1 mol. of orthocyanobenzylcyanide and the product of the reaction does not behave like anamidoxime containing an intact cynno-group but has propertieswhich show that the cyano- and amidoxime-groups have reacted oneach other. The author puts forward two possible formuke for this/C6H4*cHZ\compound NH:C <~"H"'C~>C*NH2 - and N H - C c N H7,C.u- 1.An examination of the amidoximes shows that scarcely one whenprepared from the corresponding nitrile can be isolated as such sincethe amidoxime group a t once reacts wit,h another group which ispresent.Thus hydroxylamine and ethyl orthocyanobenzoate do notreact to form ethyl henzenylamidoximeorthocarboxylate,COOEt0C6H,*C(KOH)*NH2,C H but alcohol is eliminated and phthalimidoxime CO < k$>C:NOH,is produced. The latter is easily convei-ted into phthalimide bythe action of ferric chloride and hydrochloric acid or of nitrouaazid.Rosenthal ( B e y . 22 2983) has shown that hydroxylaminereacts with a cyano-group contained in a carbon side chain ratherthan with one in the benzene nucleus. Hence orthocyanobenz ylcyanide should first yield orthocyanophenylethenylamidoxime,CN*C6H,.CHz.C(NOH).NHz from which a compound of the formulaNH:C <c6H4*CH2 > C:kOH would be formed.- NH-If the latter compound were then converted into a shble isomeridewhich does not contain a free oximido-group does not lose ammoniaunder the action of acids and bases and has slight basic properties,this compound will probably ha,vc the constitution expressed by thesecond formula given above. The author reserves the further con-sideration of this compound for a later date.I n conjunction with F. Garny he brings forward results in supportof the above views.Trimethylene cyanide is converted by hydroxylamine at 60-70"into the normal products that is glutarendiamidoxirne,NH2.C (NOH)*CHz*CH,*CHz*C (NOH)*NH,,C H aiid glutarenimidodioxime OEI*N:C< ZH6> C:N*OH.If however molecular proportions are used and the action isallowed to take place at the ordinary temperature a compound isformed similar t o that described above as obtained from orthocyano-benzyl cyanide. The a*uthor expresses the constitution of this com-pound by the formula NH2*C-NH-CC. ,C3H6\,\O-N/136 ABSTRACJTS OF UEEMICAL PAPERS.If the reaction takes .place at a somewhat higher temperature,ammonia is evolved and glutarimidoxime CO<%2> C:NOH isformed.Ethylene cyanide and hjdroxylamine react in molecular propor-tion to yield succinimidoxirne GO<$:> CXOH just as glutar-inlidoxime is formed from trimethylene cyanide.Succinimidoxime is also easily obtained by the action of nitrousacid (1 mo1.j on succinenimidodioxiine by the further action ofnitrous acid succinimide is obtained. The author points out thatthis reaction supports the formula CH2*Co>NH I for succinimide.Glutarimidoxime is obtained in an analogous way from glutaren-imidodioxime.In the glutaric series the tendency to ring formation is so greatthat glutarimidoxime is produced by replacing an oximido-group inglutarendiamidoxime by oxygen and evaporating the solution ofbutenylamidoximecarboxylamide so produced.By the actionof hydroxylamine on succinimide succinaminehydroxamic acid is firstformed and then 2 m o k condense to form disuccinimidodihydrox-amic acid NH( CO.CH,*C:H,.CO.NH*OH),.In conjunction with H.Modeen the author has examined the actionof hydroxylamine on ethyl cyanacetat4e and finds that the productconsists of methenylamidoximacetohydroxamic acid,C H,.C 0Succinimidoxime cannot be prepared in this way.O H K C ( NH2j -C H2-C O*NH*OH,a compound which is both an amidoxime and hydroxamic acid.Finally in conjunction with IJ.Michaelis t,he author has preparednicotenylamidoxime C,NHA.C(NH,):NOH (see this vol. p. ZOS),from p-cyanopyridine. It is inore stable than the aliphatic amidoximes,and behaves like benzenylamidoxime. E. C. R.Action of Hydroxylamine on Derivatives of Succinic andGlutaric Acids. By I?. GAI{NY (Eer. 24 3426-3437) .-Ethylenecpnide the compound from which the first series of compoundsdescribed in this paper is derived is prepared according to Pinner'smethod by heating equal weights of ethylene bromide and potas-sium cyanide in nlcoholk solution for two hoiirs in a reflnx apparatuson the water-bath.The mixture ;is kept neutral by successive addi-tions of dilute sulphuric acid. The product is then fractionallydistilled.Su.ccininaidoxime CO<%2>C:NOH is prepared by digestingethylene cyanide (1 rnol.) dissolved in alcohol with an aqueous solu-tion of bydroxylyamine hydrochloride (1 mol.) and sodium carbonate (4 mol.) for eight hours a t 60-70" in a closed vessel ; on evaporat-ing the solution to dryness ammonia is evolved; the residue isextracted with absolute alcohol and filtered hot. On cooling thORQANIC OHIEMISTRY. 137compound separates i n white crystals melt,s at about 197" withdeccmposition and turns brown before melting. It is soluble inwater sparingly so in hot alcohol insoluble in ether benzene lightpetroleum and chloroform has both acid and basic properties andclissolvcs i n sodium hydroxide solution with a bluish-green ccloration.The /qdrochZoride is soluble in alcohol crystallises in radiating needles,and melts a t 98". The piciafe is precipitated on allowing a con-centratecl solution of succinimidoxime and picric acid to remain sometime and melts at 212".Silver nitrate gives no precipitate. Thecopper salt is moss-green ; the Zeud salt wliite. With ferric chloride,i t gives a reddish-brown coloration ; when boiled with Fehlinm'ssolution a reddish-brown crystalline precipitate is obtained. ItDisconverted into succinimide on adding sodium nitrite t o an t-iqueoussolution and then gradually adding Iiydrochloric acid t o t,he well-cooled mixture.Succinimidoxime is also pretmred by the following methods :-1.Drouin (Compt. rmd. 108 675) has obtained t h e nitrile ofsuccinaminic acid by heating ethylene cyanide with alcoholic am-rtioni;t a t 110". This nitrile is treated with hydroxylamine hydro-chloride RS described above ; on evaporating the solution to dryness,ammonia is evolved and on extracting the residue with absolutealcohol fiuccinimidoxime is obtained.2. Semhritzki ( B e y . . 22 2958) ~ L A S obtained sncci~rendiamidoxime(m. p. 18%") by the action of hydroxylamine (2 mols.) on ethjlenecyanide at the ordinary temperature; if howei.et* the mixture beheated ammonia. is eliminated and succinenimidodioxime is produced.The latter contains 2 mnls.of water of crystslliswtion and melts at'207"; aft,er drying i t melts at 198". Succinimidoxime is obtained byadding sodiiirn nitrite (1 mol.) to this product dissolved in hydro-cliloric acid.Succinendiamidoxime is produced by the action of hydroxylamine(1 mol.) on ethylene cjanide (1 mol.) i n the cold.I n the hope of preventing the hydrolysis of the succinimidoxime,which takes place when i t is prepared according to the fii-st methodgiven above ethylene cyanide dissolved i n absolute alcohol wasdigested in a closed vessel for eight hours at 70" with hydroxylaminehjdrochloride dissolved in a,bsoliite alcohol and the quantity ofsodium ethoxide required to neutralise the hydrochloric acid. Butunder these conditions succinendiamidoxime is formed.The author draws a.ttention to t h e fact that although t,he mixturewas heated ammonia is not eliminated from both amidoxime groups ;only a very smali quantity of succirienimidvdioxime could bedetected.Benzoy lsucc inirnidoxime CO<$Z>C:NOBz is obtained b j addingthe equivalent quantity of benzoic chloride to succinimidoxime.dis-solved in the calculated quantity of sodium hydroxide. The mixtureis shaken as long as the odonr of benzoic chloride can lie detected,and then allowed to remain for 12 hours with dilute ammonia. inorder to remove the benzoic acid which is formed. The precipitateis collected dissolved in chloroform and precipitated with petroleum,FOL. LXII. 138 ARSTRAOTS OF CIHEMICAL PAPERS.and finally crystallised from chloroform.It fmms a white powder,melts a t 184" is soluble i n alcohol benzene. and chloroform sparinglyso in ether and insoluble in water and light petrolenm. It dis-solves in hydrochloric acid hut not in potassium hydroxide.Glutarin&&w CO < %2> C:NOH.-Trimeth ylene cy anid c fromwhich t.his conipound is obtained is prepared in the same way asethylene cyanide lmt the action is much slower.Biedermann (Ber. 22 2967) obtained crlutarendiamidnxime(m. p. 233") and glutarenimidodioxinie (m. p. 193") by the ackion of2 mols. of hydroxylamine on trimethylene cyanide a t 60-70". Bythe action of 1 mol. of hydroxjla.mine on trimethvlene cyanide at t'heordinary t>emperature he obtained tt componnd which is isomeric withyc~anobutenylnmidoxime.and melts a.h 103".In order to obtain a compound of the plut~.ric series malogousto succinimidoxirne trimethylene cyanide (1 rnol.) is digested in aclosed x-essel with hydroxylamine (1 mol.) and sodium carhnnate($ mol.) in dilute alcohol for eight honrs at 60-70". On cooling aprecipitate is obtained which consists mainly of g1 utaren d ianii d oximc..Ammonia is evolved when the filtrate is evaporated to dryness andglutarimidoxirne is ohtained by extmcting the reRidue with absolutealcohol. It melts a t 196" is soluble in hot water and alcohol almostinsoluble in ether benzene light petroleum. and chloroform. a.nddissolves both in hydrochloric acid and potassium hydroxide. Silvernitrate gives no precipitat,e. The copper salt is bright green the.leadfialt white. With ferric chloride it gires a brown with Fehling'ssolution a green coloration bnt no precipitate is formed. When dis-solved in hydrochloric acid and treated with the cnlcnlated quantityof sodium nitrite i t yields glutarimide ; the latter crystallises fromalcohol and melts at '152".Glutarimidoxime can also be prepared by t,reatinc glutarendiamid-oxinie dissolved in hydrochloric acid with sodium nitrite.The compound melting a t 103" and described by Biedermann isnot formed under the above conditions.Benzoylglutariiizidoxime is obtained in the same way as benzoyl-succinimidoxime. It crystallises from alcohol in npedles melt,s at160" and is soluble in alcohol benzene and chloroform almost in-mluble in ether and insoluble in water a,nd light petroleum.Itdissolves in hydrochloric acid but not in potassitim hpdi-oxide.Disuccinimidodl:hydroxnmic acid NH.(CO*C H2*CH2.C0.NH*OH) isobtained by digesting succinimide (1 mol.) wit,h hydroxylaminehydrochloride (1 mol.) and sodium carbonate ($ mnl.) at 60-70".The product is evaporated to dryness and extracted with aloohol ; onallowing the alcohol t o evaporate slowly beautiful. lustrous needlesof the new compound are obtained. It melts a t 171" is very solublein water less so in hot alcohol and only sparingly in et,ber; it is in-soluble in benzene light petroleum and. chloroform. The aqneoussolution has an acid reaction. With ferric chloride i t gives an intense,dark cherry-red coloration characteristic of the hydroxamic acids.The vapour density cannot be determined as the substance decom-poses when heated above its melting point ; neither can the moleculaORGANIO CHEMISTRY.139weight be determined by Raoult's method. The sileer salt is white butrapidly blackeus in the air. The sodiunr salt is formed by addingsodium ethoxide to an alcoholic solution of the acid. The copper saltis bright green the lead salt white. When boiled with hydrochloricacid it is converted into succinic acid. The picrate forms yellowneedles and melts at 266". The tetrabenxoyl derivative melts a t 123",and is soluble in alcohol ether benzene light petroleum and chloro-form very sparingly so in hot water.I n the hope of obtaining succinhgdroxamic acid succinamide wastreated at 60-70" with free hydrolxylamine (1 mol.) but under theseconditions also disuccinimidodi~ydroxamic acid is formed.E.C. R.Action of Hydroxylamina on Ethyl Cyanacetate. Bp H.MODEEK ( Ber. 24 3437-3439) .-Nitriles are converted by hydroxyl-xmine into amidoximes ; and certain ethereal salts are converted byhydroxylamine into hyclroxaniic acids the etlierea.1 group beingeliminated as alcohol. According to Muller (Ber. 18 2485 and 19,1491) aromatic compounds which are both nitriles and ethereal salts,when treated with hydroxylamine are converted into amidoximes,and the ethereal group yemains unattached.The author has examined the behaviour of ethyl cyanacetate acyano-ethereal salt of the aliphatic series with hydroxylamine andobtains a 1-esult quite different from that of Miiller.OH*N:C(NH,)*CH,*CO.NH*OH,is obtained by heating a clear alcoholic solution of ethyl cyanacetate(30 grams) hydroxylamine hydrochloride (40 grams) and sodiumcarbonate (82.3 grams) for 3-4 hours at 40".On cooling the com-pound separates in snow-white crystals. I t crystallises in well-formed prisms is insoluble in ether ethyl and methyl alcohols light,petroleum benzene chloroform carbon bisulphide acetic acid andacetone sparingly soluble in cold water easily so in hot water sodiumhydroxide ammonia and dilute hydrochloric sulphuric or nitricacid. It turns brown 0 1 1 heating decomposes about 150° and givesoff ammonia when heated on platinum foil. The aqiieous solutionhas an acid reaction gives a deep-red coloration with ferric chloride,and a dirty-coloured precipitate with Fehling's solution.Methenylamidoximacetohydrosamic acid is also formed by the actionof hydroxylamine on ethyl cyanacetate a t the ordinary t,emperature.If hydroxylamine insuffcient to decompose the ethereal salt be em-ployed part of the latter remains unaltered; the rest is convertedinto the above compound.Hence the cyano- and carboxyethyl-groups are equally attacked. The author has prepared a number ofderivatives of the new compound and hopes to describe them a t alater date. E. C. R.Mt~herLy Zamidoximacethydroxamic acid,Saponification by Sodium Ethoxide. By I(. OBKRM~~LLER(Zeit. phrlsiol. Chem. 16 152-159 ; compare Abstr. 1890 1474 ;1891 1143).-Sa,ponification by sodium ethoxide is more rapid thanby the methoxide.(which is slowest) or the amyloxide. It was found1 140 ABSTRACTS OF CHEMICAL PAPERS.that the addition of ether to the mixture stops the process ofsaponification. The whole process can be divided into two stages,fivst a formation of sodium glycerol and an ethyl salt of the fattyacid which is more easilg saponified than the f a t ; this is saponi-6ed by the sodium hydroxide which is formed from the sodinmglycerol and the water present. W. D. H.Metallic Fomnates. By W. TIOPSEK and G. Voss (Anwalen 2 6 6 ,:33--52).-The statements of Hensser (Pog. Ann. 8 3 3 7 ) that bariumformate is isomeric with the corresponding manganese zinc andcopper salts and that strontium and copper formates are isomeric areincorrect.Copper formate crystnllises in various forms according to the con-ditiotis of the experiment ; by slowly evaporating an aqueous solutionof the salt a t 75-85' anhydrous cr\ stals are obtained b u t a t 50-609monoclinic crystals ( a b c = 1.33073 1 1.22445 / j = 96" 37'),having the composition (CHO,),Cu + 2H,O separate from the w l u -tion ; when copper formate is crystallised from hot concentratedformic acid a salt containing 4 mols.H,O is obtained. The followingdouble salts were prepared :-B(CHO,),Ba (CHO,),Co -+ 4H20 Triclinic*2(CHO,),Ba,(CHO,),Cu + 4H202(CHO2),Ba,(CHO,),Zn + 4H,O2(CHC),),Ba,(CHO,),Ni + 4H1,0(CH02),Ra,(CH0,),Cd + 2H20.F. S. K. I ~ ( C H O ~ ) ~ S Y (CHO2)ZCu + 8HZO.Prcpionates.Ry R. GAZE (drch. P72ar17t. 229 486-492 ; com-pare Abhtr. 1887 654) .-Calcium propionate crystallises both in long(7 cm.) transparent needles with 3 mols. HzO and in transparentlamine with 1 mol. H,O. barium propionate crystallises with 1 mol.H,O as heretofore accepted. Zinc propionate was obtained in an-hydrous tabnlar crystals ; Renard (Abstr. 1887 654) obtained i t inneedles with 1 mol. H,O. Copper propionate crystallises with 1 mol.H20. Cadmium propionate ci~ystallises in silky opaque laminae,which are stable in air and contain 2 niols. H,O (compare Renard,Zoc. cit.). Magnesium propionate can be obtained i n small crystalswith 1 mol. H,O. Lend propionate was obtained in lamin= whichwere anhydrous (compare Renard Zoc. cit.).A table is given com-pariiig the formates acetates and propionates as to their water ofcry stallisat ion.Ethyl Acetoacetate. By J. U. NEF (Annulen 266,52-138.)-Theauthor has made a very carelul study of the reactions which take placeon treating e t h j l acetoacetate and its sodium derivative with halogens,acid chlorides and. alkyl halogen compounds ; he comes to the ~011-clusion that the course of these reactions can only be satisfactorilyexplained by assuming that etlryl sodacetoacetate has the coristitu tionyepresented by the formula ONa-C Rle:CH*COOEt. l h i s view accountsfor the marked similarity in behaviour between ethyl sodacetoacetateA. G. BORQANIC CHEMISTRY. 141on the one hand and the sodinm derivatives of ethyl succinosuccinateand ethyl dihydroxytereplithalnte on the other; it has been pre-viously shown thatl in the last-named coinpounds the sodium is( lirectly combined with oxysen.An important fact in considering the constitution of ethyl sodaceto-acetate is that this substance interacts with alkyl halogen compoundswith grea,t energy and usually a t the ordinary temperature.Now if,in such reactions as these the sodium is directly displaced by thenlkyl radicle the reaction should be even more energetic in the caseof the coppc~ lead or mercury derivative of ethyl acetoacetate. Asa matter of fact this is not the case ; solutions of the copper and leadderivatives for example do not react wit8h ethyl iodide even a t loo" and do so only very slowly a t 130". This fact alone renders itprobable that no direct substitution of the sodium takes place and astudy of the action of bromine on ethyl sodacetoac:etute proved thecorrectness of this view (see below).It was also found that nosimple replacement of sodium takes place when ethyl sodacetoacetateis treated with acid chlorides or alkyl halogen compounds ; in thecase of benzyl chloride for example there is first formed a veryunstable additive product of the constitutionONa*ChleCl*CH(CH,Ph).COOEt,which immediatelj- loses 1 mol. of hydrogen chloride with formationof ethyl sodiobenzy 1 acetoace tate ONa*CMe:C ( CH,Ph) *C OOE; t ; theIrydi-ogen chloride produced in this way reacts with the two sodiumderivatives now present and to the greater extent with that of thehuhstance having the less powerful acid properties so that ethylbenzylacetoacetate and smaller quantities of ethyl acetoacetate areformed.Some of the etjhyl sodiobenzylacetoucetate also combinesdirectly with a further quantity of benzyl chloride yielding a com-pound of the constitution OKa*C&feCl-C(C B,Ph)z*COOEt which isfinnlly converted into ethyl dibenzylacetoacetate by the elimination ofsodium chloride. Tf t h i s explanation of the reaction is the true one,then the more negative the group introduced into the molecule ofethyl acetoacetate in the first stage of the reaction the larger must bethe proportion of the di-substitn tion product formed ; experimentsfully confirmed this conclusion as will be shown later.Hitherto it has been found impossible to introduce two acid radiclesinto the molecule of ethyl acetoacetate ; the author shows that suchdi-substitution products can be obtained by treating metallic derivative8of ethyl acetoacetate with benzoic or acetic chloride and he discussesai some length the mechanism of these reactions.The constitution of ethyl acetoacetate is next considered ; thebehaviour of this compound with phenylhydrazine (see below) andwith ammonia and amides and the fact that it has distinctly acidproperties all poitit to its being a hydroxy-compound.Ths fact thatethyl acetoacetate and its methyl and ethyl derivatives are notreduced on treatment with sodium in ethereal solution whereas thecliethyl derivative which is a true ketone is almost completely coil-verted into ethyl diethylhydroxybutyrate and a pinacone-like sub-stance which is soluble in alkalis is also strong evidence against th142 ABSTRACTS OF CHEMICAL PAPERS.ketone constitution in the case of the tirst-named compounds. Further-more if ethyl acetoacetate has the ketone constitution ethyl malonatemust have even more strongly marked acid properties ; as a matter offact i t has no acid properties whatever and does not interact withsodium in absence of alcohol; it also differs from ethyl acetoacetatearid the mono-substitution products of the latter in being unacted onby bromine chlorine nitrous acid and fuming nitric acid in the cold.Ethyl acetoncetRte is therefore in all probability ethyl P-hydroxy-crotonaie OH*CMe:CH-COOEt and its mono-substitution productsthe corresponding a-substitution products of ethyl /3-hydroxycrotonate.Thebe compounds show no tautomerism or desmotropism and theabove view of their constitution accounts satisfactorily for all theirreaccicjns; the idea of a labile form may therefore be dismissed asregards these substances.It is interesting to notice to what a great extent the displacementof the a-hydrogen atom affects the behnviour of the hydroxy-groupin ethyl acetoacetate ; when the substituting group is more positivethan hydrogen the product ethyl ethylacetoacetate for example hasmore rnayked alcoholic properties. When on the other hand thesubstituting group is strongly negatit-e the product has a pronouncedacid character ; the acetyl benzoyl and carboxyethyl derivatives ofethyl acetoacetate decompose carbonates although their etherealsolutions do not react with sodium.This fact led the author tostudy the action of sodium on ethereal solutions of various acids ; hefound that in the case of mellitic phthalic succinic and cinnamicacids these is no reaction whilst with benzoic acid and picric acid aslight reaction takes place probably owing to the presence of im-piirities ; an ethereal solution of pure phenol reacts very energetic-ally with sodium.E th y I pheny I-p-h ydrazocrotonate N,H,Ph*CMe C H-C 0 0 E t can beobtained in a crystalline condition by gradually adding phenyl-hydrazine (10 grams) to a well-cooled ethereal solution of ethylacetoacetate (12.5 grams) containing fused calcium chloride thenwabhing the solution with 10 per cent.soda and dilute sulphuricacid successively drying over calcium chloride and evaporating oversulphuric acid; the crude product (16 grams) is spread r3n porousearthenware and then repeatedly washed with light petroleum. Thepure compound (11 grams) crystallises in long colourless needle+,melts at 50" and is very readily soluble in all ordinary organicsolvents except light petroleum ; its solutions rapidly turn yellow,and even when in a dry condition the hydrazide giadunlly changesinto a yellow fluorescent oil. I t is readily decomposed into its com-ponents by concentrated hydrochloric acid and when heated a t 200"i n n vacuum it is converted quantitatively into phenylmethyl-pyrazoloiie.When treated with acetic chloi-ide in well-cooled,etlereal solution it yields an oil which boils a t 24-5-250' under apressure of 350 mm. and has most probably the constitution expressedby the formula C H, C M e.NAc*NPh A c.A compound of the composition C,,H,,NO is obtained in colourlesscrystals when the hydrazo-derivative just described is dissolved inconcentmted sulphuric acid the solution kept for ten minutes anORQAN10 CHEMISTRY. 143then poured into a large volume of water. This substance crystallisesfrom alcohol in compact colourless needles melts at 134" is verystable and is in all probability an indole derivative ; it is only veryslowly acted on by boiling alcoholic potash but when melted withpotash it gives a strong odour of indole ; its alcoholic solution gives adeep-red coloration with ferric chloride.Ethyl phenyl-p-nzocrotonste NPh:N.CMe:CH*COOEt is formedwhen an alcoholic solution of the bydrazo-compound is warmed withyellow mercuric oxide ; it melts a t 51" and is identical with the com-pound obtained by Bender (Abstr.1888 -53) by the action of phenyl-hydrazine OG ethyl a-chloracetoacetnte.The ethyl a- bromacetoacetate prepared by Schonbrodt's method(Abstr. 1&90 %7) is a. pure compound as is shown by the followingf'acks :-When treated with ethyl sodacetoacetate it yields only ethyldiacetosuccinate (see below) and on oxidation with fuming nitric acidin the cold it gives ethyl bromisonitrosoncetate NOH:CBr*COOEt.The product obtained by treating ethyl acetoacetate with bromine asdescribed by Duisberg (Ahstr.1882,1193) is not pure ethyl rpbrom-acetoacetate as was supposed by Hantzsch (Abstr. 1890 1238) andby Steude (Abstr. 1891 742) but is a mixture of approximatelyequal quantities of the x- and y-bromo-derivatives and contains inaddition a litt,le dibromo-derivative and some unchanged ethyl aceto-acetate ; this is proved by the fact that on oxidation with nitric acid,it yields a mixture of ethyl isonitroso- and ethyl brornisonitroso-acetoacetate and also by a study of its behaviour with ethyl sodaceto-acetate (see below). The product obtained by treating ethyl sodaceto-acetate with bromine is also a mixture of the a- and y-bromo-deriva-tives; the formation of both these compounds in this way is bestexplained by supposing that the addit,ion of bromine first takes place,yielding a compound of the constitution ONa-CMeBi-CHBr-COOEt,from which hydrogen bromide is immediately eliminat.ed giving thea-bromo-derivative ONa*CMe:CBr*COOEt ; the hydrogen bromidethus produced acts on a further quanti5 of ethyl sodacetoacetatewith formation of ethyl acetoacetate which is then attackcd by thebromine yielding both the a- and the y-bromo-derivatives.COOEtG (:CMe*OH).CH,*C (OH):CH*COOEt,is formed together with its isomeride ethyl diacetosuccinate andethyl dihydroxyterephthalate when an ethereal solution of ethylbromacetoacetate prepared by the action of bromine on ethyl aceto-acetate (or its sodium derivative) is treated with ethyl sodacetoacetateat the ordinary temperature ; after keeping for two hours the solutionis filtered and the residue repeatedly washed with small quantities ofcold water to free i t from sodium bromide and traces of ethyl sodaceto-acetate.The undissolved substance is a sodium deri\-ative of ethylacetylhydroxyhydromuconatc of the constitutionEth y 1 a-acety l-$'-hydroxy hy dronauconat e,C 0 OE t*C (1 C Me*ONa)*CH,*C ( OH) :C H CO 0 E t ;it is very sparingly soluble in cold but more readily in hot water andit separates fiaom warm alcohol in colourless granular crystals. O144 ABSTRACTS OF CHEIIICAL PAPERS.treatment with dilute sulphuric acid i t is converted into ethjl acetyl-hydroxghydromuconate ; this compound cryst,allises from ether incolonrless needles melts a t about 65" and its alcoholic solution givesa blue coloration with ferric chloride; it is very unstable and onkeeping quickly changes into an oil probably a farfuran derivative,water being eliminated. The formation of an isorneride of ethyldiaceotsuccinate in the above reaction is a fiirther proof that Duis-berg7s ethyl bromrtcetoacetate contains the ybromo-derivative.Ethyl 1 2-metl~ylcarboxyeth~l~yl~rolineacetate,CMe*N H COOEt*C<- CH>C*CH,*COOE' t,is obtained when the sodium derivative just described is boiled witha glacial acetic acid solution of ammonium acetate and the productprecipitated with water ; it crystallises from dilute alcohol or glacialacetic acid in needles melts at 186" and gives the pine-chip reactioni n a very marked manner.Ethyl djacetosnccinate melts a t 88" and is dimorphous ; when crys-tallised slowly i t forms rhoinbic plates but when quickly crystallised,it is obtained in iieeclles ; the crystals are monosjmmetric a b c =0.857% 1 Wi9288 /3 = 73" 53'.A'EIthyl a-tromomethy Zncetoacefate C7HI1O3Br is obtained as soleprodnct when bromine is gradually added to a well-cooled ethereals o h tion of ethyl sodiomethylncetoacetate ; this substance a.nd not the./-derivative as is generally supposed is also the principal product ofihe action of bromine on ethyl methylacetoacetate.It is a colour-less oil boils at 107"under a pressure of 30 mm. (at 121" 50 rnm.).and is not acted on by fuming nitric acid or by bromine in cold chloro-form solution.I t is insoluble in soda and when heated a t 100" forsix hours i n a sealed tuhe it is converted into tetric acid witheliniination of ethyl bromide ; this acid has probably the constitutionrepresented by the EormulaCH2:C(OH)*CMe<Co.o>CMe*C(OH):CH2. 0430Ethyl a-bromethylucetoacetate CsHlaOsBr is formed from ethylethylacetoacetate under the same conditions as those described in thecase of the methyl derivative; it is a colourless oil boiling a t 110"under a pressure of 22 mm. (at L3l0 50 mni.). Its bebaviour withbromine and with soda resembles that of the methyl derivative;when heated at 100" in a sealed tube it yields ethyl bromide andpentic acid the constitution of which is probably analogom to thatof tetric acid.Some experiments are then described the results of which confirmEliou's statement that there is only one ethyl sodacetoacetate.The interadion of ethyl sodacetoacetate and benzoic chloride is thendiscussed and it is pointed out that about 10 per cent.of ethyl di-benzoylacetoacetate is invariably present in the crude product ; theformation of this compound is explained by assuming that an additivr!productl of the constitution ONa.CMeCl*CHBz*COOEt is produced,and that the latter immediately loses 1 mol. of hydrogen chloride a ORGANIC CHEMISTRY. 145the same time (when the double linking is in a sort of nascent state)combining with benzoic chloride to form the di-substitution product ;ethyl sodiobenzoylacetoacetate when once formed that is to say whenthe double binding is no longer nascent does not react with benzoicchloride.Ethy Z dibenzoylacetoacetnte C20H,805 is however best prepared byadding benzoic chloride (150 grams) to the copper derivative ofethyl acetoacetate (50 grams) which has been previously mixed to apaste with pure ether and then heating for a short time on the water-Imth.The yield of the pure compound is 32 grams. It is decomposedby a cold alcoholic solution of sodium ethoxide yielding ethyl benzoate,sodium benzoate ethyl acetoacetate and condensation products andwhen treated with phenglhydmzine it gives beiizoic acid /3-benzoyl-phenylhydrazine (m. p. 16S0) and probably also ethyl acetoacetate.E t h y l triacetylacetate CAc,*COO Et is formed in small quantitywhen ethyl sodacetoacetate suspended in ether is treated with aceticchloride ; it is best prepared by adding acetic chloride to the copperderivative of ethyl acetoacetate suspended in ether.It boils a t 102"under a pressure of 12 mm. (at ill" 22 nim. ; at 116" 29 mm.) with-out decomposition and under the ordinary atmospheric pressure a t212-214" with slight decomposition ; i t is volatile w i t h steam,and doesnot combine with bromine but i t is dccornposed by fuming nitric acidin the cold. It exhibits the same behaviour with sodium ethoxide andw i t h phenylhydrazine as the dibenzoyl derivative just described.B t h y l acetyZca,.bintrical.bozylate COOE t.CAc(COOEt) is formed,together with ethyl acetylmalonate and regenerated ethyl acetoacetate,by the interaction of ethyl sodacetoacetnte and ethyl chlorocarbonateunder the usual conditions.It boils a t 129" under a pressure of29 mm. is volatile with steam is not acted on by cold fuming nitricacid and does not combine with bromiiie ; when treated with sodiumethoxide it is decomposed in to ethyl sodacetoacetate and ethyl carbon-;ite. The ethyl acetylmnlona,te formed i n t'he above yeaction boils a t120" under a presoure of 17 mm. and is identical with the compoundobtained by the action of acetic chloride on ethjl sodiomalonitte ; itdecomposes carbonates and gives a dark-red coloration with ferricchloride in alcoholic solution but its ethereal s o l d o n is not acted onby sodium.E t h y l phenylhydrazine-P-carboxylate NHPh*NH*COOEt is obtainedwheu ethyl acetylc~rbintricarboxylnte is treated with phenylhychzinein ethereal solution ; it crystallises in colourless needles meltinga t 82".A compound of the constitution HgCl*O*CMe:CAc*COOEt isformed together with mercuric chloride and an oily product whenlbcetic chloride is added to the mercury derivative of ethyl aceto-acetate suspended in ether ; it separates from ether in heavy colour-less asymmetric crystals a b c = 1.7712 1 0.83292 melting at105".CorLstitzLtion of 5-PymzoZone Derivatives.-A further iiivestigation ofKnorr's 1 .3-phenylmet~hylpyra~zoloiie has confirmed the views pre-viously expressed by the author regarding its constitution; theexperiments described below together with the fa& that the con146 ABSTRACTS OF OHEMICAL PAPERS.densation product of ethyl acetoacetate and phenylhydrazine has beenshown to be a hydrazo-compound prove that phenylmethylpgrazolonehas the constitution represented by the formula I I >NPh andthat its acid properties are due to the presence of an imido-group.CMe-NHCH-CO9 Me*N Bz1 2 ; 3-Phenylbenzoylmethylpyrazolone >NPh is formedwhen an alkaline solution of phenylmethylpyrazolone is shaken withbenzoic cliloride ; it can a,lso be obtained from the silver derivative ofthe pyrazolone in like manner.It crystallises from dilute alcohol orlight petroleurn in needles melts at 75" and is very readily soluble inall ordinary organic solvents excepl light petroleum ; it is insolublein water dilute acids and a,lkalis and is not acted on by nitrous acid,but is decomposed by alcoholic potash and by concentrated snlph-iiric acid yielding benzoic acid and phenylmethylpyrazolone.>NPh can beobtained by strongly heating phenylmethylpyrazolone or its benzoj 1derivative with berizoic chloride ; it crystallises from alcohol incolourless needles arid melts at 157".CH-COEMe-NBz1 ; 2 ; 4 3-Pheizyldihenzoylmethylpy~axolone CBZ-CO$Me-NHCBx.CO 1 3 4-Phenylmethylbenzoylpyraxolone >NPh is producedwhen the preceding compound is decomposed with cold concentratedsulphuric acid o r with boiling alcoholic potash ; it crystallises fromdilute alcohol in yellowish needles melts at 86" and is not decom-posed by boiling alkalis ; when its solution in potash is shaken withbenzoic chloride it is reconverted into the dibenzoyl derivative (m.p.157").giMe-NBzCBr-CO1 2 4 ; 3-Pher~ylbenzoylb~o~o~~~ethyl~yrazolone >NPh,can be prepared by treating the benzoyl derivative (m. p. 75") de-scribed above with a glacid acetic acid solution of bromine and alsoby shaking an alkaline solution of 1 3 4-phenylniethylbromop~r-azolone with benzoic chloride ; i t crjstallises from a mixture of etherand light petroleum in long colourless needles melts a t 825" and isdecomposed by concentrated sulphuric acid and by alcoholic potashwith elimination of the benzovl group. Y Y II e*NBzCMe CO 1 2 3 4-Phen~lbenzoyldimethylpyrazolone Gv >NPh pre-pared from phenyldimethylpyrazolone crystallises f porn dilute alcoholand light petroleum in long colourless needles melts at 99" and isreadily decomposed by concentrated sulphuric acid and by alcoholicpotash.Bis-1 2 3-phenylbenzoylmethylpymzolone C31H26N.101 obtained bytreating an alkaline solution of bis-phenylmethylpyrazolone withbenzoic chloride separates from glacial acetic acid in colourless,granular crystals melts a t 203" and is insoluble in alcohol ; it is de-composed into its components by alcoholic potash and by concentratedsulphuric acidORGANIC CHEMISTRY. 147When 1 3-phenylmethylpyraxolone ( 5 grams) is treated withsodium met,hoxide and methyl iodide as described by Rnorr it yieldsnot only Knorr's 1 3 4 4-phenyltrimethylpyrazolone (1.15 grams),but also an even larger quantity (1.8 grams) of l:2:3-phenyldi-methylpyrazolone (antipyrin) and 1 2 3 4-phenyltrimethylyyrazol-one (1.4 grams) ; 1 3 4-phenyldimetliylpyrazolone under the sameconditions yields approximately equal quantities of 1 2 3 4-phenyl-trimet,hylpyrazolone (methylantipfrin) and 1 3 4 4-phenyltri-methylpyrazolone. These reactions are easily explained if i t beassumed that not only is the sodium of the iniido-group directlydisplaced but also that an addition of methyl iodide takes place atthe double linking ; this view is borne out by numerous facts.In conclusion the author draws attention to other cases of supposedtautomerism and desmotropism such as those of carbostyril isatin &c.;in his opinion all the reactions of these compounds cau be explainedwithout assuming the existence of labile or pseudo-forms.F.S. I(.Condensation of Levulinic Acid with Aldehydes. By H.ERDWANN (Ber. 24,3201-~204) .-In this paper the author criticisesthe results of Ludwig and Kehrer's investigation (Akstr. 1891,1456)on the action of furfuraldehyde on sodium levulinate and fromthe corresponding results obt8ained by him in the case of benzalde-hyde believes that the compound described as p-furfurallevulinic:acid is in reality 8-furfurallevulinic acid,C,O Hi,.CB :CH*CO*CHz*CH2*COOH.The anticipation of Ludwig and Kehrer that t h i s compound wouldyield derivatives of naphthafurfuran will therefore probably not bei'ulfilled as such cornpounds could only be formed froin thep-derivative.It should however be converted into dilevulinic acid,by the action of hydrochloric acid.H. G. C.Reduction of Ethyl Oxalacetate. By W. WISLICENUS (Ber.,24 3416-3417).-Inactive malic acid is obtained by the reductionof ethyl oxalacetatc with sodium amalgam in acid solution. Themalic acid can be isolated and purified by means of the lead salt ; theyield is 50 per cent. of'the theoretical.Reduction of Acetonedicarboxylic Acid. By H. v. PECIIMANNand K. JENSCH (Ber. 24 3.L50-~'L5.t).-1-3-H?ldr~zyg7utui.i~ acid,OH-CH (C H2-COOH)2 is obtained by reducing crude ace tonedicarb-oxylic acid containing about 75 per cent. of the pure acid (100grams) dissolved in water (1200 c.c.) and neutralised with sodiumcarbonate (180 grams) with 4 per cent. sodium amalgam (900-1000grams) ; the reduction extends over two days the solution being kepta t 0" and a current of carbonic aiihydride passed through ; an excessof hydrochloric acid is then added and the solution evaporated todryness extracted with alcohol and the brown syrup which isobtained converted into the copper salt by boiliug it with diluteJ.B. TI48 ABSTRACTS OF CHENICAL PAPERS.copper acetate solution ; the salt is decomposed by hydrogen sulphideand from the aqueous solution oE the acid a colourless syrup isobtained which ultimately solidifies the yield being 50 grams. Itslowly separates from its aqueous solution in stellate groups ofneedles melts att 95" and is readily soluble in water and alcohol butinsoluble i n other solvents ; on distillation under diminished pressure,glutaconic acid is formed and the same compound is obtained onIioiling it with 60 per cent.sulphuric acid. An aqueous solution oft,he sodium salt gives precipitates with silver lend mercury andcopper salts but not with calcium barium zinc and cadmium salts.The copper salt is a blue crystalline precipitate ; the phenylhydrazide,C,H,O,(PhN,H,)? produced by heating the acid with three times itsweight of phenylhydrazine crystallises from glacial acetic acid inaggregates of delicate needles and melts a t 234-235". The acid isnot identical with that obtained by Simpson (Annalen 133 76) froma-dichlorhydrin and potassium cyanide which is said to melt at 133",(the melting point of glutaconic acid). When /%hydroxjglutaricacid is heated with eight times its weight of fuming hydriodic acid ina sealed tube at 180" €or four hours glutaric acid is obtained.A.R. L.Alkyl Acetonkdicarboxylic Acids. By H. v. PECHMANN and K.JENISCH (Rer. 24 3248-3249.)-1t has been pointed out by Dunsch-inann and v. Pechmann (Abstr. 1891 674) that the alkyl substitu-tion derivatives of acetonedicarboxylic acid having an asymmetricalstructure are unstable ; as however the asymmetry of these deriva-tives can be conceived in a two-fold sense first in regard to the rela-tive positions in the molecule of the substituents secondly in regiirdto the nature of the lsttcr ;tnd as the compoundshitherto examined have complied with both these conditions anattempt was made to prepare ethyl methylbenzylacetSonedicarboxyl-ate a compound which only posse~ses asymmetry in respect to thenature of its substituents. When ethyl acetonedicarboxylate issuccessively ethylated and benzylated or when the order of the;dkylatioii is reversed an oily product which does not show a con-stant boiling point is obtained ; on mixing with Rlcoholic potash thefractions pashing over at every 10' between 215" and 270" under apressure of 40 mm.and decomposing the potassium salts with anacid carbonic anhydride is t h s chief product o d y minute quantitiesof oi1.y acids incapable of solidification being obtained. This resultfavours the view that these acids are only stable when they are sym-metrical both as regards thc position and nature of the substituentalkyl groups.A. R. L.asynimet,ricdBehaviour of Certain Ketonic Acids t o wards SodiumHydrogen Sulphite. By 0. HIKSBERG (Her. 24 3235-3237).-When dihydroxytartaric acid is added to a concentrated aqueoussolution of sodium hydrogen sulphite at 80-100" i t dissolves wit,ht.he evolution of carbonic anhydride and on cooling crystals of t h esodium hydrogen sulphite compound o € glyoxal separate ; attemptst o prepare glyoxalic acid by working at a lower temperature(60-70") were unsuccessful; a small quantity of glyoxal is obtaineORGASIC OH EMTSTRT. 149when nitrotarhric acid is treated in a similar manner. Pyruvic acid.when heated with a concentrated solutJion of' the sulphite in R seaIedtube a t 170" appears to be unaltered; no deconiposition produrtswere recognised.Chloracetic acid dissolves in the sulphite solution;It the temperature of the water-bath; b u t does not yield chlor-acetone ; ethyl aceto8cet:ite remains unaltered even when heated withthe same solution a t 100" for a l o n g time. A. R L.Alkaline Citrates. By T. SALZER (Arch. Pharrn. 229 547-552).-According to the author's rules (Abstr. 1884 Wci) normalsalts contain more or at least as much water of crysta-llisation as thecorresponding acid salts. Heldt however (Amaleri 43 157) statesthat tripotassium citrate crystallises with 1 mol. H20 dipotassiunici trate is anhydrous and monopotassium cit,rate crystallises wit,h2 mols. H,O ; the aut,hor has therefore reinvestigated the alkalinocitrates.Monopotassium citrate is anhydrous when crystallised a t the ordi-nary temperature and dissolves in 4 p r t of hot water and some-what more than 2 parts of cold water; when obtained at a lowtemperature i t crvstalliscs with 2 mols.H20. Dipotassirim citrate isalso anhydrous. kripotassium citrate is soluble in $ p a ~ t of water a t15" ; it c a n be heated a t 170" without loss but at 200' it loses 1 mol.water of crystaJlisat,ion.The author failed to obtainpure disodium citrate. Trisodium citrate crystallises both with 3 andwith 54 mols. H 2 0 ; the fernier crystals dissolve in abont 1;- parts ofwater a t 15" the latier in about 1 part of water at 25" and 5 part ofboiling water. A. G. B.Formation of Uric Acid from Cyanacetic Acid and Carb-amide. By E.l ~ o m ~ s m ( B e y . 24 :+419-3420) .-8rnflll quantitiesof uric acid are formed on heating R mixture of carbamide mid cjan-acetic acid. Cyanacetic acid (0.5 gram) is cautiously heated wit,hcarbamide (2 grams) over a Bunsen b u r n e r a continuous stream ofgas is evolved from the melted mass and on further heatAng themixtiire solidifies. The solid mass is dissolved in sodium hydroxitic thesolution saturated with ammoiiium chloride and ammonia a mixtureof magnesium mixture and ammoniacal silver solution added and thewhole allowed to remain filtered washed with water and the silversalt. decomposed with sodium sulphide. The silver sulphide is filteredoff the filtrate acidified with hydrochloric acid and evaporated to asmall bulk ; the uric acid then separates out.1 gram of cyanaceticacid and 4 grams of carbamidc yielded 20-30 milligrams of pureuric acid. E. C. R.Monosodium citrate is anhydrous.Hydantoi'ns and Bases derived from them. By W. MARCK-WALL) N. NEC'MARK and EL. STELZKER ( B e y . 24 3278-.3298).-Thio-hydanto'ins have been known hitherto only in the aromatic series,having been obtained (Aschan Abstr. 1884,907) by melting togetheraromatic thiocarbamides and amido-acids of the fatty series.No such reaction takes place in the case of the fatty amido-acids150 ABSTRACTS OF CBEMICAL PAPERS.Probably these do not exist in the free state as RCH(NH,)*COOH,but as R.CH<CO:>O. If however an alkaline solution of theacid which donbtless contains the acid in the form of the saltR*CH(NH,)*COOM is treated with a thiocarbimide the reactiondoes occur and both aromatic and aliphatic thiohydantoh wereobtained by dissolving the amido-acid in an equivalent quantity ofconcentrated aqueous potash.and adding an equivalent amount ofthe thiocarhimide in alcoholic solutlion. on adding hydrochloricacid the thiohydantoic acid first separat,es as an oil which rapidlyloses water and becomes converted into crystals of the thio-N Hhy dantoin.NPh-70'"'NH CHMe' prepared from phenjl- Yhenylmethylthioh ydantoi;??,,thiocarbimide and almine is colourless and melts a t 210" ; the yellowsubstance melting a t ItrO" which Aschan described was impure.t,hiocarbimide and glycocine forms white plates melting a t 136' anddissolves easily i n acetic acid chloroform and benzene sparingly inether and light petroleum.U I N(CoH,Me)*(?Orthotolylmet7i~Zthiohydantozn CS< CHlfe from ortho- NH --tolylthiocarbimide and alanine resembles the last-mentioned coin-mound. and nielts a t 198". I - ' N( C,H,Me~)o~oCHG from1 3 ' 4-XylylmethyZthiohydanto~~~ CS<NH-xylyltliiocarhimide (Me NCS = 1 3 4) and alanine forms whiteneedles melts a t 165" and dissojves readily in ether alcohol chloro-form and benzene very sparingly in light petroleum.from 51-naphthylthiocar.bimide and alanine melts a t 242" and is but spar-ingly soluble in most solvents ; i t dissolves readily however in hotacetic acid.Nph'yo from phenylt,hio-N ( ClOH,) yocs<NH- CHMe'a- Nap h t h y [met h y 1 thioh y clan to in,cs<NH - CMe,'Phen y ldimethy lthiohydnntoitb,cwrbimide and a-amidoisobutyric acid forms white crystals melts a t67" and dissolves readily in most solvents but ouly sparingly inwater and aqueous alcohol.Paratolyldimethy lthiohydantozn CS< N(c6H1Me)> CO from Pam-tolylthiocarbimido a n d a-amidoisobutgric acid melts at 85" aud israther more soluble than the preceding compound.Ort 71 otoly Zdim e t h y It hioh y d a d ozn fro m or tho toly 1 th iocarbimide anda-amidoisobutyric acid forms colourless needles melting at 175" andis less readily soluble than t'he para-compound.It dissolves however,in hot alcohol acetic acid chloroform and benzene.NH-CMeORGANIC CEEMISTRY. 151NMenQ 0Me/ hy lthiohy dantoih CS<NH .CHo from methylthiocarbimide~~ ~and glycocine forms colourless needles melting at. 161" ; i t dissolvesreadily in ether alcohol and hot water less readily in cold waterand clhoroform and only very sparingly in light petroleum.NMe* Q 0Uimethylthiohydantoi'n CS <NH CH3fe from methyltbiocarb-imide and alanine forms lustrous rhombic prisms melting a t 166.5",and dissolves readily in all solvents except light petroleum.NMe.(? from methylt hiocarbitnideNH CMe,'Trimethy lthiohy dantoih CS <and a-amidoisobutyric acid forms white crystals melting a t 53" andless soluble than the preceding compound in most solvents but mmeso in light netroleum. U LAllylthiohydantoin CS< TU'(C3H5)'(?0 from allylthiocarbimide andNH - CH2glycocine crystallises only with difficulty. It forms white crystalsmelting at 108"' and dissolves easily in hot water alcohol and aceticacid sparingly in cold water chloroform benzene and lightDetroleum. Lfrom allylthiocarb- N(C,H5) $30NH - CHMe'Allylmeth ylthiohydanLo?n CS<imide an; alanine crystallises still less readily.It forms colourlesscrystals melting a t 83*5" and dissolves readily in alcohol ether,benzene acetic acid and particularly so in chloroform sparingly incold water and light petroleum.Incidentally an improvement on Tiemnnn and Friedlander's mdhod(Abstr. 1882 56) for preparincr a-amidoisobutgric acid is described.The sulphate of this acid C4H,N02,H2S04 + 2 H 2 0 was obtained forthe first time. It forms long pointed lustrous crystals.The thiohydantohs described all show the characteristic propertiesof thiocarbamides.They yield insoluble silver and mercury salts,wliich readily decompose forming the metallic sulphides. Theydissolve i u alkalis arid when the solutions are boiled salts of thecorresponding thiohydantoic acids are formed. But as the firstresult of the action of the alkali componnds of another nature areformed which have not been isolated but derivatives of which havebeen prepared. Tako as an example the methylthiohydantoYnsderived from nlanine. These may react according to either of the" NR'F.'O When boiled withNR*$lOformuls CS< NH-CHMe and sH'C<N-CBMe*potash they react according t o the first yielding salts of methylthio-hydantoic acid.But if they are dissolved in potash and methyliodide is added they react according to the second formula andan take up two methyl groups. This may give SMe*C<imidazolone or the thiohydanto'in may react in yet another form,SHOC<~-!~~ of the second of the two formulae given above,NR.70N-CMe<NR. C -0 152 ABSTRACITS OF CHEMICAL PAPERS.yielding SMe< NRof?o'Je an imidazole.N-CMeI n reality the compoundformed has the last formula for it is different from the substanceCS<NH*CAle that is obtained when the dimethylhydanto'in(derived from a-amidoisobutyric acid) takes up one methyl group underthe same circumstances ; this substance must evidently have theformula SMe-CG NR'(?o and is in fact the other compound thatmight theoretically be formed when the metlhylhydantoYn takes upt w o merlijl groups.The imidazoles described below were preparedI,y treating the methylthiohgdanto'ins derived from alanine with2 mols. each of potash and methyl iodide in dcoholic solution ; theimidazolones by treating the dimethylhydnnto'ins derived from a-amidoisolnutyric acid wit,h 1 mol. each of potash and methyl iodide inalcoholic solution.NR.70N-CMe,'v-Yheti yl-a-metlioxy-~-nzethyZ-~-thiornetl~ylinzidaxole,forms an oil which can only be obtained in white crystals withgreat dificulty ; i t melts a t go" and dissolves I*( adily in most solvents,sparingly in water. The hydwchloride C,zH,4N,S0,HCI formspmall white crystals melting a t 140" and easily soluble i n water andalcohol.The plntinorhloride (C,,H l,N2SO),,H2PtC16 forms yellowish-red crostals melts with decomposition at 213" and dissolves readilyin water sparingly in alcohol. The picrate C,zHl,N,S0,C6E13N307,lorrus yellow needles riielting with decomposition a t 192" and dis-solves sparingly in water readily in alcohol.v- Pa~atolyl-/~-metlty l-a-~nethoxy-~-thiomet~ylim~dazole,resembles the preceding compound ; it forms small white lustrousplates melting a t 109". The Izydyochloride C13H16N2S0,HC1 forms awhite crystalline powder melting a t 123" and is very soluble in water.The pltctinochloride is yellow and decomposes at 210" without melt-ing. The picrate is yellow and melts a t lS0".v- @thoto7 y I-B-meth~t-a-methozy-p-thiomef hylirnidazole,N (C,H,Me) OMeCMe ' SMe.CqN-is more easily obtained crystalline than the two preceding com-pounds.It forms large white plates melts a t 118-120" and dis-solves readily in alcohol ether chloroform and benzene sparingly inwriter. The hydrochloride Cl,H,,N,SO,HC1 is white and melts at120". The plafinochlnde (C,,H,,N,SO),,H,PtCI is orange-red anddecomposes a t 205" without melting. The su7phate melts a t 205ORGANIC CHEMISTRY. 153The yellow picrate Cl3Hl6N,SO,CfiH3N3O melts with decompositionat 200" and dissolves readily in alcohol sparingly in water.up-Dimethyl-a-methox~-~- thiomethylirnidazole,is a liquid.line powder soluble in alcohol insoluble in ether.ide ( C7Hl,N,S0)2,H2PtC16 forms a yellow precipitate.The acid sulphste CTH12N2SC)4 foivms a white crystal-The platinochlor-SMe* C GNPCMe,,is a coloixrless liquid boiling without decomposition at 222-225".The hydrochloride C,,HI4N2SO,HC1 is very soluble in water andalcohol.The platinochloride ( ClrH,,N,SO),,H,PtCI forms reddish-yellow needles melting at 132" and dissolves readily in alcohol,sparingly in water. The picrate C1,Hl,N,SO CfiH3N307 forms dark-yellow prisms melting with decomposition at 174" and dissolves easilyin alcohol and ether sparingly i n water.NPh.70Y- Pheny 1-P-dimethy 1 -p-thionzethy limidazolone,u-Paratoly 1-P-dimeth y I-p- t}Liomethylimidazoloize,N(C6H4Me)*y0 S Me CGN- CMe,'forms a colourless oil which decomposes when distilled. Thesulphate melts at 210". The platinochloride ( C,,H,6N,so),,H,PtC1fi,forms dark-red needles melting at 152".The picrate,CisH16N2 s 0 Cf&N307,forms yellow prisms which decompose at 190".U - Orthotolyl-~-d.imethyl-p-tkiomethylimidazolo~~e,N ( C6H4Me)*Q 0SMe*CGN-CMe,'is an oil which decomposes when distilled. The white hygroscopich~ydrochloride C,3H16N2S0,HC1 melts at 118" ; the acid sulphats at308". The platinochloride ( C,,H16N8 0) ,,H,PtCI is red dish-yellow,and dissolves readily in alcohol and ether sparingly i n water. Thepicrate Cl,Hl,N2S07C~H3N307 forms yellow prisms melts withdecomposition at 212" and dissolves easily in alcohol sparingly inwater.is anoil. The yellow platinochloride ( C,HI&ZSO)Z,H~P~CI~ melts at 150" ;the white acid sulphaie C7H13N2S0,H,S0 at 138".Tri-sulphones. By E.LAVES (Arch. Pharm. 229 448-456 ; compareAbstr. 1889 1232).-Methyldiphenylsulphone phenyl sulphide(Abstr. 1890 988) melts at 176" ; to convert it into the correspond-ing trisulphone which melts at 213" (compare Zoc &.) it is dissolvedin an alkali saturated wit!i carbonic anhydride and poured into per-manganste solution ; the oxidation is complete in two days.up- Trinzethpl- p-thiomet Jy limidazo lone SMe-C<N-CMc N M q OC. F. B.Chemical and Physiological Relations of Sulphones.VOL. LXiI. ?154 ASSTRAOTS OF CHEMICAL PAPERS.Ethyl trithioacetate CMe(SEt) is obtained by heating ethylmercaptan ( 3 mol. proportions) with 20 per cent. aqueous solution ofsodium hydroxide ( 5 mol. proportions) and methyl chloroform(I+ mol. proportions) in a strong flask at 100" for two or three days.It is a thick oil of unpleasant odour.~rietl~ylsulphonernethylmethans CMe( SO,Et) is prepared by dis-solving the foregoing compound in a little benzene and shaking it witha 3 per cent permanganate solution containing half its volume of 3 percent.sulphuric acid the mixture being kept cool until the end of thereaction when it is slightly warmed and the benzene removed by acurrent of air; the manganese dioxide is dissolved by the addition ofsulphurous acid when the trisulphone remains as an amorphous,white powder. I t crystallises from hot alcohol i n vitreous whiteneedles which melt at 140"; i t dissolves easily in chloroform butnot in cold alcohol or ether; at 40" it dissolves in 200 parts ofWater and at 15" in 500 parts. It is indifferent to alkalis and isvery stable ; its taste is very bitter resembling that of quinine.3 grams of the powdered sulphone were administered to a dog of9 kilos.body weight ; slight symptoms of lassitude were exhibited atthe beginning of the second hour and lasted for half an hour butthere was no further important change ; the urine of the next nightwas found to contain 0.9 gram of unaltered trisulphone. The authoradministered a dose of 1 gram t o himself and experienced very slightlassitude but his pulse fell in the course of an hour from 75 to 60,and after three hours returned to 72; another dose of 1.5 grams,taken four hours after the first intensified the action ; the urine of thefolloviing 24 hours contained 0.85 gram of the unaltered trisulphone.It would appear that the greater part of the trisulphone is not de-composed in the organis-m and is therefore without action.Ethyl Acetothienoneoxalate.By A. ANGELI (Gazzetta 21,4$4-449).-Part of this paper has alppeared before (Abstr. 1891,550).Acetothii'noneoxcr Zic acid C8H,*CO*CH.CO*COOH is obtained bydissolving ethyl acetothihoneoxalate (5 grams) in concentrated snlph-uric acid (40 grams) and heatling the mixture for a few minutes on thewater-bath. The salt is readily soluble especially on warming. Onpouring the product into much cold water a bulky precipitate ofminute rose-coloured crystals falls ; this is recrystallised from dilutealcohol precipitated several times from its solution in ethyl acetateby light petroleum and finally crjstallised from boiling benzene.The Emall yellowish needles thus obtained turn intensely yellow at150" become reddish-brown at 1'70" and melt with evolution of gasat 180".The acid dissolves with effervescence in alkali carboilates ;it is precipitated from the solution thus obtained by hydrochloricacid but not by acetic acid. It is readily soluble in alcohol and ethylacetate less so in water only sparingly in benzene and chloroform,and almost insoluble in light petroleum. The solution of theammonium salt gives an orange-yellow precipitate with silver nitrate,white with mercuric chloride pale yellow with lead acetate green,soluble on heating with copper sulphate yellowish with bariumA.G. BORGANIC CHEMISTRY. 155nitrate and dark red wihh ferric chloride solution.pose the acid into acetothienone and oxalic acid.Alkalis decom-W. J. P.Bromine Carriers. By W. MACEERROW (Bey. 24 2939-2947).-The author has already determined that the extraordinary activityof the halogen carrier when oiie nitro-group is present in the benzenering entirely fails if two or three nitro-groups are present. I n thelatter case the bromine displaces the nitro-group in preference to a.hydrogen atom and then the influence of the halogen carrier inducesfurther brominat ion.Metadinitrobenzene when treated with bromine alone at 230-235",gives together with a large proportion of unaltered material sym-metrical tetrabromobenzene and metabromonitrobenzene.The actiongoes further in the presence of ferric chloride. Dinitrobenzeiie(10 grams) bromine (1 mol.) and ferric chloride (2 grams) wereheated for 14 holm at 180". The product consisted of a large quan-tity of unaltered dinitrobenzene with some perbroniobenzene. Whenbromine ( 3 rnols.) and 8-10 grams of ferric chloride are employedand the mixture heated for 24 hours at 180-190" and then for 15hours at 220" the product contained hexabromobenzene chloropenta-bromohenxene dic12lorotetl.abro?i~o~e~zene7 and some unchanged dinitro-benzene. The two new compounds cry stallise in snow-white needles,we very like hexabromobenzene and are soluble in alcohol verysparingly so in hot ether but easily in boiling acetic acid and benzene.When heated on a watch glass they sublime without melting ; heatedin a capillary tube dichlorotetrabromobenzene melts at 277-279",chloropentabromobenzsne at 294-295".Dichlorotetrnbromobenzeneis the more easily soluble and hexabromobenzene less soluble inbenzene.Since chlorination takes place when ferric chloride is used as 8bromine carrier the author has employed ferric bromide. Dinitro-benzene (10 grams) was heated for 20 hours at 180-190" with ferrousbromide (5 grams) and bromine (3 mols. plus the calculated quan-tity to form ferric bromide). The product consisted of unaltereddinitrobenzene a minute quantity of a compound melting at 40-50",and hexabromo benzene.Symmetrical trinitrobenzene when heated with bromjne (3 mols.)for 50 hours at 230-235" gave dibromoritrobenzene and an oilyproduct which was not examined.An attempt was then made toprepare mouobromodinitrobenzene by heating trinitrobenzene withbromine (1 mol.) for one hour at 200-210"; a large quantity ofunaltered trinitrobenzene was recovered and a product obtainedwhich melted at 75-76" and seemed to be the monobromo-com-pound mixed with some dibromonitrobenzene. With bromine andferric bromide trinitrobenzene yielded hexabromobenzene. Withbromine and ferric chloride it gave a new tetrachlorodibromobenzene.TetrachlorodibromoZ,enxenB is obtained by heating trinitrobenzene(5-3 grams) with bromine (12 grams) and ferric chloride (5-6 grams)at 230-235" in a sealed tube. The product is washed with water asmd1 quantity of trinitrobenzene extracted with alcohol and the re-sidue crystallised from hot benzene. It crystallises in beautifnl17L 156 ABSTRACTS OF CHEMICAL PAPERS.white needles melts at 241-2242' is insoluble in alcohol sparinglysoluble in hot ether and somewhat easily so in boiling benzene andwetic acid.When heated on a watch glass it sublimes withoutmelt in g.a-Nitronaphthalene and bromine behave in the way already de-scribed by Guareschi (AnqLaZen 122 184). The presence of ferricchloride seems t o be without influence on the reaction.Picric acid gives with bromine alone and in the presence of ferricbromide orthobromorthoparadinitrophenol melting at 116.5". Withferric bromide the reaction is complete in 12 hours at 100" ; without,it requires 20 hours heating at 160-170" and a t this higher tern-perature some tetrabromoquinone is formed.Bromodinitrobenzene [Br NO NO = 1 2 41 is almost un-altered when heated with bromine and ferric bromide for 14 hours at130-140".A small quantity of hexabromobenzene is formed,how ever.Pyridine when treated with bromine and ferric chloride yieldsdibromopyridine.Metanitrobenzoic acid when heated with bromine and ferricbromide for 10 hours a t 130-140" is for the most part unaltered.Since in the above experiments chlorinated compounds are obtainedwhen ferric chloride is employed as a bromine carrier the author hasexamined the action of ferric chloride alone on dinitrobenxene. At180" no action takes place and at 200-910" the tube burst with aviolent explosion.On performing the experiment i n open tubes itwas observed that at 210" gas was evolved and at 230" the evolutionof gas was very violent. The gas was found t o be a mixture of carb-onic anhydride nitrogen hydrogen chloride and chlorine and theresidue consisted of carbon ferric chloride ferrous chloride and ferricoxide. E. C. R.Condensation Products of Ally1 Alcohol with Methyl-benzenes. By G. KIUEMER and A. SPILKER (Ber. 24 3164).-In their paper on the condensation products of allyl alcoholwith methylated derivatives of beiizene (A bstr. 1891 1462) t h eauthors overlooked the fact that an oily hydrocarbon of highboiling point was obtained by Baeyer (this Journal 1873 885)by the condenaath of allyl alcohol with mesitylene by means of con-A.R. L.Bromo-derivatives of Carvacrol. By G. MAZZAI~A and G.PLANCHER (Gazzetta 21,470-4'72) .-Dibromocareacrol [ Br Pr Br =1 2 31.-Carvacrol (50 grams) is dissolved in glacial acetic acid(50 grams) cooled and bromine (107 grams) dissolved in glacialacetic acid (120 grams) slowly added ; the product is now poured intomuch water and the heavy oil which separates is steam-distilled.The pure substance is thus obtained as an oil which does not solidifyat - 18". On nitration dibromocarvacrol yields dinitrocarvacroltogether with much resin. The benzoyl derivative of dibromocarvacrolis obtained by heating it a t 160" with benzoyl chloride. The productis washed with potassium carbonate solution and on repeated crystal-lisation from alcohol and light petroleum is obtained in cdourlesscentrated sulphri<- acidORGANIC CHEMISTRY.157pamllelopipedons melting at 97-98-5". The substance is very solublein light petroleum less so in alcohol. When heated with alcoholicpotash i t yields benzoic acid and the potassium salt of dibromo-cgmenecarboxylic acid. W. J. P.Behaviour of Carvacrol towards Reducing Agents. By E.BAXBERGER B. BERLI$ and L. STRASSER (Ber. 24 3208-3212),-Neither phenol nor carvacrol is acted on by alkaline reducingagents but the latter is attacked by phosphorus and hydriodic acid ah225-235O with formation of a gaseous hydrocarbon apparentlypropane and an oil consisting mainly of hydrocarbons. The latter,after repeated fractionation was resolved into seven fractions which,with the exception of the two largest appear t o be mixtures of hydro-cymenes of different composition containing also in some casestoluene.The two chief fractions boil at 162-163" and 165-168"respectively and are mobile pleasant-smelling colourless liquids,which in many respects closely resemble menthene. The lattercompound however readily combines with 1 mol. HCI whilst thefraction 162-163" only combines with one-sixth of that amount,and is therefore probably a mixture of several tetmhydrocymenes oneof which may possibly be identical with menthene.Attempts have also been made to reduce phenol by electrolysing itssolution in fused potash but they failed owing to the difficulty offinding any material which would resist the combined action of thefused potash and the electric current.By the electrolyfiis of a solutionof phenol in potash and a little water the authors obtained inaddition to salicylic acid a small quantity of xanthone,C6H4<$6> CSH4. H. G. C.Preparation of Primary Amines by means of PotassiumPhthalimide. By S. GABRIEL (Bey. 24 3104-3107).-Potassinmpht,halimide has been shown to react with halogen derivatives of thefollowing classes of compounds :-Hydrocarbons nitro11 ydrocarbons,nitriles alcohols and alkoxy-derivatives of phenols ketones andethereal salts. So far only primary halo'id derivatives have beenshown t o react excepting picryl chloride CsH3(NO2),C1 and desylbromide CKPhBr-COPh but it is probable that the halogen in thesetwo compounds is rendered more easily replaceable by the neighbour-hood of the negative gronps (GO) and (NO,).To ascertain ifsecondary halo'id derivatives react at all with potassium phthalimide,the action of normal propyl bromide has been compared with that ofisopropyl bromide. The latter substance does react but mnch lessreadily than the normal compound.Normal propyl bromide (6 parts) was heated with potassiumphthalimide (4 parts) for five hours in a sealed tube at 150-160".The product was boiled with water ; propylphthalirnide,C8H4O2:N*CH2*C €€,Me,separated on cooling and was obtained by crystallisation from smal158 ABSTRACTS OF CHEMICAL PAPERS.quantities of a.lcoho1 in colourless prisms or plates melting at 66" andboiling at 282-283" under a pressure of 756 mm.Isopropyl bromide was heated in the same way with potassiumphthalimide for seven hours at 160-170" but the potasRium salt WRSnot attacked.The tube was then heated for eight hours at 190". Onopening it an escape of propylene was observed. The contents wereboiled with water t o expel the excess of bromide and the insolubleresidue powdered repeatedly treated with diliite aqueous soda andrecrystallised from small quantities of warm alcohol ; isopropyZphtha1-imide C,H,O,:N*CHMe was thus obtained in long colourless needlesmelting at 85" and boiling at 272-273" under a pressure of 256 mm.Since isopropylphthalimide is easily converted into isopropylamine,the above-mentioned reaction of isopropyl bromide will afford the mostconvenient method of preparing the amine which has hitherto beenobtained only by the reduction of isopropylcarbamine.Oxidation Products of Paramidophenetoil (Paraphenetidine).By W.KINZEL (Arch. Pham. 229 329-355).-The specific gravityof paramidophenetoll is 1.0613 at 15" and its boiling point is254-2-254.7" (corr.) at 760 mm. ; Liebermann and Kostanecki givethe boiling point as 253" (Ber. 17 876; Abstr. 1884 1146) andelsewhere (Phamn. Centr. 1890 6 66) it is given as 242.5".Seidel (Abstr. 1890 490) has shown that the dye obtained byoxidising orthnmidophenol is triphenodioxazine C,sH,oN20,.By oxidising paramidopheneto'il a brown colouring matter is ob-tained which has the formula C2iH2,N205 arid yields evidence ofthree ethoxyl groups when treated by Zeisel's method; it maytherefore be regarded as trietho~~tl.ii~henod~oxuzine C19H7( OE t),N,O,but further investigation of the matter is required.It is bestobtained by heating a solution of paramidopheneto'il (41-1 grams)with sulphuric acid (83 grams) water (500 c.c.) and tt 3 per cent.solution of hydrogen peroxide (680 grams) at loo" and after somedays evaporating with more sulphuric acid and hydrogen peroxideuntil no more carbonic anhydride is evolved; the crystals whichseparate are boiled several times with much water and finallydigested twice with 300 grams of alcohol a t GO". 134 grams ofpararnidophenetoY1 yield 57 grams of the dye. The new compoundforms a cinnamon-brown crystalline powder which partially sublimesin iridescent brown needles.It is a feeble base and with concen-trated mineral acids yields violet 01' blue salts which are soluble inexcess of the acid with an intensely blue colour ; when such solutionsare diluted the original compound is precipitat,ed unchanged.1 milligram of the compound will impart a sky-blue colour t o 1000C.C. of concentrated sulphuric acid. Triethoxytriphenodioxazine dis-solves in about 900 parts of alcohol more easily in xylene benzene,aniline and chloroform and most easily in glacial acetic acid fromwhich it will crystallise and in pyridine; in water and ether it isalmost insoluble. The acetyl derivative is of uncertain composition ; itappears to contain more acetyl than would suffice to replace the threeethoxyl groups. The platinochZoride is unstable and dissolves insulphuric acid with a blue colour.The leuco-base C,,H,,N,O ob-C. F. BORGANIC (IHEMISTRF. 159taincd by heating the dye with xylcne and phenylhydrazine (compareSeidel Zoc. cit.) crystallises in microscopic white needles which areconverted into the original dye during the process of drying. ThehydrochZoride C2,H2,N20,,2HCI forms crystals which are violet byhansmitted light and nearly black with a greenish lustre by reflectedlight.Quinone carbonic anhydride acetic acid oxalic acid and resinoussubstances are also produced by the oxidation of paramidophenetoxl ;when the oxidation is effected by potassium permangannte in the cold,the yield of carbonic anhydride and quinone is much less and parazo-pheneto'il melting at 159" (Beilstein Handbuch gives 157" and 160")is produced to a considerable extent.This is the product of theoxidation which gives a blood-red colour with sulphuric acid and theauthor attributes the red colour of the earlier samples of commercialphenacetin to the presence of this substance.From the mother liquor of the permanganate mixture from whichthe parazophenetojl had crystallised out brownish needles of a cma-pound CuH,,N,03 + H,O were obtained; these melted at 178" andtheir formula corresponds with that of parazoxypheneto'il. As thissubstance has not yet been described the author prepared it (seebelow) and found that the crystals melting at 178" are not identicalwith it ; so the constitution of the said ci-ystals is still uncertain butinasmuch as they give the same carmine-red colour with fused chloralhydrate as azoxy-compounds including parazoxypheneto'il generallydo there is strong evidence that they are paroxyazopheneto'il.Paraxoxypherzetoi'l C16H,,N20 is prepared by reducing paranitro-phenetoil (5 grams) in 95 per cent.alcohol (100 grams) with 10 percent. sodium amalgam a t lo" keeping the mixture at 0" for twohours with frequent shaking. When recrystallised it forms bright-yellow tables which melt at 136.6" (uncorr.) and dissolve easily inhot alcohol.Yarahydrazophenetoil obtained by reducing parazophenetoil withammonium sulphide in alcohol cryfitallises in white needles whichmelt at 118-119".The red colour of commercial carbolic acid is probably to be attri-buted to the preseiice of the colouring matter described in this paper.Action of Nitric Acid on Dimethylorthanisidine (Dimethyl-orthomethoxyaniline).By P. VAN ROMBURGH (Compt. rend. 113,505-508) .-Grimnux and Lefhvre o,btained a substance me1 ting at135" by heating dimethylorthanisidine with ordinary nitric acid and,when nitrous vnpours appeared immediately precipitating with water.They gave to this compound the Eormnla01Sle-C6H2( N0,),-NMe*CH2-N02(Compt. Tend. 112 727). This result appears to differ from what hasbeen observed in coiinection with other aromatic amines bv the authorA. G. B.(Rec. trau. Clzim. 3 409) and confirmed by Gattermark (Ber. 18,1482).The author has prepared the product melting a t 135" by the methodgiven by Grimaux and Lefevre. It contains 22.2 per cent.of nitrogen 160 ABSTRACTS OF CHEMICAL PAPERS.a substance of the above formula would contain 19.58 per cent.When boiled with phenol the solution becomes red and on the addi-tion of alcohol a reddish-orange product is obtained melting at 168".The author has shown that nitramines under t,hese circumstances havea nitro-group displaced by hydrogen (Rec. trav. Chim. 5 241); henow finds the fiame reaction to occur with nitrosamines. The orange-red product is also obtained on boiling the nitramine of dinitro-methylorthanisidine with phenol.O~~e.C6H,(NOz)zgNHMe.To prove that the substance melting at 135" has the compositionOMe~C6H,(N0,),~NMe." the author has prepared it from the corre-sponding nitramine certainly containing only one methyl group.Thepreparation melts at 135" and has the same charact,ers as the substanceprepared by the method of Grimaux and Lefavre.Phenacetin. Metethoxyorthophenylenediamine. By W.AUTENRIETH and 0. HINSBERG (Arch. Pharna. 229 456-467.)-Todistinguish between antifebrin antipyrin and phenacetin the sub-stance is boiled for a short time with 10-12 pcr cent. nitricacid ; under these conditions phenacetin colours the solution yellow t oorange and an intensely yellow nitro-derivative crystallises on cooling.Orthonitropkenacetin,nT0,.C6H,(OEt).NH*COMe [OEt NO NHCOMe = 4 2 11,is prepared as described above. It crystallises from water in long,soft silky yellow needles melts at 103" and dissolves in hot water,hot dilute alcohol absolute alcohol ether and chloroform.Whendissolved in hot alcohol and boiled for a short time with rather morethan the theoretical quantity of potassium hydroxide i t is convertedinto orthonitrophenetidine N02*CsH3( NH,) OOEt [ OE ti NO NH =4 2 13 which crystallises as the solution cools in brilliant red,lustrous prisms melts at 113" and dissolves in hot alcohol ether,and chloroform.Netethox yon! hopken y Zenediamine C,H,( NHJ ,-OE t [ OE t (NHJ= 4 2 11 is prepared by reducing orthonitrophenetidine withsiac-dust in boiling alcoholic soda; the frothing of the solutionindicates the end of the reaction ; the liquid is filtered and evaporatedin hydrogen; the residue is treated with a little water whichseparates the diamine as a brown oil ; this is washed with water driedon a porous plate and distilled.The new compound when freshlydistilled forms long white slender needles which rapidly resinifyand become red or brown in air. From ether it crystallisea inbrilliantly lustrous greyish-white lamina? which are pretty stablewhen dry. It melts at 71-72" and distils between 294" and 296" ; itdissolves partially in water and easily in alcohol ether and chloroform ;it is a fairly strong base turns litmus blue and forms crystalline saltswith bibasic acids of which the szdphate and oxalate are described.Its composition is a.s follows :-W. T.Metethoxy dih ydrox y pzcinozalineOEGANIC CHEMISTRY. 161is prepared by heating metcthoxyorthophenylenediamine with excesaof oxalic acid in an oil-bath at 140-150" for half an hour (com-pare Annalen 237 327) treating the product with sodium hydr-oxide solution filtering and precipitating the quinoxaiine from thefiltrate by strong hydrochloric acid.It crystallises from alcohol inslender pale-yellow needles melts above 280° and dissolves sparinglyin cold water and alcohol but hardly at all in ether. The sodiumsalt was obtained.Metethoxydiacety loorthophe fiylenedianzine,OEt*c6H3(NHAc) [OEt (NHAc) = 4 2 11,obtained from the dinniine and acetic anhydride crystallises fromwater in lustrous colourless prisms which melt at 189" ; it dissolvessparingly in cold water but rather better in hot water alcohol andether. The coyresponding dibenzoyl derivative OEt*C6H3(NHBz),[OEt (NHBz) = 4 2 11 is obtained by shaking an aqueoussolution of the diamine with benzoic chloride and excess of sodiumhydroxide ; it crystallises from alcohol in slender white needles,melts at 191-192" and is insoluble in water but somewhat freelysoluble i n hot alcohol.M e t e t h o z y d i ~ h e n y l s u ~ ponortho~heizy lenediamilze,OEt*C,H3(NH*SO2Ph) [OEt (NHSO,Ph) = 4 2 11,is obtained when the diamine is shaken with phenylsulphonicchloride and sodium hydroxide (compare Abstr. 1891 49) ; the pro-duct is dissolved in dilute sodium hydroxide solution and reprecipi-tated by strong hydrochloric acid ; it crysta,llises in slender whiteneedles which welt at 159-160" and dissolves in alcohol and ether,but not in water.The diethyl derivative OEt-CsH,(NEt*S02Ph),,formed by heating the diphenylsulphone compound with excess ofethyl iodide and sodium hydroxide in a reflux apparatus crystallisesin slender needles and melts at 121". A. G. B.Action of Diazobenzene on Acetonedicarboxylic Acid. ByH. V. PECHMANN and K. JENLSCH (Bey. 24 3255-3260).-The actioriof diazobenzene salts on certain fatty compounds containing amethylene group the hydrogen atoms of which are displaceable doesnot always give rise to compounds of the same type for example,Japp and Klingemann (Trans. 1888 521 538) showed that theso-called benzeneazoacetone from acetoacetic acid and diazobenzencchloride is pyruvaldehydrazone ; whilst Beyer and Claisen (Abstr.,1888 827) obtained azo-compounds by the action of diazobenzenechloride on derivatives of acetone.Disbenzeneazoccetone CO (CH,*N,Ph) is produced when crudeacetonedicarboxylio acid (50 grams) is dissolved in water (5 parts)cooled t o 0" a solution of diazobenzene chloride (2 mols.) carefullystirred in and sodium acetate added ; the red precipitate is collected,dried washed with benzene and crystallised from dilute alcohol whenit separates in stellate groups of yellowish-red needles and melts at175-176".It has both acidic and basic properties in a slight degree,and dissolves in concentrated mineral acids with a violet colour. O162 ABSTRAOTS OF OHEMIOAL PAPERS.adding concentrated hydrochloric acid to its almholic solution small,blue needles separate which become red on exposure to the air; itis soluble in boiling sodium hydroxide solution ; it can be reduced bytin and hydrochloric acid and when heated with an equal weight ofphenylhydrazine at 120" f o r half an hour it yields the hydrazone,NHPh-N:C( CH,*N,Ph) which crystallises in hexagonal plates meltsat 166" and dissolves in concer;trated sulphuric acid with a greencolour.When the hydrazone is boiled with 3 to 4 times its weight of -N Ph-IN acetic; anhydride thepym.de derivative CMe<C(N2pll) >C CH,*N,Ph,is formed ; this crystalliscs from light petroleum in lustrous goldenplates and melts at 125". I n conclusion attention is dr.awn to thefact that the above-described azo-compound is quite distinct from thecompound Cl5HI4N4O obtained by Bamberger and Wulz (Abstr.,1891 1449) by the action of acetone on diazobenzene chloride in thepresence of alka,li.A. R. L.Action of Phenylhydrazine on Acetonedicarboxylic Acid.By H. v. PECHMABN and I(. JENISCH (Bey. 24 3252-3255).-Whena mixture in molecinlar proportions of crude acetonedicarboxylic acid,dissolved in water (8 parts) conccntrated hydrochloric acid andphenylhydrazine is heated on the water-bath f o r several hours andsodium carbonate is added to incipient turbidity met,hglphenyl-pyrazolonecarboxylic acid (Abstr. 1891 673) separates after a timein crystals and a further quantity is obtained on adding sodiumcarbonate to the filtrate. When the last-mentioned acid is heated at160" and then distilled under a pressure of 100 mm. Knorr's methyl-phenylpyrazolone passes over.When crude acetonedicarboxylic acid (50 grams) is dissolved in a,little water neutralised with sodium carbonate cooled to O" andtreated with a solution of phenylhydrazine hydrochloride (2 mols.) inwater (400 grams) carbonic anhydride is evolved and yellowishneedles separate ; the substance is insoluble in cold water but solublein the hot liquid and is perhaps the pheiaylhydrazine salt of the hydr-uzone clf ucetoacetic acid N2HPh:CMe*CH,*COOH,N2H,Ph. It remainsunaltered for several days in the presence of water but in the drystate decomposes with the evolution of carbonic anhydride yielding anoil of disagreeable odour; when the latter is dissolved in dilute hydro-chloric acid reprecipitated with alkali and dissolved in 50 per cent.alcohol the addition of alcoholic oxalic acid causes a precipitate ofphenylhydrazine oxalate whilst acetonephenylhydrazone boiling at195-200" (20 mm.) can be extracted from the filtrate by means ofether.A. R. L.Symmetrical Bisphenylhydrazone of Mesoxaldehyde. ByE. BAMBERGER (Ber. 24 3260-3264) .-Pyruvaldehydephenyl-hydrazone is not the sole compound formed from acetoacetic acidand diazobenzene chloride (see Japp and Klingemann Trans.,1888 538) the author having separated a compound C15H,JJ"0,melting at 134-135" identical with that recently described by him-self and Wulz (Abstr. 1891 1449) by allowing the benzene filtratORGANIC CHEMISTRY. 163from the crystals of the pyruvaldehydrazone to evaporate treating t h etarry residue with alcohol and finally crystallising from boilingalcohol.The following facts prove that this compound is InesozaZde-h~debis~herL~Zhydrazone CO (CH:N,HPh),. When an aqueous solutionof acetoacetic acid (1 mol ) is treated at 0" with one of dinzobenzenechloride (2 mols.) and a large excess of 20 per cent. sodium hydroxidesolution cautiously added the mesoxaldehydebisphenylhydrazone isprecipitated; it is the chief product and t h e same compound isformed when a concentrated aqueous solution of diazobenzenechloride (1 mol.) is added to pyruvaldehydrazone (1 mol.) dissolvedi n alcohol. The azo-derivative C15H,4N40 obtained by V. Pechmannand Jenisch (preceding abstract) from acetonedicarboxylic acid isformed in small quantities simultaneously with the isomeric mesox-stldehydebisphenylhydrazone and the further investigation of it isbeing carried on by the auihor.A. R. L.Action of Oximes on Diazo-compounds. By J. BIN (Ber. 24,3418).-0n adding diazobenzene chloride in aqueous solution t o benz-aldoxime dissolved in soda a volnminons precipitate is formed whichquickly becomes dark yellow; the compound crystallises from amixtare of alcohol and ether and is colourless when pure. It tirob-ably has the formula PhN,-O-N:CHPh and is to be .regarded eitheras an ether or a8 an hydroxylamine anhydride derivative. On treat-ment with dilute hydrochloric acid benzaldehyde and diazobenzene-imide are obtained.Similar compounds are formed from isobenzaldoxime acetoxime,and ethylaldoxime and as other diazo-derivatives may be substitutedfor the diazobenzene chloride the reaction appears to be a generalone. J.B. T.Molecular Transformations of the Aldoximes. By R.BEHREKD (Bey. 24 3088-3090) .-The author (Abstr. 1891 1032)has obtained a- and P-~iaranitrohenzaldoccimes by treating dinitroso-paranitrobenzyl with potash and found that while the p-oxime isconverted into the a-variety by the action of hydrochloric acid on itsethereal solution the a-oxime undergoes no corresponding change. Henow finds that as Goldschmidt has informed him by letter the latterchange does take place when an ethereal solution of the a-oxime issaturated with hydrogen chloride whereas t o convert the p- into thea-oxime the ethereal solution of the former should be treated withonly a moderate amount of hydrogen chloride.Synthesis of Weselsky's Resorcinol Blue.By R. NIETZK~(Rer. 24,3366-3369 ; compare Abstr. 2890,156).-Resazurin is pre-pared by dissolving niti~osoresorcinol and resorcinol in molecular pro-portion in alcohol ; the solution is cooled mixed with finely-dividedmanganese dioxide (1 mol.) and sulphuric acid (2 mols.) dilutedwith an equal bulk of water is slowly added the liquid becomescherry red and as soon as a drop brought on to filter paper givesa pure blue coloration with ammonia the manganese dioxide isfiltered off and the compound precipitated with water ; on treatingC. F. B164 ABSTRACTS OF CHEMICAL PAPERS.the product with soda green crystals of sodium resazurinate areformed.The mother liquid contains sodium resorufinate. Wesel-sky's me thad of preparing resazurin consists in treating resorcinolwith a mixture of nitrous and nitric acids; the nitrosoresorcinol,which is probably first formed immediately condenses with the excessof resorcinol whilst the nitric acid acts as an oxidising agent and isreduced to nitrous acid.N*O The author suggests the formula CsH,0<-O>C,H3*OH [O:N 0= 1 3 4 ; OH 0 0 = 1 3 41 for resazurin which differs fromresorufin inasmuch as it contains the quinonoxime group instead ofthe quinonimide radicle ; the objection that the formula representsthe compound as a ring consisting of 7 atoms may be met by writing-the oximido-group O:N*H with a pentavalent nitrogen atom.I IJ. B. T.Aromatic Secondary Chlorocarbsrnides and Tetra-substi-tuted Carbamides. By S. v P ~ ~ (Ber. 24 2905-2930).-The author has prepared a number of new aromatic derivatives ofcarbarnide.Thiodiphenylcarbamic chloride S<c6H4>N.COCl is prepared by CJ3-4heating thiodiphenylamine (10 grams) dissolved in benzene (250grams) with twice the theoretical quantity of a 20 per cent. toluenesolution of carbonyl chloride for 2+ hours on the water-bath. Theyield amounts to 75 per cent. of that required by theory. It crys-tallises from hot alcohol in small pale-yellow lustrous prismaticneedles from toluene in large well-formed greenish prisms and meltsat 171-172'. The crystals belong t o the monosymmetric system ;a :'b c = 2-3615 1 1.4465.I t is sparingly soluble in alcohol andether easily so in hot benzene and toluene sparingly in the cold.At 17.5" one part dissolves in 219 parts of alcohol (96 per cent.) andi n 34 parts of benzene.Phen9l thiodipheny lcarbamate is obtained by heating an alcoholicsolution of the preceding compound with sodium plienoxide on thewater-bath. It crystallises from alcohol in white lustrous needles,melts at 164"' and is soluble in hot alcohol ether benzene and aceticacid. At 16" one part dissolves in 410 parts of alcohol and in 50%parts of benzene.Unsymmetrical thiodiphen7_JZcarba~~~i~de S:(C6HJ2:N*CO*NH2 is ob-tained by heating thiodiphenylcarbamic chloride with alcoholic am-monia on the water-bath €or two hours. It crystallises in colourlesstablets melts at 201-20it0 and dissolves copiously (but with diffi-culty) in boiling methyl and ethyl alcohols and etherj easily in benzene.At 17*5" one part dissolves in 331.5 parts of alcohol and in 48.4 partsof benzene.When heated in a sealed tube with alcoholic ammoniafor three hours at 140-150" it yields thiodiphenylamine and carb-amide. The same two substances are formed when it is distilled froma retort into aqueous ammonia.Thiutriphervylcarbamide S (C,H,),:N*CO*NHPh is obtained by heat-ing thiodiphenylcarbamic chloride dissolved in hot xylene with ORGANIC CHEMISTRY. 165slight excess of aniline. I t crystallises from boiling alcohol in white,lustrous needles which turn red on exposure to air melts at 16S-169",and dissolves copiously but with difficulty in boiling alcohol andether easily in benzene and chloroform. At 17*5" one part dis-solves in 387 parts of alcohol and in 26.7 parts of benzene. Whenheated with excess of aniline it is e a d y converted into diphenyl-carbamide and thiodiphenylamine.The same products are formedby heating thiodiphenylc,zrbamic chloride with excess of aniline.I)ithiotetrnphenyZcarbnmide CO [N:(CsH,),:S] is obtained byheating a mixture of thiodiphenylcarbamic chloride with thiodiphenyl-amine in molecular proportion at 220-260". It crystallises from a,mixture of alcohol and benzene in colourless needles having a redlustre melts at 231" and is very sparingly soluble in alcohol ether,and acetic acid copiously in cold and very easily in hot benzene.At17" one part dissolves in 2300 parts of alcohol and in 24 parts ofbenzene. It is also formed when thiodiphenylcarbamic chloride isheated with thiodiphenylcarbamide for two hours at 200-280".When heated with concentrated hydrochloric acid at 240-250",hydrogen sulphide is produced together with a solid dark-green pro-duct. Unlike tetrnp henglcarbamide it does not yield carbon dioxideunder these conditions (Ber. 11 711).MorzothiotetraphenzJlcclrbamide NPh,*CO-N:( C6H4),:S is obtained byheating molecular proportions of thiodiphenylcarbamic chloride anddipbenylnmine at 220-240" for three hours. The product is purifiedby dissolving it in benzene and passing hydrogen chloride into thesolution when diphenylamine hydrochloride is precipitated ; thefiltrate is then evaporated to dryness and the residue washed withalcohol and crystallised from hot alcohol.It forms colourless,six-sided plates softens at 163" melts at 165" and is soluble in coldalcohol and ether easily in cold benzene and boiling alcohol and ether,and very easily in boiling benzene.Thiotriphernyl-P-?aa;uhthzJZcarbamide C,,N,*HPh.CO.N:(C,H*)~:S isobtained by heating thiodiphenylcarbamic chloride with phenyl-P-naphthylamiiie for three hours at 240-260". It crystallises fromalcohol in greyish-white nodular aggregates melts at 169-170" andis easily soluble in boiling alcohol and ether very easily so in benzeneand acetic acid. At 15" one part dissolves in 190.7 parts of alcohol,and in 29.5 parts of benzene.ThiodiphAnyldi-P-n~~hthylcarbamide N( ClnH,),*CO.N:(CsHa), S ob-tained from di-/3-naphthylamine in a similar manner to the pre-ceding compound crystallises from a mixture of benzene and alcohol innodular aggregates melts at 225" and is sparingly soluble in boilingalcohol and ether easily in benzene and acetic acid.One part dis-solves at 16" in 801 parts of alcohol and in 181 parts of benzene. - -Thiodi-P-rza~hthylcarbamic chloride S <~~~':>N*COCl is obtainedby heating thiodi - p - naphthylamine with. carbonyl chloride at160-170" for fire hours. It forms small white needles melts at254-255" is almost insoluble in cold alcohol very sparingly soluble inhot alcohol and cold benzene more so in hot benzene and cold xylene,and easilyin boiling xylene.St 16*5" one part dissolves in 1420 part166 ABSTRACTS OF CHEMIOAL PAPERS.of alcohol and in 134 parts of benzene. When boiled with alcoholic,soda it yields thiodi-P-naphthylamine.Phenyl thiod~-~-iaaphthylcarhamate S:( C,,H,),:N*COOPh is obtainedby heating the preceding compound with alcoholic sodium phenoxide ;it forms small greyish-white needles melts at 215" and is sparinglysoluble in both cold and hot alcohol and ether cold benzene andacetic acid but easily in hot benzene and acetic acid. At 16" onepart dissolves in 489.5 parts of alcohol and in 83 parts of benzene.Uiasymmeti-ical thiodi-P-nap hth y Earbanzide S (C ,OH6) ,IN- CI 0.NH2 isobtained by heating thiodi-/3-naphthylcarbamic chloride with excessof alcoholic ammonia at 140-145" for three hours ; it crystallises frombenzene in almost colourless needles which turn green on exposuret o air decomposes at 215" without melting and is almost insoluble incold alcohol ether and benzene sparingly soluble in boiling alcoholand ether more so in boiling benzene and easily in xylene.~hiodi-f3-Iza~72thy~7he.lzylcarbam,ide S:(CloH6),:N.CO~NHPh is ob-tained by heating thiodi-/J-iiaphthylcarbamic chloride dissolved i nxylene with twice the moleciilar proportion of aniline for 4 hour in areflux apparatus.It darkens at 180" decomposes at 215-220" withoutmelting and is sparingly soluble in alcohol ether and cold benzene,xylene and chloroform fairly soluble in hot benzene and easily so inhot xylene and chloroform. At 17.5" one part dissolves in 275.2 partsof alcohol and in 551.5 parts of benzene.When boiled with excessof aniline it yields th iodi-p-naphthylamine and carbanilide.Ditlziotetra-p-napl~thy lcarbnnzide C'O [ N:( CloHs),:S] is prepared byheating a mixture in molecular proportion of thiodi-/%naphthyl-carbamic chloride and thiodi-P-naphthylamine dissolved in xyleneat 280" for five hours. It crystallises from benzene in yellowish lus-trons leaflets melts above 350" and is very sparingly soluble in coldalcohol ether benzene and acetic acid sparingly so in the boilingsolvents but easily in hot xylene.Carbamides containing the gronp N ( CloH,),:S like thiodi-p-naph-thylamine give a violet coloration with concentrated sulphuric acid.h'th y I p heny 1- /3-nap hthy Zcarbmate C10H7*N P h-C 0 0 E t obtained bythe action of sodium ethoxide on phenyl-/3-naphthylcarbamic chloridein warm alcoholic solution crystallises in long white silky needles,melts at 93" and dissolves somewhat easily in cold easily in hotalcohol and ether and very easily in cold benzene.Phenyl phenyl-lS-naphthyZcarbama~e is prepared in a similar way tothe preceding salt crystallises in white neadles melts at 149" issparingly soluble in cold alcohol ether benzene and acetic acid,easily so in the hot solvents.At 17" one part dissolves in 278 partsof alcohol and in 43.4 parts of benzene.S y mmetrica 1 d @hen y ldi-P-naphth y Ecnrbamide C 0 (XP h*ClOH7) is ob-tained by heating a mixture of phenyl-P-nap hthylcarbamic chloridewith phenyl-P-naphthylamine in molecular proportion for five hoursat 240-260°. It crystallises from alcohol in pale-y ellow polyhedralgranules melts at 185-186" and dissolves sparingly in cold alcoholand ether easily in cold and very easily in hot benzene.Whenheated with concentrated hydrochloric acid for four hours a t246-250" it is decomposed into carbonic anhydride &I-naphtholORGANIC CHEMISTRY. 167and aniline. It is not altered by heating with ammonia or anilineat 270" or with aqueous potash at 240-250° and distils almost un-changed at 460".T~-~~l~en~~l-p-na~~hthylca.1.baiizide NPh2*CO*NPh*CloH; ia obtained byheating phenyl-p-naphthylcarbamic chloride with diphenylamine a t200-240" for two hours. It forms a pale-yellow crystalline powder,melts at 12E0 and is easily soluble in cold alcohol and ether veryeasily in benzene.Uns y m n e trical dip heny ldi-p- nap ht lay 1 curb anaide NP h2* C 0.N ( CJ&) 2,is best obtained by heating diphenylcarbamic chloride with /3-dinaph-thylamine for two hours at 200-220". I t is also obtained by heatingdi-/?-naphthylcarbamic chloride with diphenylamine f o r three houras at860" ; tetra-/3-naphthylcarbamide (m. p. 293-294") (Kym Ber. 2 3.1542) being formed at the same time. It melts at 103-lo$" and issomewhat easily soluble in cold easily in hot alcohol and ethcr orcold benzene and very easily in hot benzene.N( C ,,H,) 2* C 0 *N P h. C 10H7 i s o b -taiued on heating di-p-naphthylcarbamic chloride w i t h phenyl-P-naph-thylamine at 240-260" for three hours.It crystallises from aceticacid in white nodules melts at 168" and is sparingly soluble in cold,easily in hot alcohol and ether and more easily i n benzene and aceticacid. At 16" one part dissolves in 104.5 pavts of alcohol and in 22parts of benzene.Cadazole and Carbonyl ChZoride.-Various experiments were madewith the object of preparing a carbamic chloride by the action ofcarboiiyl chloride on carbazole but without success. Carbonyl chlorideis without action on carbazole at loo" 130" or 200" whilst at 250"carbonised products are obtained together with unaltered carbazole.The potassium derivative of carbazole gives no better results.Ph en y 1 ti+- /3 -nap h t / L y 1 curb amid e,E. C. R.Reduction of Aromatic Aldehydes.By I?. TIEMANN (Ber. 24,3169-3175).-1n a former paper the author has shown (Abstr. 1886,460) that whilst benzaldehyde readily yields benzyl acetate on treat-ment with zinc-dust and acetic acid orthohydroxybenzaldehyde isthus converted into diorthohydroxyhydrobenzoin diesoanhydride.Purther investigation has shown that thc reduction of aromatic alde-hydes with zinc-dust and acetic acid proceeds differently according tothe conditions under which it is carried o u t ; thus parahydroxybenz-aldehyde which usnally yields the corresponding alcohol or its acetate,can even be converted into paracresol by long-continued boiling withthe reagents. If the reduction proceeds slowly SO that mixtures ofthe alcohol and aldehyde are subjected for some time to the action ofzinc acetate and acetic acid condensation takes place with formationof substances resembling hydrobenzoin according t o t'he equationRGHO + P,*CH,*OH = R*CH(OH).CH(OH).R.The compound obtained by the author by the reduction of salicyl-aldehyde and described its diorthohydroxyhydrobenzoYn diesoan-hydride is in reality a mixture of two isomerides melting at 116 -11 7168 ABSTRACTS OF CHEMICAL PAPERS.and 67-68" respectively both of which have probably the constitu-tional formula IC 6H4* $3 H*QO-CH*C,H,'Hydrobenzoyn itself contains two asymmetrical carbon atoms andshould therefore exist in three isomeric forms ; the anhydride of di-orthoh ydroxyhydrobenzoln should also according to theory form asimilar number of isomerides both of the above compounds are,however optically inactive and could not be sepmated into opticallyactive constituents.The one melting at 67-68' is converted onboiling in acetic acid solution into the higher melting isomeride.If the reduction is carried out quickly and at as high a tempera-ture as possible a portion appears to be converted into diorthohydr-oxyhydyobeizzoin H0.C6H,.CH,*GH(OH)*CGH,.0H which on distilla-tion splits up into diorthohydl.oxystiZberze C2Hz(C6H,oOH)z a,nd water.The experimental details of this research are given in the follow-ing abstract. H. G. C.Reduction of Salicylaldehyde by Zinc-dust and Acetic Acid.By C. D. HARRIES (Bey. 24 3175-3180 ; see also previous abstract).-In order to prepare the diorthohydroxyhydrobenzofn diesoanhydridemelting at 116-117" a solution of salicylaldehyde in acetic acid isboiled for 12 hours with an excess of zinc-dust the solution dilutedwith water neutralised with soda and extracted with ether.Afterdistilling off the ether the residue is treated with potash and the in-soluble portion recrystallised from alcohol. The anhydride is thusobtained in transparent needles readily soluble in ether and benzene,sparingly in alcohol and acetic acid and only slightly in hot water ; ithas a pleasant aromatic odour resembling that of fennel and geranium,dissolves in sulphuric acid with a red coloration and is not altered byheating with dilute mineral acids o r alkalis.I f the action of zinc is allowed to take place at IOO" a mixture of bheforegoing compound with an isomeride of lower melting point is formed,which may be separated into its constitu.ents by repeatedly precipitat-ing the alcoholic solution with hot water. The more soluble portionis thus obtained in crystals melting a t 67-68'. Both anhydridesappear to distil in a vacuiim wihhout decomposition but the compoundof lower melting point is completely converted into its isomeride byboiling in acetic acid solution for some time.The anhydride of higher melting point is acted on by bromine inacetic acid solution with formation of two dibromg-derivatives havingthe composition Cl4H,O2Br2 which commence to sublime at 235" and245" respectively.If the reduction of salicylaldehyde be carried out at 1.20" and theproduct distilled potash extracts from the distillate diorthohydroay-stilbene C2Hz*(CGH4*OH) which melts at 95" is sparingly soluble inwater readily in alcohol and ether and forms a blue fluorescent solu-tion in alkalis.Its diberizoyl derivative C2H2(CsH4*OBz)z crystal-lises from alcohol in matted aggregates of needles melting at 107-108",amd unites directly with bromine forming dibeiazoyldiorthohydroxy-stilbene dibromide C28H2,Br204 melting at 58-59'. H. G. CORGANIC CHEMISTRY. 169Methyl Orthohydroxycinnarnyl Ketone (Methyl Ortho-cumaroketone) and its Derivatives. By C. D. HAREIES (Bey.,24 3180-3184).-Tiemann and Kees have shown (Abstr. 1885,1073) that helicin nndergoes condensation with acetone and alkali,forming methyl gluco-orthocumaroketone which is converted by theaction of emulsin into glucose and methyl orthocumaroketone.Thelatter compound may also be readily obtained by the action of dilutealkali and acetone on snlicglaldehycle ; the mixture after remainingfor two days is acidified with hydrochloric acid and freed from un-altered salicylaldehyde by distilling in a current of steam. Theinsoluble product remaining in the liquid after cooling is recrystal-lised from benzene with the addition of animal charcoal and then meltsat 139" as given by Tiemann and Kees. It is readily soluble in alcohol,ether and hot water and is coloured bluish-violet by ferric chloridein aqueous solution. When the ketone is dissolved in alcoholic sodiumethoxide and et,her added the sodium compound separates in purecondition as a deep yellow substance.When methyl orthocun~aroketone is treated with benzoic chloride inalkaline solution i t yields the benxoyl derivative CloH9O?Bz whichcrystallises from dilute alcohol in white needles melting a t 87-88' ;the acetyZ and ?nsthyZ derivatives are oils.The ketone also readilycombines with phenylhydrazine and hydroxylamine forming thephei,yZlnyh-axone C,,H,,0:N2HPh and the o,i:ime C,,,H,,O:N-OH ; theformer separates in yellow flakes which after recrystallisation fromdilute alcohol melt a t 159-160" and the latter forms white crystalsmelting a t 84-85'.On reduction with sodium amalgam methyl orthocumaroketone isconverted into secoudary me thylort hoc umaryl alcohol,HOB C6HI,*CH:CH-CHMe*OH,which after purification forms compact phtes melting at 47-48".It is readily soluble in alcohol ether benzene and hot water gradu-ally becomes pink in the air dissolves i n sulphuric acid with a red-dish-violet colour and does not form an anhydride resemblingcoumarin.Reducing agents appear to have no effect on the ethylenelinking i n the side chain nor does the ketone unite directly withbromine. H. G. C.Action of Sodium on Ketones and Aldehydes. By E. BECK.MANN and T. P A u r (AnnuZen 266 1-28 ; compare Abstr. 1889 78).-The authors have made a study of the sodium derivatives of variousketones and of benzaldehyde ; their experiments have shown thatmany of these sub3 tances resemble the organo-metallic compounds inbeing very readily oxidised on exposure to the air in being imme-diakely decomposed by water and in combining with carbonicanhydride to form salts of carboxylic acids.The sodium derivativeswere prepared by treating a solution of the ketone or aldehyde inpure ether or benzene with excess of sodium in the form of wire orribbon air and moisture being excluded as far as possible ; the pro-ducts were then washed and dried in an atmosphere of pure hydro-gen i n an apparatus specially devised for the purpose ; in spite of allVOL. LXII. 4170 ABSTRACTS OF CHEMICAL PAPERS.precautions it was found impossible to avoid partial oxidation andt,he preparations usually contained a little metallic sodium. Whendrp carbonic anhydride is passed into ether containing one of thesesodium derivatives in solution or in suspension combination generallytakes place accompanied usually by a change in colour; the com-pounds produced in this way are extrkmely hygroscopic and decom-pose on exposure to the air.The sodium derivative of benzophenone (Znc.cit.) is immediatelydecomposed by water yielding benzopinacone (m. p. 184") beneo-phenone and banzhydrol (m. p. 67") the relative quantities of thesethree products depending greatly on the conditions of the experi-ment. It combines with carbonic anhydride under the conditionsjust stated being thereby converted into a yellow powder; this sub-stance is decomposed by water yielding approximately equal quanti-ties of the sodium salt of benzilic acid and benzophenone. Thesereactions are best explained by assuming that sodiobenzop henone andits cai-hoxyl derivative have the constitutions expressed by the formulaeC Ph2Na.0.C Ph,* ONa and C 0 ONaG Ph2*0 C Pb2*0.C 0 ONa respec-tively; analyses of the two compounds gave results in accordancewith these formula?.The sodium derivative of phenyl a-naphthyl ketone is a greenish-yellow powder and is decomposed by water yielding a yellow oil ;this oil is doubtless 8 mixture of various compounds and was provedt o contain a crystalline substance melting at about B O O which ismost probably phenyl-a-naphthylpinacoline. When phenyl sociio-a-naphthyl ketone is treated with carbonic anhydride it is convertedinto a yellow powder which on decomposition with water yields thesodium salt of phenyl-a-iiaphthylglycollic acid and phenyl a-naphthylketone ; it seems probable therefore that this carboxy-derivative hasa constitution analogous to that of the corresponding benzophenonederivative a view which is in agreement with the analytical results.Pherz~l-u-nap7ifhylglycoll~~ acid C18H1403 can be conveniently pre-pared from phenyl sodio-a-naphthjl ketone as it is unnecessary topurify the carboxy-derivative.It crystallises from hot water or dilutealcohol in colourless well-defined plates or needles which contain2 mols. H20 and melt a t log-115" with elimination of water; itseparates from benzene aud carbon bisulphide in anhydrous shortprisms melting at 148".When acet>opheizone is treated with sodium the ethereal solutionturns greenish and then a colourless powder is deposited ; if how-ever this powder is left in contact with sodium for a long time itfirst turns brown and then dark-violet.On decomposing sodaceto-phenone with water acetophenonopinacone (m. p. 122.5") aceto-phenone and other compounds are formed. When the sodiumderivative is treated with carbonic anhydride i t yields a yellowishsubstance which is decomposed by water ; i f the alkaline solution isextracted with ether the same compounds are obtained as fromsodacetophenone and benzoylacetio acid (m. p. looo) remains i n t h eaqueous solution. The constitution of these two sodium compoundsis probably expremed by the formulae ONa*CPhMe*CPh (OH)*CH,Naand COONa-O*CPhMe*CPh(OH) *CH2*COONa respectively171 ORGANIC CHEMISTRY.The sodium derivative of deoxybenzoh is very readily soluble inether and is best obtained by treating a concentrated solution of theketone in pure benzene with sodium it is a very hygroscopic pale-yellow substance and is readily decomposed bv water yielding deoxy-benzo'in.The benzene mother liquors obtained in the preparation andpurification of this sodium deri va hive contain deoxy benzohpinacone(m. p. 213") and toluylene hydrate (m. p. 62"). On passing carbonicanhydride into an ethereal solution of sodiodeoxybenzoin a reddish-yellow substance is precipitated ; this compound is decomposed bywater yielding deoxybenzo'in and an acid which could not be isolated,but which is most probably phenylbenxoylacetic acid. When theaqueous solution of the acid formed in this way is quickly separatedfrom the ethereal solution of deoxybenzo'in and then treated withhydroxylamine a crystalline acid which melts at 159.5" and whichhas probably the constitution 1 1 >CPh*COOH is obtained.Fromthese reactions and from the results of analyses of the two sodiumderivatives the authors conclude that they have the constitutionC 0Ph.C HNaPh and C 0 Ph-C H Ph*C 0 ONa respectively.When an ethereal solution of benzile is treated with sodium thereis formed a yellow flocculent substance which afterwards changes toa deep violet powder ; this compound oxidises very energetically onexposure to the air and is decomposed by waber into beuzile andbznzoin but it seems to be unacted on by carbonic anhydride; itsconstitution is probably expressed by the formulaN-C PhC 0 P ha C P h ( ONa > C Ph ( 0 Na) C 0 P h.The compound formed by the action of sodium on a benzene solu-tion of benzaldehyde is a dark-green powder which becomes muchlighter in colour when washed and dried ; it oxidises very readily onexposure to the air and when treated with water it gives hydro-lxnzoi'n and a trace of benxoic acid.It combines with carbonicanhydride yielding a brownish-yellow substance which is quicklydecomposed by water with formation of hydrobenzoin sodium hydro-gen carbonate and a trace of benzoic acid. The following formulze,ONa*CHPh*CHPh*OXa and COONa.O*CHPh*CHPh*O*COOWa prob-ably represent the constitutions of these two sodium deriva hives.F.S. K.Brornination of Bromobenzoic Acids. By A. CLACS and A.REH (Annalen 266 203-209).-Dibromobenzoic acid [COOH Bra= 1 3 41 is formed in small qnantities by the bromination ofbenzoic acid but the reaction is a very complicated one; by thebromination of metabromobenzoic acid at 220 -230" the 3 4-dibromo-:wid is produced in even smaller quantities if at all. When benzoicacid is treated with nascent bromine in very dilute aqueous solution,a t a temperature below 70-80° not incmsiderable quantities of para-bromobenzoic acid are obtained but dibromo-acids are not produced inany appreciable quantity.When orthobromobenzoic acid is heated with bromine (1 mol.) andwater at 150-160" for 8 to 10 hours dibroinobenzoic acid [COOH Bra?L 172 ABSTRACTS OF OHEMIOAL PAPERS.= 1 2 51 is produced; parabromobenzoic acid is not acted on a t180" but a t 200" it is converted into tribromobenzoic acid [COOH Br,= 1 3 4 51 some of the monobromo-acid remaining unchanged.These experiments show that i n benzoic acid substitution is notlimited solely to the meta-position relatively to the carboxyl group butt,hat under certain conditions the ortho- and para-hydrogen atomsmay also be displaced.By A.CLAUS andN. DAVIDSEN (AmaZen 265 341-350) .-The following experimentsprove that the nitrochlorotoluic acid (m. p. 180O) previously de-scribed (Abstr. 1889,988j has the constitntion [COOH C1 Me NO,= 1 2 4 51 ; the magnesium salt of this acid is readily soluble i nwater from which it crystallises in large hexagonal plates containing8 mols.H,O.Nitrochloropa.l.atot~~~d~ne [NH C1 Me NO? = 1 2 4 51 is bestprepared by treating dry chlorotoluidine nitrate with pure sulphnricacid cooled to about -15' ; the yield is quantitative. It crystallisesfrom hot alcohol in orange-red plates melts at 129.5" (uncorr.) and isonly sparingly soluble in boiling water and dilute acids but readily inether alcohol &c. The ucetyl derivative N0,*C6H,ClMe*NHAc,crystallises from alcohol in small almost colourless needles melts at143" (uworr.) and is not decomposed by boiling sulphuric acid ; whenheated w i t h filming hydrochloric acid a t 150" it is reconverted intonitrochloro par a t oluidi n e .Nitrochloro~aratoluidille [NH C1 Me NO = 1 2 4 61 isformed when dry chlorotoluidine nitrate is treated with 80 per cent.sulphuric acid cooled to about 0"; it is best obtained by treatingchloroparacetotoluidide with nitric acid of sp.gr. 1.5 at about 20" andthen decomposing the product with sul phuric acid. It crystallisesfrom alcohol in orange-coloured plates melts at 70.5 and is readilyvolatile with staam. The acetyZ derivative crystallises in almostcolourless needles and prisms melting at 196" (uncorr.).Nitrochloropal.atolurzitrile [CN C1 Me NO = 1 2 4 51 is easilyobtained from the corresponding amido-derivative ; the yield of thepure compound is 70 per cent. of the theoretical. It crystallises fromether or alcohol in long almost colourless needles melting at 93"(uncorr.) ; when boiled with sulphuric acid or with very dilute potash,it is converted into the iiitrochloroparatoluic acid (m.p. 180-181*5")referred t o above.Amidochloropurntoluic acid [COOH C1 Me NH = 1 2 4 51,prepared by reducing the corresponding nitro-derivative (m. p.180-181.5) with tin and hydrochloric acid in alcoholic solution crys-tallises from hot water in colourless needles melting at 220" (uncorr.).The hydrochloride crystallises in slender colourless needles and meltsat about 245" with decomposition. The stannochloride is readilysoIubIe in water and crystallises in colourless needles. When thediazo-derivative of the amido-acid is treated with cuprous chloride i tis converted into dichloroparatoluic acid [COOH C1 Me =1 2 5 41 melting at 187" (uncorr.).The barium salt of this acidcrystallises from cold water in needles contGining 4 mols. H,O.F. S. I(.Nitration of Orthochloroparatoluic AcidORGANIC CHEMISTRY. 173BromochZoroparatoIIiic acid [COOH C1 Br Me = 1 2 5 41,prepared by decomposing the diazo-derivative of the amido-acid withcuprous bromide is almost insoluble in water but readily in alcohol,from which it cry stallises in colourless nacreous needles melting a t192-193" (uncorr.). The barium salt is readily soluble in water fromwhich it crystallises in colourless needles containing 1$ mols. H,O.Nitrochloroparatoluic acid [COOH C1 NO? Me = 1 2 3 41 isformed in small quantities on nitrating orthochloroparatoluic acid,and is best prepared from the isomeride (m.p. 1 8 1 O ) referred toabove by means of its magnesium salt with 3+H,O which is moresoluble in water than that cf the isomeric acid. It crystallises fromdilute alcohol in colourless needles melts at 192' (uucorr.) and is in-soluble in light petroleum ; when treated with a mixture of nitric andsulphuric acids it is converted into the dinitrochloroparatoluic acidpreviously described. 1'. S. K.Nitration of Metachloroparatoluic Acid. By A. CLAUS and P.B~CHER (Annaleiz 265 35 1 4 6 3 ) .-Three isomeric nitro-derivativesare invariably produced when metachloroparatoluic acid is nitrateduuder various conditions; 60-70 per cent. of the crude prodnctconsist's of the acid of the constitution [COOH C1 Me NO =1 3 4 61 20-30 per cent.of the corresponding 1 3 4 5-deriva-tive and 5-10 per cent. of the 1 3 4 %acid. Tho three com-pounds can be separated from one another by systematic fractionalcrystallisation of the free acids and thcir barium salts alternately ;they are all very readily soluble in acetone ether and alcohol butonly sparingly in light petroleum and very sparingly in benzene.The 1 3 4 6-acid can also be obtained i n a pure condit,ion fromnitrochloparatoluidine in the manner described below.NitrochloroparacetotoZuide [NHAc C1 Me NOz = 1 3 4 61 isprepared by nitrating chloroparacetotoluidide with acid of sp. gr. 1-52? ;it crystallises from alcohol in lustrous plates and in small needles,both forms melting at 113" (uncorr.).Nitrochloroparatoluidine [NHz C1 Me NO = 1 3 4 61 ob-tained by decomposing the acetyl derivative with boiling alcoholicpotash crystallises from hot alcohol in which it is readily soluble inlustrous golden plates melts at 165" (Encorr.) and is only spaxinglysoluble in hot matel.; it is readidly volatile with steam.The correspond-ing nitrile crystallises i n large plates sublimes without decomposition,melts at 157" (uncorr.) and is readily soluble in alcohol. The corre-sponding acid obtained by treating the nitrile with concentrated sulph-uric acid at about 200" crystallises from alcohol in colourless needles,melts at 184-185" and sublimes without decomposition. The bariumsalt with l$H,O crystalli ses in large colourless hexagonal platesThe caZcium salt arid the bluish-green copper salt are anhydrous butthe potassium salt crystallises in plates containing 8 mol.H,O.Arnidochloroparatolzcic acid [COOH C1 Me NH = 1 3 4 61is obtained when the nitro-acid just described is reduced with ironand hydrochloric acid ; it crystallises from alcohol in colourlessneedles and melts a t about 280". When its diazo-derivative is treatedwith cuprous chloride dichloroparatoluic acid (m. p. 187") is ob174 ABSTRACTS OF CHEMICAL PAPERS.tained. This fact proves that the nitro-acid has the constitutionassigned to it above.Nitrochloroparatoluic acid [COOH C1 Me NO = I 3 4 51is moderately easily soluble in water from which it crystallises inslender colourless needles melting at 159" (uncorr.) ; i t is identicalwith the acid obtained by Clam and Beysen from dilute nitroparatoluicacid and both conipounds yield one and the same dichloroparatoluicacid (m.p. 188"). The barium salt crystallises from water in which it,is readily soluble in short thick prisms containing 1 mol. H,O. ThecaZcizcm salt crystallises in coloui-less anhydrous needles. The am-monium salt and the potassium salt are readily soluble in water butthe silver salt is insoluble.Nitrochloro~aratoluic acid [COOH C1 Me NO = 1 3 4 23crystallises from water in which it is readily soluble in colourless,iiacreous plates and melts at 211". The barium salt with 1$H20,crystallises in characteristic stellate forms. The caZcium salt crystal-Iises in lustrous anhydrons needles.Nitration and Bromination of Orthobromoparatoluic Acid.By A.CLAW and J. HERBABNY (Annalen 265 364-378j.-Whenorthobromoparatoluic acid is treated with nitric acid two isomericnitro-derivatives are obtained ; the compounds are most easily sepatrated by means of their magnesium salts.I? s. K.The nitrobromoparatoluic acid of the constitution[COOH Br Me NO = 1 2 4 51is formed in by far the larger quantity it crystallises from alcoholincolourless nacreous plates melts at 203" (uncorr.) and is very readilysoluble in ether and moderately easily in hot benzene but only spar-ingly in hot water. The sodium salt with 4iH20 crptallises in large,efflorescent plates and is readily soluble in water and alcohol. Thepoiassiuum salt with lH,O and the barium salt with 5H,O crystallise inneedles; the calcium salt witth 5H20 forms large efflorescent plates orprisms.The magnesium salt with 7iH,o crystallises in lustrous plates.The chh-ide N02*C6H2BrMe*COCl crystallises from light petroleum incolourless plates melts at 60' (uiicorr.) and is readily soluble in chloro-form. The amide N02*C6H,BrMe*CO-NH crystallises in colourlessneedles melts at 191" (uncorr.) and is readily soluble in alcohol,but more sparingly in water. The ethyZ salt NO,*C,H,BrMe*COOEt,melts at 61°(uncorr.) and crystallises from alcohol in colourless lustrousneedles. When the acid is oxidised with potassium permanganate ityields a bromomonitroterephthalic acid ; this compound cr-ystallises&.~rn hot water in colourless needles which seem to melt at 260-261".[NH Br Me NO = 1 2 4 51 iseasily obtained by dissolving orthobromotoluidine nitrate in sulphuricacid eooled to 0" ; it crystallises from glacial acetic acid or alcohol inpale-yellow needles melting at 121" (uncorr.).The correspondingnitrile [CN Br Me NO2 = 1 2 4 51 melts at 132" (uncorr.) andis readily soluble in alcohol ether benzene and chloroform but onlyspai*ingly il; hot water ; when boiled with moderately concentratedsulphuric acid it is converted into the nitrobromoparatoluic acid(m. p. 203") described above.NitrobromoparatoIuidinORGANIC CHEMISTRY. 175~itrobromo~aratolvic acid [COOH Br NO2 Me = 1 2 3 41is only formed iu small quantities (6-8 per cent.) in nitrating ortho-bromoparatoluic acid ; it crystallises from alcohol and hot water inslender colourless needles melts at 214" (uncorr.) and sublimes inslender needles.The magnesium salt with 3$H20. crystallises in colour-less plates and is more readily soluble in water than the correspondingsalt of the isomeric acid described above. The barium salt wiCh 4H20,crystallises in large rhombic plates.Nitrobromoparatolzionitl.ile [CN Br Me NO2 = 1 2 4 61 Carlbe prepared by diazotising nitrobromotoluidine (m. p. 64") in ice-cold70-80 per cent. sulphuric acid solution and immediately adding asolution of copper sutphate and potassium cyanide ; it crystallises fromalcohol in yellowish needles melts a t 130" (uncorr.) and is very spar-ingly solnble in hot water but readily in benzene ether and chloroform.~~trobromoparatoluamide [CO*NH2 Rr Me NO = 1 2 4 61is formed when the preceding compound is boiled with dilute(1 1) sulphuric acid for 8-10 hours ; it; crystallises from boilingwater in colourless needles melts at 171" (uncorr.) and is readilysoluble in alcohol ether benzene and chloroform.[COOH Br Me NOz = 1 2 4 61is obtained in small quantities when the corresponding amide isheated at 220-2330" with 20-25 per cent.hydrochloric acid; itcrphallises from boiling water in small colourless needles melts at206" and is very readily soluble in ether alcohol chloroform &c.When orthobromoparatoluic acid is heated with bromine and water(at 90-95" for 4-5 hours the sole product is a dibromoparatoluic acid,[COOH Br2 Me = 1 3 6 41 melting at 199" (uncorr.) whichhas been previouslyprepared by Schultz and Fileti.The sodium salt ofthis dibromo-acid crystallises in large plates contaiuing 7 mols. H20.The chloride C6H2BrzMe*COC1 forms colourless lustrous needles andmelt's at 60".Dibro112o~aratrrl?l,ic acid [COOH Bra Me = 1 2 3 41 was ob-tained in small quantities from the corresponding nitrobromoparatoluicacid ; it forms colourless crystals and seems to melt at 194".Dibromo~aracetotolzLidide [NHAc Br2 Me = 1 2 6 41 can be pre-pared by heating dibromoparatoluidine (ni. p. 73") with acetic chlorideat 100"; it crystallises in long colourless needles melts at 183"(uncorr.) and is reconverted into dibronioparatoluidine by boilingalcoholic potash.Dibromopayatoluonitrile [CN Br Me = 1 2 6 41 preparedfrom dibromoparahluidine crystallises in long colourless needles,melts at 156" (uncorr.) sublimes in needles and is readily volatile withsteam ; it is insolukile in water but dissolves freely in alcohol ether,benzene and chloroform.When boiled with 50 per cent.. sulphuricacid it is converted into the corresponding amide; this compoundcrystallises from boiling water in small colourless plates melting at,148" (uncorr.) and is raeadily soluble in alcohol ether and chloroform.Dibromoparatoluic acid [COOH Br2 Me = I 2 6 41 is ob-taiued when the arnide just described is heated with concentratedsulphuric acid at 240"; it crystallises and sublimes in colourless needles,melts at 182" (uncorr.) and is only sparingly soluble in hot water,but dissolves freely in ether alcohol and chloroform.Nitrob?-omoparatoluIc acidF. S.K176 AMTRACTS OF CHEMICAL PAPERS.Dibromoparatoluic Acid. By A. CLAUS and R. SEIBERT(Annulen 265,3'78-380).-Dibromoparatoluonzitrile [CN Br Me =1 3 5 4J prepared from the correspoiiding dibrornotoluidine,crystalliscs from alcohol in lustyous needles melting at $9" (uncorr.) ; i tis readily volatile with steam and dissolves freely in alcohol ether,chloroform and hot water. The corresponding acid is obtained whenthe nitrile is boiled with potash ; i t crystallises from alcohol in slenderneedles melts at 235-236" (uncom.) and is readily soluble in alcohol,ether and chloroform but only sparingly in water.The sodium salt,with lH,O y o t u ~ s i z m salt with l+H,O and the barium salt with 4H20,are colourless crystalline compounds. The chloride C6H,Br,Me*COCI,crystallises from ether in colourless needles melting at 80" (uncorr.).The ainide separates from ether in small needles and melts at 117"(uncorr.). The ethyl salt C6H2Br2Me*COOEt crystallises from alcoholin colourless needlea melting at 79-80' (uncorr.). F. S. I(.Nitration of Orthonitroparatoluic Acid. By A. CLAUS and5. JOACHIM (Anfzalen 266 209-222 ; compare Rozanski Abstr.,1890 52) .-Two dinitro-compounds are formed when ort'hoiiitropara-toluic acid (m. p. 164") is heated at about 100" for 4-5 hours with nmixture of nitric and sulphuric acids ; the two products are separatedby fractional crystallisation from water.The diriitroparatoluic acid of the constitution [ COOH (NO,) Me= 1 2 3 41 is always produced in by far the smaller quantity,and is much more sparingly soluble in water than the isomeridedescribed below ; it crystallises in short colourless lustrous prisms,melts at 248" (uncorr.) has an intensely bitter taste and is readilysoluble in alcohol. The barium salt with 3H20 and the calcium salt,with 1iH20 are colourless crystalline compounds only moderatelyeasily soluble in water.Diamidoparatoluic acid [(NH,)* = 2 31 prepared by rcducingthe preceding compound with tin and hydrochloric acid crystallisesin yellowish needles melts a t 192" decomposes at a higher tempera-ture and is only sparingly soluble in cold water but readily inalcohol and hot water ; in its aqueous solution ferric chloride pro-duces n red flocculent precipitate and its solutions in acids yield withrhodizonic acid a brown azine which dissolves in alkalis with a violetcoloration. The hydrochZoride C,H,,N,02,2HCl forms granularcrystals which soon Rssume a reddish hue.The barium salt ismoderately easily soluble in water and crptallises in small reddish-yellow plates.[COOH (NO,) Me = 1 2 5 41 isthe principal product of the nitration of paratoluic acid ; it is readilysoluble in alcohol and moderately easily in hot water crystallising incolourless plates which melt at 194". The barium salt with 2H20 andthe calcium salt with 2H20 are colourless crystalline compounds,only moderately easily soluble in water.The corresponding diamido-compound crystallises from boiling water in lustrous blue or violetneedles melts at 240" (uncorr.) with decomposition and is very readilysoluble in alcohol; when heated with ferric chloride in aqueous solution,Dinitroparatoluic aciORGANIC CHEXISTRT. 177a reddish-brown precipitate is formed and .a strong odour of tolu-quinone is observed.Dinitroparatoluic acid [COOH (NO,) Me = 1 3 5 41 is thesole product of the nitration of metnnitroparatoluic acid ; it melts a t159" (uncorr.). The barium salt and the calcium salt contain wakr ofcry stallisation. The coiresponding diamido-acid crystallises from wa.teri n light grey needles melts a,t 212" (uncorr.) without decompositionwhen quickly heated and is readily soluble in alcohol; its aqueoussolution even when very dilute gives an intense yellow colorationwith nitrous acid.The barium salt crystallises in anhydrous lightgrey plates. F. S. I(.The hydrochloride forms brownish-red crystals.Dinitroparatoluic Acids and their Derivatives. By A. CLAUSand C. BEYSEN (Annalen 266 223-239) .-DinitroparatoluonitriEe[CN (NO,) Me = 1 2 G 41 can be obtained by adding sodiumnitrite in small portions at a time to a well-cooled sulphuric acidsolution of 2 6-dinitroparatoluidine and after keeping for a shorttime pouring the mixture drop by drop into ice-cold water; thesolution is filtered from unchanged dinitroparatoluidine mixed inthe cold with a solution of copper cyanide and then warmed on thewater-bath to complete the reaction.It crystallises from alcohol ingolden needles melts a t 103" (uncorr.) and is readily soluble in alcohol,ether chloroform benzene and glacial acetic acid but only sparingly inhot water. The corresponding arnide prepared by boiling the nitrilewith moderately concentrated sulphuric acid crystallises in yellowneedles melts at 255-257" (uncorr.) and is readily soluble in alcohol,etheP chloroform and hot water.Dinitroparntoluic a d [(NO,) = 2 61 is formed when the amidejust described is heated a t 220-230" for 8 hours with concentratedhydrochloric acid ; it crystallises from boiling water i n almostcolourless plates or prisms melts a t 2.26" (uncorr.) sublimes in needles,and has an intensely bitt'er taste ; i t dissolves freely in alcohol ether,benzene chloroform glacial acetic acid and hot water but is onlysparingly soluble in cold water.The barium salt with 1H20 crystal-Ziaes in yellow prisms and is very readily soluble i n hot water.1 * NH Azimidoparatoluic acid COOH*C,H,Me<- N>N is formed when3the hydrochloride of the 2 3-diamido-acid already described (comparepreceding abstract) is treated with sodium nitrite in aqueous solution ;it crystallises from hot water or alcohol in colourless lustrousneedles melts at 295" (uncorr.) with decomposition and is readilysoluble in ether and chloroform. The bai+um salt with 3H20 and%he calcium salt with 2H20 crystallise in colourless needles and arevery readily soluble in hot water.When the diamido-compound obtained from the 2 5-dinitrotoluicacid (loc.cit.) is diazotised and the product treated with cuprousbromide it is converted into dibromoparatoluic acid [COOE Br Me= 1 2 5 4 ] .Nitra?nido~aratolz1ic acid [ C 0 OH NO Me NH = 1 2 4 51 i178 ABSTRAOTS OF CHEMIOAL PAPERS.obtained when a solution of the 2 5-dinitro-acid in warm con-centrated ammonia is treated with hydrogen sulphide ; i t crystallisesfrom boiling water in long yellow prisms and needles melts at 220"with decomposition and i8 readily soluble in alcohol ether and hotwater. The barium salt crystnllises in yellowish-brown plates o rprisms and is anhydrous.Nitrobromoparatolzcic acid [COOH NO Me Br = 1 2 4 51 pre-pared by decomposing the diazo-derivative of the preceding compoundwith cuprous bromide crystallises in colourless needles melts at 181"(uncorr.) and is readily soluble in hot water alcohol ether and chloro-form but almost insoluble in cold water.The corresponding cbloro-derivative obtained in like manner melts at 184" (nncorr.) and isidentical with the metachloroparatoluic acid previously described byClans and Bocher (this vol.,p. 173).[COOH NO Me NH2 = 1 3 4 51,obtained by reducing the corresponding dinitro-compound (see pre-ceding abstract) with ammonium sulphide o r with the theoreticalquantity of stannous chloride in alcoholic hydrochloric acid solution,crystailises from water in lemon-yellow lustrous needles melts at 214"(uncorr.) and sublimes without decomposition ; it is only sparinglysoluble i n cold water but readily in alcohol ether and hot water.The barium salt with 4H,O calcium salt (anhydrous) sodium salt,with +H20 and the wagnesium salt with 5H,O are yellow crystallinecompounds.The mitrobromo-acid [COOH NO2 Me Br = 1 3 4 51,prepared by decomposing the diazo-derivative of the amido-acid withcuprous bromide crystallises from dilute alcohol in small colourlessneedles melts at 1131" (uncorr.) and is readily soluble in ether alcohol,and chloroform but only sparingly in boiling water ; its barium saltcrystallises from boiling water in which it is readily soluble in com-pact needles. The corresponding nitrochloro-acid prepared in likemanner melts a t 158" and is identical with the acid obtained byClaus and Bocher (loc.cit.) by nitrating metachloroparatoluic acid.Dichloroparatoluic acid [COOH C1 Me = 1 3 5 41 was pre-pared from the diamido-acid (m. p. 212') described in the precedingabstract; it was found to be ideiiticnl with the compound obtainediVitramidoparato1uuic acidfrom chloronitrotoluic acid (m. p. 159") by Claus and Bocher (loc. cit.).F. S. I(.Derivatives of Ethyl Dinitrophenylmcetate. By M. DITTRICHand V. MEYEK (Annalen 266 29-30).-Claus has pointed out thatsome of the compounds lately described by the authors (Abstr. 1891,1224) were prepared by him a short time ago (Abstr. 1890 979) ;Diphenylmale'ic Anhydride. By S. GABRIEL and G. COHN (Beis.,24 3228-3230) .-From the constitutional formulae of male'icanhydride and phthalic anhydride it seems probable that both com-pounds would show similar reactions and observations have alreadybeen made which confirm this supposition ; thus both yield ketonicacids with aromatic hydrocarbons as for example,COPh-CH:CH.COOH and COPh*CsH4-COOH ;the authors acknowledge Claus' claim to priority.1'. s. KORGANIC CIHEMISTRT. 119and both are converted into fluorescehs by the action of resorcinol(Abstr. 1882 1074; 1884 1340).The authors have further examined the behaviour of diphenyl-male'ic anhydride towards phenylacetic acid and find that it acts in asimilar manner to phthalic anhydride forming a substance closelyresembling benaalphthalide (Abstr. 1878 734 ; 1886 265).Thediphenylmalei'c anhydride was prepared accordiug to the methodgiven by Reirner (Abstr. 1881 l69) and was heated with phenyl-acetic acid and sodium acetate at 190" the temperature being raisedto 220-225" as soon as the reaction had moderated. The product ispowdered freed from impurities by extraction with alcohol and re-crystallised from acetic acid when i t is obtained in yellowish needles,having the composition C2,H,,OZ ; it is sparingfy soluble in alcohol,readily in acetic acid and acetone and very easily in chloroform andboiling benzene. It is formed according to the equationCPh*C(CHPh) CPh-COCPh-CO CPh- GO >O + CH,Ph*COOH = 1 1 >O + CO + H20. I Iand may therefore be termed benznldip7~e?zyl.l?zalei'de. In all itsreactions it closely resembles benzalpli thalide.Diphenylmale'ic anhydride also combines with phenol resorcinol,and dimethylmetamidophenol forming coloured compounds andwith qainaldine yields a colouring matter resembling quinophthalone.All these substances are being further investigated.H. G. C.Composition and Crystalline Form of Barium Isophthalate.By W. LOSSEN and C. RAHNEKFUHRER (dnnalen 266 30-33).-When a solution of barium inophthalate evaporates at the ordinarytemperature well-defined triclinic crystals of the cornpositionC8H40aBa + 6H,O are deposited ; these crystals rapidly efflorescewhen kept over sulphuric acid but only slowly in the air. Theauthors' experiments point to the non-exist,ence of the salts contain-ing 3 and 3$ mols. H20 which have been described by Fittig andVelguth and by Kelbe respectively.3'. S. K.Opianic Acid. By G. GOLDSCHMIEDT (Jlonatsh. 12 474-478).-When a solution of opianic acid (10 grams) and acetone (6 grams)in water (750 grams) is treated with a 10 per cent. solution of sodiumhydroxide (30 c.c.) and allowed to remain for 24 hours a t theordinary temperature condensation takes place with formation of thecompounds C2,H2,0 and Cl,HllO,. The former crystallises fromalcohol in which i t is but sparingly soluble in felted needles doesnot dissolve in cold solutions of the alkali carbonates is not changedby bromine in ethereal solution and melts at 151". The latter whichis the chief product of the reaction crystallises from dilute alcohol inwhite needles melts at 117" and resembles the former compound inits behaviour towards bromine and the alkalis.Under like conditions opianic acid and acetophenone give t h ecompound C18EE1606 which crystallises from alcohol in beautiful180 ABSTRACTS OF CHEMICAL PAPERS.glistening plates and melts at 127-126".It also is unacted on bybromine and by cold solutions of the alkalis.The three new compounds above described are not acids nor dothey contain doubly-linked carbon atoms. Their constitution is>c013 C H2(OMe),probably to be regarded as CO[CH,*CH<06 -YO - O> CHGH,COPh re- co-spectively. It is obvious in this case that opianic acid does notbehave as an ddehydic acid ; f o r if it did feeble unsaturated acids ofthe formuke CO[CH:CH*C6H,(OMe)2*COOH J2,C 00 H*C6H2(0&Ie),* CH:CH*C OMe and'>CH*CH2*COMe and IC'6H,(OMe)2 C6H2(OMe)2COOH*C,H,(O~!e),*CH:CH.COPh,respectively would result from the condensation with acetone andbenzophenone (compare Goldschmiedt and Egger Abstr.1891 1371).G. T. M.Oximes of Opianic and Phthalaldehydic Acids. By 0.ALLENDORFF (Ber. 24 3'L64-3266) .-In a recent paper (Abstr.,1891 1369) the author stated that the oxime of opianic acid was notknown he having at the time overlooked its description by W. H.Perkin jun. (Trans. 1890 1069). A. R. L.Metahemipinic Acid. By 0. Iloss~x (Monatsh. 12 486-500 ;*compare Goldschmiedt Abstr. 1889 167) .-This acid has the con-stitution C6H2(OMe),(COOH> [= 1 2 4 51 and forms an ethylhydrogen salt which melts at 127" and a diet&? salt which i n an un-crystalliPzble syrup and can be distilled unchanged under a reducedpressnre of 160 mm.The acid is converted by concentrated nitricacid into dinitroveratid C8H806N3 which crystallises from dilutealcohol in pale-yellow needles nielts at 131-132O is only slightlysoluble in water and appears to be identical with Merck's dinitro-veratro'il (AnnaZen 108 60). On heating the acid vith hydriodic orhydrochloric acid noiwzetahemipi& acid C&i606 [(OH) (COOH),= 1 2 4 51 was obtained. It crystallises with 1 mol. H,O whichis not expelled on heating a t 100" under the ordinary pressure and isonly slowly given up a,t that temperature in a vacuum. This acid isreadily soluble in alcohol dissolves sparingly in ether crystallisesfrom water i n rhombic prisms [ a b c = 1 0.08837 0.58791 andfrom acetone in beautiful needles.At 180" it gives a trace of a yellowsublimate which increases in quantity aiid turns red on further heat-ing whilst at 247.5" it melts having been converted into normeta-hemipinic anhydride.The ethyZ hydrogen salt of norliernipinic acid Cl0HI0O6 is obtained.on heating normetaheniipinic anhydride and absolute alcohol in a refluxapparatus for three hours. It crystallises from alcohol and ether inneedles which if quickly heated riielt at 182" but if heated moregradually melt at 175". The diethyl salt C,,H,,06 crystallises i181 ORGAN10 OHEMISTRT.small needles which melt at 148*5-149*5" and is readily soluble ilkalcohol. With ferric chloride both thc acid and its ethyl salts givt+an emerald-green coloration which is characteristic of substancesderived from protocatechnic acid.Derivatives of Tannin.By C. B~TTIKGEI~ (Arch. Pharm. 229,439-447 ; compare Abstr. 1890 1275) .-Ethyl ditannacetoacetate,C3,H,,0, is prepared by heating. a mixture of t'annin ('LO grams) andpotassium hydrogen sulphate (30 grams) with ethyl acetoacetate (30grams) a t 190-200" for 15 minutes and then adding more ethyl aceto-acetate (10 c.c.) and heating for another five minutes. The melt isextracted with water and ether whereby the larger quantity of the ethylditannncetoacetate is left as a semi-solid mass which is dried in adesiccator.Ethyl ditannacetoacetate is a yellowishpowder which dissolves freelyin alcohol ethyl acetate aud ethyl acetoacetate but very little in coldwater ; in hot water it; is somewhat soluble but is decomposed thereby,for on cooling slender felted needles separate which differ from theoriginal compound in containing 1 mol.less of water. When boiledwith water ethyl ditannacetoacetate is decomposed with evolutionof acetone ; when heated iii a sealed tube with water a t 160" acetone,carbonic anhydride gallic acid and tannin can be recognised asdecomposition products. Several minor reactions are given in thepaper.Ethyl tamacetoacetnte C.20H20012 is formed when the heating in theprocess for preparing the di-derivative is continued for 40 minutes.The melt is extracted as described above and the residue dissolved inalcohol mixed with ether filtered and evaporated a t a gentle heat.The semi-liquid residue is poured into cold water when the ethyltannacetoacetate is separated; it is dried in a desiccator.Ethyltannacetoacetate behaves with solvents similarly to the di-derivative,b u t does not dissolve in hot water more than in cold. When heatedwith water at 160" it behaves like the di-derivative.Hydrotannic and isohydrotannic acids are obtained when tannin(20 grams) is mixed with potassium hydrogen sulphate (30 grams)and glycerol (30 grams) and heated a t 190-200" for 54 minutes. Themelt is extracted with water and the residue dried and extracted withabsolute alcohol ; this extract is evaporated and the Bemi-liquidrcsidue is treated with much alcohol and ether; the isohydrotannicacid is thus precipitated whilst the hydrotannic acid remains i nsolution and is precipitated by pouring the solution into water.The hydrotamaic acid C13H1107 + H20 is purified by dissolving it inacetic acid and precipitating it again by the addition of water and a,few drops of hydrochloric acid.It is a brown powder which dissolveseasily in cold alcohol dilute acetic acid and warm acetic anhydride butnot in water ; when heated with zinc-dust it gives the same sharp odoui-which was noticed with hydroquercic acid (Abstr. 1891 1061). Itdissolves in ammonia with a brown colour; the solution absorbsOxygen and is reprecipitated by acetic and hydrochloric acids. Ityields a yellow acetyl derivative C1~HIIOQc~07 when heated with aceticanhydride a t 100".G.T. M182 ABSTRACTS OF CHEMICAL PAPERS.Isohyd~otannic acid ClAH1407 is insoluble in cold water and absolutealcohol but dissolves slightly in hot water and easily in hot aqueousglcobol ; it behaves similarly to hydrotannic acid and yields a brownacefyl derivative which is probably CI4HllAc3O7.The author concludes that these acids have high molecular weights,itre not glycerides and contaiu no glycerol residue. A. G. B.1 2 4-Chloronitrobenzenesulphonic Acid and 1 4 2-Chloro-nitrobenzenesulphonic Acid. By P. FISCHER (Be?-. 24 3185-3197) .-Of the ten possible chloronitrobenzenesulphonic acids onlythree have hitherto been prepared a<nd the exact constitution of theseis known in only one case namely that of the 1 4 3-chloronitro-benzenesulphonic acid (Abstr.1882 593). The remaining two wereprepared by Post and Meyer (Abstr. 1881 1037) and were alsoobtained by Allert (Abstr. 1881 902) who regarded them as a singlewid ; the latter further erroneously supposed that the chlorineoccupied the adjacent position to the sulphonic acid group and hisconclusions are therefore incorrect.1 2 4- Chzoronitl.obenxenesuzpphonic acid N020C6H3C1.S0.3H maybe obtained either by the sulphonation of orthochloronitrobenzene orby the nitration of parachlorobenzeiiesulphonic acid ; the lat termethod gives the best results as commercial orthochloronitrobenzenecontains large quantities of the para-compound. To prepare thesulphonic acid 100 grams of chlorobenzene is treated with a mixtureof 140 grams of crystallised pyrosulphuric acid and 140 grams of con-centrated sulphuric acid and the whole warmed for some time on thewater-bath t o convert into the sulphonic acid a small quantityof paradichlorodiphenylsulphone which is a1 ways simultaneouslyformed ; the nitration is carried out by adding 280 grams of bariumnitrate after which the whole is treated with a little water and thenitrous fumes removed by passing a strong current of air through theliquid.The acid is isolated as the barium salt the latter being de-composed with sdphuric acid ; it separates from a concentratedaqueous solution in slender deliqiiescent needles is soluble in alcohol,licetone arid acetic acid insoluble in ether and benzene and has apleasant aromatic odour and bitter astringent taste.The bariuin salt,(N0,*C,H,C1*S0,)2Ba + H20 forms compact yellow crystals or pale-yellow lustrous plates ; the ammonium salt colourless anhydrousneedles ; and the copper salt emerald-green needles. The sulpho-chloride NO,*C6H$1'SO2CI. crystallises from ether in large trans-parent crystals melting at 40-41" and the suZphonamide,NO,*CGET,Cl.S OZNH,,separates from water in pale-yellow prisms and from alcohol inyellowish-white needles melting at 175-176".When the above sulphonic acid is reduced with ferrous sulphateand baryta-water according t'o Claisen arid Thompson's method(Bey. 12 1946 ; 13 2126) it yields the barium salt of 1 2 4-chZor-arnidobenzenesu@honic acid (NH,*C6H3Cl.S 03),Ba + 4H20 whichcrystallises in colourless needles and only loses the last mol.of wateroi crystallisatioii at 210-215". The potassium salt forms colourlessORUANIC CHEMISTRY. 183anhydrous needles or plates. The free acid is obtained from thebarium salt by exact precipitation with sulphuric acid and separatesfrom the solution in long lustrous white needles the aqueous solutionof which is coloured dark brown by ferric chloride.1 4 2- Cla7oronit~-obe~zzenesulphonic acid is obtained by heating1 part of parachloronitrobenzene with a mixture of 4 parts of crys-tallised pyrosulphuric acid and 2 parts of concentrated sulphuric acidin a sealed tube at 120-130") and is isolated as usual by means ofthe barium salt. It crystallises in beautiful long needles or large,transparent crystals containing 2 mols.H20 and is not hygroscopic.The barium salt forms colourless lustrous anhydrous plates ; thepotassium salt iustrous white needles ; the sulphochZoride beautiful,transparent crystals melting at 89-90' ; and ihe sulphonamide,lustrous white plates or small colourless needles.1 4 2-Chloronitrobenzenesulphonic acid is also readily reduced byferrous sulphate and bezyta-water with formation of 1 4 2-chlor-amidobe.nzenesuZp~ionic acid NH2*CGH3C1*S03H which is obtained fromthe barium salt by the action of snlphuric acid and crystallises innnhydroi-ts lustrous white needles ; the barium salt with 4€I,O formscolourless needles. H. G. C,Note by Abstmctor.-l 4 2-Chloronitrobenzencsulphonic acid hasalso been recently described by Claus and Mann (Abstr.1891,1488),together with all its above-mentioned derivatives. Both descriptionsagree well together except in the case of the barium salt ofI 4 2-chloroamidobenzenesulphonic acid which according t o Clausand Mann contains 6H20 instead of 4H20 as given by Fischer.H. G. C.Diphenylenazone. By E. TAumn (Bey. 24,3081-3088 ; cornpareAbstr. 1891 5 i O ) .-Diphenylenuzone dioxide M0*?6H4 [NO PJO =NO*CRHd6 6'1 is prepared by dissolving orthodinitrodiphenyl (Zoc. tit.)(5 grams) in boiling 90 per cent. alcohol. (100 c.c.) adding 40 percent. aqueous potash (3 c.c.) and then zinc-dust (15 grams) in suc-cessive small portlions and finally boilinq for half an hour in a refluxapparatns and filtering the solution.The yield is about 25 per cent.of the theoretical. The substance crystallises from alcohol in needlesor in lustrous plates very faintly tinged with yellow. It melts withdecomposition at 240" explodes when heated and is reduced to theazone by sodium amalgam. I t is insoluble in water dissolves veryslightly in concentrated hydrochloric acid light petroleum and coldalcohol sparingly in ether and cold acetic acid rather sparingly inboiling alcohol benzene and toluene easily in hot acetic acid veryeasily in chloroform and phenol.D~heiLyZenea~oizenzonoxide O<vy6H' [N20 = 6 6'1 is obtainedfrom the mother liquor OE the dioxide and is separated from thelatter substance by a long and tedious process of recrystallisationfrom alcohol and fractional precipitation from a solution iu hydro-chloric acid by the addition of water.It can also be obtained byN.CcH184 ABSTRACTS OF CHEMICAL PAPERS.reducing orthodinitrodiphenyl with sodium amalgam. It crystallisesfrom dilute alcohol i n long pale-yellow needles with tt silky lustre,melts at 152" dissolves very readily in chlgroform readily in alcohol,boiling benzene toluene and acetic acid sparingly in hot water verysparingly in cold water and ether and not at d l in light petroleum.It dissolves readily in concentrated sparingly in dilute acids ; thesolvents have a deep-yellow colour. By sodium amalgam it is reducedto the azone.DiphenyZenazone CI2H8N2 [N N = 6 6'1 is obtained by dissolv-ing ort]hodinitrodiphenyl ( 5 grams) in methyl alcohol (200 c.c.),adding gradually 3 per cent.sodium amalgam (250 grams) to thecooled solution filtering concentrating t'o a small bulk and ad-ding water. The substance is dissolved in hydrochloric acid andprecipitated with ammonia and then recrystallised from dilutealcohol. It melts at 156" and boils above360" almost without decomposition. It crystallises with greatreadiness; especially fine crystals are obtained from a solution inbenzene. I t is pale greenish-yellow in colour and gives with acids,yellow solutions from which however no salts can be isolated. Itdissolves very readily in chloroform and acetic acid readily in alcohol,benzene and toluene sparingly in ether and light petroleum and notat all in water.When reduced with zinc-dust and hydrochloric acid ityields diphenylenehydrazone C,,H,:NZH [NH NH = 6 6'1 t h ehydrochloride of which C1,H1,JY2,HC1 forms white needles insoluble in20 per cent. hydrochloric acid. The salt and still more so the baseitself is very unstable oxidising in the air to the azoiie. It is un-affected by reducing agents.Diamid ndipheny leneazone [NH N = 4 6 and 4r 67,N*C6H,*NH,is prepared by reducing a solution of metadinitrobenzidiiie in methylalcohol with sodium amalgam. The residue left after evaporatingthe alcohol is dissolved in dilute acetic acid reprecipitated withammonia and crystallised from very dilute alcohol. It formssmall dark-red prisms CI2H,,N + 2H20 which lose 1 mol. H,Oover sulphnric acid and the second at 100".The anhydroussubstance begins to decompose at 260" and melts at 267". Itdissolves readily in alcohol sparingly in chloroform toluene benzene,and ether very sparingly in water arid not at all in light peti*oleum.When dissolved in a small quantity of hydrochloric acid it combineswith 2 mols. HC1 and forms a greenish-grey solution ; on adding moreacid i t combines with a third molecule of hydrogen chloride and thecolour changes t o reddish-violet. It is a basic dye and colourstanned cotton greenish-grey.The yield was 2 grams.9'?6H3*N H,C. 3'. B.Stilbene Thionessal and Tolallyl Sulphide (Tolane Sulph-ide).-By E. BAUMANN and M. KLETT (Uer. 24 3307-3314.)-When the polymeric thiobenzaldehyde which melts at. 8 3-90",(CsH5GHS) n = 10 or 12 is heated a t 150" it is decomposed intosulphur and stilbene CHPh:CHPh and at 190' the reaction takesplace more readily.But if the temperature rises above 20U0 somORGANIC CHEMISTRY. 185hydrogen sulphide is evolved and thionessnl formed. The two tri-thiobenzaJdehydes melting at 167" and 225" respectively behave iu asimilar manner except that the latter is not attacked until heatedabove its melting point when some thionessal is also formed.There was little doubt that the thionessal mentioned above wasformed by a secondary action of the sulphur on the stilbene and i twas found that when stilbene and sulrJGur are heated together a t250" hydrogen sulphide is evolved and fkonessal formed. Tgionessal,QPh:CPhCPh:CPh> '' which melts at 183-184" is thus t e t r a p h e n y l t l ~ i ~ p h e n ,and its formation is precisely analogous to that of thiophen itself onpassing ethylene through boiling s nlphur.Tolallyl sulphide cannot be obtained by further heating stilbene ortliionessnl with sulphur but is formed on heating berizyl sulphide orbisulphide and by distilling phenylacetic acid with sulphur ; it meltsat 174". I t was showii by Raoult's method t o have the forniulaCI1H,,S.Since tolallyl sul phide may be converted by oxidation,into oxylepiden which contains four phenyl groups it must itselfcontain pheuyl groups and has doubtless the formula I I >S. Abetter name for i t would he tolane sulphide.c PllCPhC. F. B.Action of Nitrous Acid on Tetramethyldiamidob snzo-phenone.By W. HERZBERG and M. POLONOWSRY (Uer. 24,3 197-3201) .-By the action of nitrous acid on tetramethyldiamido-benzophenone E. Bischoff (Abstr. 1888 1197 ; 1889 511) obtained apubstance to which he assigned the coiistitutionNMe,*C6H4.CO*C6H,(:NOH).NMe2.The authors find that when the reaction is carried out according toBischoff's instructions a yellow precipitate is formed amounting toabout 30 per cent. of the ketone taken ; this crystallises fromalcohol in yellow plates melting with evolution of gas at 182-183".The compound has however the composition Cl6H,,N3O2 and is inreality the nityosconine of trirnethyidiamidobenzophenons,NMe,*C6H4*C O*C6H40NMe*N0.By the action of concentrated hydrochloric acid it is converted intot rime t 11 y Zdiam id obenzop h enone NM e,* C H 4* C 0 * C6H4* N HMe which c ry s-tallises from alcohol in pale-yellow plates melts at '203-204" andyields an acrtyl derivative Cl,H,,N,O,Ac melting at 145".Thecompound described by Wichelhaus (Abstr. 1886 362) as trimethyl-diamidubenzophenme is probably a mixture of the trimethyl andtetramethyl compounds. In Bischoffs experiments he did notseparate the precipitate but added alkali and thus obtained amixture of the nitrosamine with unaltered ketone. If double thequantity of sodium nitrite be taken the yield of nitrosamine can beraised to 60 per cent. of the ketone a small quantity of a bubstancesparingly soluble in hot alcohol being then also obtained.VOL. LSII186 ABSTRAClTS OF CHEMICAL PAPERS.Nitrous acid acts in a different manner on tctrametbyldiamidodi-phenylmethane converting it partially into para>nitrodimethylaniline.Derivatives of Paraphenylbenzophenone.By G. KO LLER(Monnfsh. 12 501-511 ; compare Goldschmidt ihid. 2 437).-Paraphenylbenzophenoxime C6H4Ph*C Ph:NOH is obtained on tibeat-ing paraphenylbenzophenone in alcoholic solution with an aqueoussolution of hydroxylamine hydrochloride and potash. It crystallisesin needlep melts at 193-194" is insoluble in water dissolves readilyin alcohol aud ether and when heated a t 100" with a mixture ofacetic acid and acetic anhydride saturated with hydrochloric acid isconverted into the isomeric acid-anilide which melts a t 224" and isresolved into aniline and paraphenylbenzoic acid (m.p. 218-219")when heated a t 160' with fuming hydrochloric acid.The benzoyl derivative of the oximc C,H,Ph*CPh:NOBz crystal-lises from alcohol in slender white needles and melts a t 193". Ontreatment with sodium amalgam the oxime is reduced to the amido-base C6H,Ph*CHPh.NH which crystallises from e5her in slender,white needles melts a t 77" and forms an acetate which crystallisesi n needles melting a t 161" a hydrochloride which melts a t 252" nnitratc which melts a t 21 lo and a ptntinochloride which crystallisesi n yellow. needles containing 4 mols. HzO and melts a t 191".'The phenylhydrazone C,H,Ph*CPh:N,HPh is obtained by theaction of phenylhydrazine on pnraphenylbenzophenone and crystal-lises from absolute alcohol in yellow needles which melt at 144".Claus' Theory of the Benziloximes.By R. AUWERS andV. MEYER (Bey. 24 3267-3271).-Claus (this vol. p. 50) hasrecently put forward the view that the isomerism of the benzil-oximes is due to differences of molecular strocture rather than tothose of the relative positions i n space of the atoms within themolecule (stereochemicnl isomerism) and in defending the latterhypothesis the authors state that Claus has not taken into accountthe following facts :-Remophenone and its symmetrical di-sub-stitution derivatives yield only one oxime whereas its mono-suhstitu-tion derivative yields two for which reason such formuh as thoseproposed by Claus for the benziloximes are inadmissible for thebenzophenonoximes and it is specially to be noted that the isomerismof the oximes of both series have been proved by numerous experi-ments to be strictly analogous.Claus represents benzile-a-monoxime as a true oximido-derivative,CPhC(:NOH).COPh and benzile-y-monoxime as a nitroso-aicohol,CPhC(NO):CPh*OH and such a difference of structure wouldnecessitate a corresponding difference in chemical behavionr butthe single fact which Clsus adduces is that the a-derirative isconverted by an excess of hydroxylamine with greater eage into a.ciioxime than is the 7-derivative ; this being a difference of degreeand not of kind.In reality the a-derivative reacts with bothllydr oxylamine and its hydrochloride whereas the y- derivative onlyreacts with the free base ; towards all other reagents the two com-pound s ahow complete similarity in their behaviour ; apart fromH.G. C.G. T. MORGANIC CHEMISTRY. '187this however the formula ascribed by Clans to the y-monoxime isincompatible with the facts to be mentioned. It is well known thati-onitroso-compounds (oximes) are more stable than true nitroso-derivatives and it is difficult to understand why a nitroso-derivativeis formed by a reaction which shoiild yield an oxime as the directproduct and also that the same oxime is converted into a nitroso-derivative on heating its alcoholic solution a t 100"; it is necess:wyt o admit both of these hoaerer on Claus' hypothesis. Clans'formilla for the ybenzilemonoxime is entirely negatived by the ob-srrvation that the benzyl-derivative of this oxirne is formed by theinteraction of a-l,enzyihSdroxylamine and benzile (Abstr.'1889,; whereas t o 1193) thus :P h.7 NO.CH,PhPh-CO + NH2*O*CH2Pb = PhmQOPhGOPhfi'No is produced PhC*O-CH2Ph admit that a compound of the formulawould at once render it impossible to rely on the constitution of acompound which had been deduced from synthetical considerations.If therefore one of the benzilemonoximes is a nitroso-alcohol i t canonly be the unstable a-modification the benzyl derivative of which basnot up t,o the present been prepared from bcnzile and a-benzylhydr-oxylamine but then from this nitroso-alcohol (the a-monoxime) thea-dioxime which Claus regards as a true dioxime would be formedou treating it w i t h hpdroxylamine ; whilst the true monoxime (theymonoxime) would be converted into the nitrosohydroxglamide Ph*f?'No which according to Claus represents the v- dioxirne.Ph*C.NH*OH'Tlle authors dismiss the three benzildioximes with only a few ~~remarks and conclude with the statement' that as their invekgntionson all these compounds have shown that they have the same struc-ture they have 110 other alternative in accordance with the presentviews than to regard the isomerism as stereochemical.A.R. L.Dyes of the Triphenylmethane Group. Ry E. NOELTIKG (Rer.,24 3126-3136; 3136-:-3139 ; 3139-:3143 ; compare Abstr. 1891,727) .-Tetramet hy 2 t riamidodipheny 1 to1 y lmet hnne,3 6 1 4NH2*C6H3Me* C H ( C6H4*NMe2) 2,is prepared by mixing finely powdered tetramethyldinmidobenzhydrol(27 grams) with cooled concentrated sulphuric acid (2iO grams),adding paratoluidine (11 grams) raising the temperature to 40-50"to complete dissolution and tinally heating on the water-batb at50-60" for 6 to 8 horir~. The product is poured into water ( 3 litres),cautiously neutralised with soda and any unaltered paratoluidinediaiven over with steam ; the base is then dissolved in hydrochloricacid reprecipitated with ammonia extracted with ether and light,petroleum added to the dried et iereal solution to incipient turbidity,it being then placed over sulphuric acid in a vacuum when the leuco-base slowly separates in the form of white needles the yield being90-95 per cent.of the theoretical. I t melts at lGO" is sparingly0 "1 css ABSTRACTS OF CHEVICAL PAPERS.so uLle in light petroleum more readily in ether and alcohol andinsoluble in water.On Oxidation with lead peroxide i t yields abluish-green soluble dye homologous with metamidobenzaldehyde-green. The dibenzy I derivative COQH07NI( C7H7) is obtained by boilingthe leuco-base (1 mol.) with benzyl chloride (2.3 mols.) sodium acetate(1 mol.) and water (6-7 parts) in a reflux apparatus for 8-10 hours,the excess of benzyl chloride being then driven over with steam ; i t isdissolved in hydrochloric acid (1 5 ) concentrated hydrochloric acidadded whereby the hydrochloride melting a t 186" sepatrates in whiteneedles or for the preparation oE the free base i t is preferably con-verted into the zincochloride from which the base is obtained ontreatment with ammonia.The base when cryst<allised from a mixtureof ether and light petroleum melts a t 120" is not acted on bp aceticanhydride yields a greenish-blue dye on oxidation and is convertedinto sulphonic acids by the action of fuming sulphuric acid ; these givebluish-green dyes on oxidation which colour wool and silk i n an acid-bath. When the first-mentioned leuco-base is ethylnted a n d subse-quently oxidised a bluish-green dye is likewise obtained. The presenceof the methyl group in the ortho-position relatively to the fundamentalcarbon atom appears to have the effect of rendering the derived dyemilch bluer than those from the lower homologue. The phenol,0 H* C6I&Me* C H ( C,H,-N 31 e,) is o b t nin ed by d is sol ving tjhe le uco-base (36 grams) in a mixture of concentrated sulphuric acid (70 grams)and water ( 3 litres) diazotising the cjoled solution w i t h sodiumnitrite ( 7 grams) heating on the water-bath precipitating witharrlimonia and finally extractiug with ether; it separates from amixture of ether and light petroleum in white needles meltfi a t 156",and is sparingly soluble in light petroleum and aqueous alkalis easilyi n ether alcohol and acids b u t insoluble in water ; on oxidation ityields a dye of a less bluish shade than those obtained from theamido-derivative.3 6 1 4Tetramethy 1 triamidodiphen y ltoly lmethane,2 5 1 4N H,C6H,hle*GH ( C6HA.NMe2)2,is produced by heating a mixture of tetramethyldiamidobenzhydrol,yatratoluitiine hydrochloric acid of 22" Baumb (27 grams of each) andwater (100 c.c.) on the n-ater-batlh for 12-13 hours.The pure leuco-base crysfallises from alcohol in needles and melts at 180" the yieldheing 75-80 per cent. of the theoretical. It gives a faint bluish-violetdye on oxidation ; the dibenzyl derivative is iess readily oxidised thanthe above-described isomeride whilst on oxidising the dicccetyl deriva-tive a green dye is obtained which on treatment with hydro-chloric acid or alcoholic soda is converted into a bluish-green dyewith the elimination of the acetyl groups. The corresponding phenolcrystallises from a mixture of' light petroleum and ether in whiteneedles melts at 129-13U0 and is more soluble in light petroleumtiian its isomeride; its constitution is proved by the fact that it isobtained by condensing homosalicylaldehyde with dimethylaniline inthe prescnce of zinc chloride.The condensation of asymmetrical-metaxylidine mesidine 9-cumOROANIC CEEMISTRY.189idine isoduridine and prehnidine (consecutive tetramethylaniline) withtetramethyldiamidobenzhydrol has also been effected by the author.In the presence of sulphiiric acid asymmelrical metaxylidine yields a,lenco-base melting a t 1/38' and giving a green dye of a less bluishshade than that obtained from paratolnidine ; mesidine a leuco-basemelting at 142" giving a green dye of a more bluish shade ; whilst9-cumidine and isoduridine yield leuco-bases melting a t 132" and157" respectively the former giving a green dye of a very bluishshade and the latter one of a less bluish shade.The reactionproceeds with difficulty with prehnidine and the leuco base aith-stands oxidation to a marked extent. In tbe presence of hydro-chloric acid asymmetrical metaxylidine yields ft leuco-base melting a t145" and 9-cumidine one melting at 163-164" ; both behave towardsoxidisinq agents like the base from prehnidine whilst mesidine andisoduridine yield the same products as in the presence of sulphuricacid.Tetrethy 1 triamidodiphen y ltoly lmethane,NH,C6H,Me*CH( C6H4*NEt,),,prepared from tetrethyldiamidobenzhydrol and paratoluidine i n thepresence of concentrated sulphuric acid melts a t 103" and yields adye of a less bluish shade than that of the corresponding tetramethyiderivative.The base obtained from tetramethyldinmidobenzhydrol and dibenzgl-paratoluidine in the presence of sulphuric acid is entirely differentfrom the above-described dibenzyltetrta,methyltriamidodipbenyltolyl-methane; i t yields a pure green dye on oxidation and condensat:oiihas perhaps taken place in the benzyl residue ; that such is possibleis proved by the fact that benzjlamine condenses with the hydro1under the same conditions and the product yields a green dye onoxidation.Paraniti-odimet h y ldiamidochphen y tt 01 y lmet hane,is prepared by dissolving paranitrodimethylamidnbenzhydrol (27grams) in coucentrated sulphuric acid (300 grams) adding para-toluidine (20 grams) and heating the mixture on the water-bath a t60-70" for 12 hours.The base separates from a mixture of alcoholand benzene in yellow needles and melts a t 202" ; on oxidation withlead peroxide or chloranil a brown dye is obtained which onlyimparts a faint colour to cotton mordanted with tannin; the presenceof an amido-group in the meta-position relatively to the fundamentalcmbon atom appears to hinder the ready oxidation of the cqmpouud.The acetyl derivative cr,ystallises in white needles and on oxidationM ith chloranil yields a dye which colours mordnnted cotton orange-red; the shade remains unaltered when tlie acetyl groups are eliminatedby heating the dye with acids.Dirneth yltriamidod~ppkenllZtolylmet~ane,3 6 1 4 INH,-C6H,Me*\,H( C6&'N&1ez) *C6H4*1?( &190 ABSTRACTS OF GHEMIOAL PAPERS.is obtained by reducing the last-described nitroleuco-base with tidand hydrochloric acid; it crystallises from a mixture of ether and'light petroleum in white needles melts at 154" and on oxidation withlead peroxide? yields a bluish-green dye; whereas the acetyl deri-vative on oxidation with chloranil yields a dye colouring cottonmordanted with tannin a beautiful red.When the base is dissolvedin methyl alcohol and heated in a reflux apparatus with methyliodide and soda hexamethyltriamidod~~heieyltolymetl~arL~ is formed ; i tcrystallises from a mixture of ether and light petroleum in whikplates melts at about lOO" and yields a bluish-green dye onoxidation.TetramethyltriamidotPiphenylmethane prepared by the condensn-tion of paranitrobenzaldehyde with diniethylaniline and also froni.tetramethyldiamidobenzhydrol and aniline (I).R.-P.87032) melt's at151-152" and n o t at 65" as slated by Nathmsohn and Miiller(Abstr. 1M9 1190) ; it has furthermore the consiitution4 1 4NH,.C,~,.CH(C,H,.NIMe,),;the cornpound of the constitution given b y NathauRohn and Miiller is,described by 0. Fisches and Schmidt (Abstr. 1884 1315) and meltsat 134-135" ; the methiodide melts at 193" with decomposition.Te trame tli y ld iamidw d ippheny.1 puinol y lir L et h an e,&l 4C9NHs*CH ( C6H4mN&!e2)2,is obtained by heating a mixture of tetramethyltriamidotriphenyl-metbane (4 grams)? glycerol (3.8 grams) sulphuric acid (6 grams),and nitrobenzene (0.9 g r a m ) at 140-150" for 10-12 hours.I tcrystallises from alcohol in white needles which become greenish inthe air melts .at 165" is soluble in ether and benzene and insoluble inlight petroleum and water and yields a green dye on oxidation ; thehydrochloride C26H2,N3,3HC1 is readily soluble and the platinochloridcsparingly soluble in water.~etra.methyltm'amidodiyk~.nylnzethoxytolylmelha~ze,4 2 5 1 4NK,. C6H2Me(0 Me) mCH( C,KI-NMe2)2,is prepared by heating a mixture of te tramethyldiamidobenzhgdrol(10 grams) ttmidomethglrnethoxybenzene NH,*C,iH3Me.0hTe[2 4 1 J (5.3 grams) and 36 per cent. hydrochloric acid (10-3 grams)on the water-bath for 4 hours ; it crgstallises in white needles meltqa t 158-159" is somewhat sparingly soluble in alcohol and ether,and very readily in benzene and yields a beautiful blue dye onoxidation.l'etramethy Ediamidodiph enylmetlioxymet hy lpuinoly lmethane,4 2 3,l 4C9NH4Me( 0Me)GH ( C6HI-NMe2),,is prepared from the last described base it being however foundexpedient to employ picric a,cid instead of nitrobenzene in its prepam-tion ; the compound crjstallises from a mixture of l i g h t petroleuORGANIC CHEMISTRY.191and benzene in white needles melts at 183" and yields a green dyeon oxidation. A. R. L.Benzeneazo-a-naphthylglycocine. By A. DONNER (Bey. 24,2902-2904) .-Azo-dyes have previously only been prepared fromsubstituted amines in which the amido-hydrogen atom is replaced 11.yalkyl groups. The author has now obtained azo-dyes from anlines inwhich the amido-hydrogen atom is replaced by a group containingcarboxyl group.Berueneazo-a-naphthy lglycocine is prepared by adding a solutionof a-napthylglycocine dissolved in dilute hydrochloric acid to asolution of diazobenzene chloride a t a tempemture not exceeding 0".After remaining 12 hours the hydrochloride of the new compoundseparates as a dark-brown crystalline precipitate ; it is collected,washed with dilute hydrochloric acid aud dried.It crystallises fromalcohol in needles meltls a t 170" with evolutiorr of gas is sparinglysoluble in water more so in concentrated hydrochloric acid and easilyin alcohol. The solutions are intense reddish-blue and t u r n yellowish-red on the addition of a1ka)lis. I n concentrated sulphuric acid it dis-solves with a deep-blue coloration which changes to violet on theaddition of water.The hydrochloric acid solution dyes silk a violetcolour. By continued washing with water the hydrochloride under-goes partial decomposition into the free base.Benzeneaxo-a-naphthylglycocine behaves as an amido-acid andforms salts both with acids and bases. The potassiuna salt is ob..tained by adding a slight excess of potassium hydroxide to the hydro-chloride. It crystsllises in bronze-red tablets which rapidly discolourin the air and must be dried in a vacuous desiccator over calciun~chloride and potassium hydroxide ; it dissolves easily in alcohol a,ndwarm water more sparingly in the cold. The aqueous solution gives,with silver nitrate a red and with copper sulphate a brown precipitate-.The ainmowium salt is prepared in a similar way to the potassium saltand crystallises in well formed yellowish-red needles.Silk is dyedgolden-yellow by solutions of the alkali salts.The f r e e buse is best prepared by adding the theoretical quantityof potassium hydroxide to a solution of the hydrochloride evaporat-i n g to dryness and extracting wit,h alcohol. It crystallises in snlttll,lustrous green needles melts a t 133" with evolution of gas and issparingly soluble in water more easily in alcohol and ether. Thesolution is brown. The free base can also be prepared by decompos-ing the potassium salt with carbonic acid but a t the same time acompound is formed which crystallises in reddish- brown needles andwhich the author believes to have the constitutionNzPh CloHs*NH*CH2*C 0 ONH,(CH,m C 0 OK)*C,oHe*N,Ph.E.C. R.Hydronaphthoic Acids. By A. v. BAEYER R. SCHODER andE. E. BESEMFELDER (Annalen. 266 169-202).-This paper has beenpubiished somewhat sooner than was intended because of the appear-ance of an article by v. Sowiriski (Abstr. 1891 1380) on the samesubject ; it will be seen by comparing the two papers that there arenumerous points of disagreement between them for which reason th192 ABSTRACTS OF CHEXICAL PAPERS.nuthors think that the publication of their results is by no means asuperfluous proceeding.Labile A2-dihydro-a-naphthoic acid CCOOH = 11 is obtained bydiesolving a-naphthoic acid (5 grams) and the theoretical quantity ofsodium carbonate in water (50 c.c.) and then adding 4 per cent.sodium amalgam (60 grams) to the well-cooled solution throughwhich a stream of carbonic anhydride is at the same time passed ;when the solution is found to be free from naphthoic acid it isneutralised with dilute sulphuric acid filtered mixed with excess ofsulphuric acid and the precipitated acid purified by means of itsbarium salt which is very readily soluble in water (the impuritiesremaining undissolved).It crystallises from light petroleurn jxislender colourless monoclinic needles melts a t 91" and is readilysoluble in ether ethyl acetate alcohol and caxbon bisulphide butmore sparingly in benzene light petroleum and cold water (1 i n 552parts) ; it seems to be decomposed by boiling water and unlike theh2 5-dehydroterephthalic acid with which i t bas many properties incommon it immediately decolorises an alkaline solution of potassiumpermanganate being converted into phthalic acid resinous products,and an acid which has the odonr of acetic acid.The silver salt sepa-rates from water in reddish needles. The dibromide C10H9Br2*COOH,prepared by treating the acid with bromine in well-cooled carbonbisulphide solution separates from a mixture of ether and lightpetroleum in the form of a crystalline powder melts at i32" and isreadily soluble in ether and carbon bisulphide but more sparingly inbenzene and light petroleum; it is stable towards potassiiim per-manganate the violet colour disappearing only on prolonged keeping.It is readily reduced by zinc-dust and glacial acetic acid being re-converted into the original dihydro-acid and when warmed withalcoholic potash it yields naphthoic acid.Stable A'-dihydro-a-naph-thoic acid is formed when the labile acid is boiled f o r a few hourswith soda ; it separates from ethyl acetate in well-defined monocliniccrystals a b c = 1.5399 1 1.5657 = 59" 12' melts at 125",and is moderately easily soluble in alcohol but orily very sparingly(1 i n 3512 parts) i n cold water. The silver salt crystallises from hotwater in colourless needles which soon turn reddish on exposure tothe air. The acid is immediately oxidised by potassium permanganate,yielding orthxarboxyhydrocinnamic acid (m. p. 165") and smallquantities of phthalic acid ; the formation of the first-named corn-I'ound proves that the dihydro-acid has the constitution assigned toi t above.The dibromide separates from a mixture of ether andlight petroleum in yellowish crystaJs melts at 152O and is reconvertedinto the original dihydro-acid on reduction with zinc-dust and glncialacetic acid ; it is very stable towa,rds potassium permanganate but isdecomposed by boil irig methyl alcoholic potash yielding a-nayhthoicacid and the dibydro-acid.Tetrahydro-a-naphthoic acid is formed when a-naphthoic acid oreither of its dihydro-derivatives is treated with sodium amalgam inwarm alkaline solution ; when reduction is a t an end the neutralisedsolution is filtered and then treated with sodium carbonate andpotassium permanganate until the solution retains its violet co2ouORGANIC CHEMISTRY.193f o r a Rhort time. The acid is then precipitated with sulphurous andPulphuric acids and repeatedly recrystallised from ethyl acetate fromwhich it separates in well-defined triclinic crystals melting at 85" ;i t is soluble in 1052 parts of cold water and is moderately stabletowardR potassium permanganate the violet colour disappearing onlyafter keeping for R few minutes. The silver salt crystallises from hotwater in which it is moderately easily soluble in colourless needleswhich soon assume a reddish hue. When the chloride of the acid istreated with bromine in the cold and the product then warmed withconcentrated formic acid a yellow crystalline compound seemingly Hmonobromo-substitution product of the tetrahydro-acid is obtained.The amide crystallises from alcohol in colourless needles and melts at116".Two dihydro-acids are formed when P-naphthoic acid is reducedwith sodium amalgam as described i n the case of the correspondingor-compound (except that potassium carbonate is used instead of thesodium salt) ; on acidifying the two acids are precipitated i n an oilycondition but this oil quickly solidifies and afher recrystallisationfrom hot water a seemingly homogeneous substance meltirig at10.3-1 04" is obtained ; it is possible however by fractional precipit.a-tion to resolve this prodiict into the two acids described immediatelybelow.Labile A3-dihydro-fl-naph thoic acid crystallises from dilute alcoholin microscopic seemingly rhombic prisms melts at 104-105" and issoluble in 1734 parts of water at 14" ; it is immediatelg oxidised bypotassium permanganate in sodium carbonate solution yieldingphthalic acid and oxalic acid but on oxidation with potassium ferri-cyanide it is reconverted into 6-naphthoic acid.The silver salt isdecomposed by boiling water.The lactone of a bromohydroxytetrahydronaph thoic acid is formedwhen the preceding compound is treated with bromine in well-cooledcarbon bisulphide s o h t8ion in the dark the solution then evaporatedat the ordiiiary temperature (whereon hydrogen bromide Is evolved),the yellowish-red residue dissolved in ether and the solution shakenwith sulphurous acid and sodium carbonate successively.I t separatesfrom ether in monoclinic crystals. melts at 124" with decomposition,and is insoluble in cold Bodium carboilate ; when treated with zinc-dust and glacial acet8ic acid it is reconverted into the labile dihydro-acid and alcoholic potash transforms it into P-naphthoic acid. Thislactone has doubtless the constitution represented by the formulaCH-CHBr-CH and its formation from the labile acid shows thatthe latter is the A3-dihydro-derivative ; the dibromide from whichthe lactone is produced could not be obtained in crptals.St,able dihydro-/%naphthoic acid is formed when the labile acid isboiled with soda but the conversion is never complete and inpresence oE air naphthoic acid is also formed; it is therefore moreconveniently prepared by boiling a solution of the potassium salt ofp-naphthoic acid with 3 per cent.sodium amalgam. until the whnle ofthe naphthoic acid has been reduced. The stable acid is then separated/C Hz* CJL\'co-0a-Naphthoic acid .. . . . .A'-llihydro-a-acid . .. ..n2-Dihydro-a-acid . . . . .Tetrahydro-a-acid . . . . .I( = 0.0197K = 0-OU80X = 0.0114K = 0.00445&Nap' tlioic acid.. .. I( = 0-00523A2-Dihydro-B-acid ... I( = O'UO290A3-Dihydro-#l-acid . . K = 0.00615Tetrahydro-@-acid . . . K = 0'0025ORGANIC CHEMISTRY. 195fusing naphthionic acid with sodium hydroxide under pressure(D R.-P. 46507) ; the products from the two methods are dissimilarin appearance as are also to some extent the azo-dyes obtained fromthem but the latter after repeated crystallisation are found to beidentical.On reducing these dyes with an acid solution of stannouschloride (Witt Abstr. 1839 270) a sparingly soluble amidonaphthol-sulphonic acid separates after a time in the form of iridescent,greyish needles and plates; this can be purified by repeatedlydissolving in disodium sulphit,e solution reprecipitating by hydro-chloric acid and finally washing with water alcohol and ether ; i tcontains 1 mol. H,O. It is probable that the impurity in the naph-tholsulphonic acid prepared by the fusion method is due to thepresence of an isomeride which may perhaps be produced by intra-molecular change during the fusion hut the acid prepared by Nevilleand Winther's method also contains an impurity the nature of whichhas not as j e t been determined,P-Nitroso-a-na~hthol-a-~ulp~~onic acid is obtained when sodiuma-naphthol-a-sulphonate (24.6 grams) is dissolved in water (300 c.c.),39 per cent.hydrochloric acid (19 c c.) added and sodium nitrite(6.9 grams) in concentrated solution slowly dropped into the cooledmixture ; the precipitated compound is collected and crystallised froma mixture of water (500 c.c.) and hydrochloric acid (50 c c.) when itseparates in brownish-yellow lustrous crystals the yield being 20grams. It contains 34 mols. HzO and is rendered anhydroiis at 115",after which i t is very hygroscopic; it is easily soluble in water antialcohol ; concentrated sulphuric acid dissolves it with an orange-redcolour which on dilution hecomes yellow whilst nitric acid onheating converts it into dinitronaphthol.The acid dissolves inammonia and in sodium hydroxide solution with a reddish-browncolour forming the normal salts and from these solutions on additionof barium chloride and alcohol a gelatinous barium scclt is pr.ecipit,ated.The salt OH*C,oH,(NO)*SO,Na separates on adding an excess ofsodium acetate to the hot aqueous solution of the acid in the form oforange-yellow needles and prisms ; the barium sult ( CloH6NS0,),Ba +3H20 is precipitated i n small vermilion crystals on adding bariumchloride to a solution of the preceding sodium salt. The acid gives ared colour with cobalt salts and a green colour with iron salts;when heated with aniline naphthaquinonedianilide (Zincke Abstr.,1882 967) is formed.It reacts with orthodiamines with the produc-tion of scarlet dyes probably belonging to the eurhodine group ; thebase obtaiued with 1 2-diamidotolueiie forms golden-yellow zieedles,and melts a t 257". On careful reduction with acid stannous chloridesolution or when heated with sodium hydrogen sulphite solution ityields the same amidonaphtholsulphonic acid as the azo-dyes derivedfrom a-naphthol-a-sulphonic acid (see above) and must thereforehave the constitution [OH NO SO,H = 1 2 45.Sodium P-na~hthaquinone-a-sul~honate ClnH502*S03Na is preparedby gentIy heating the last-mentioned amidonaphtholsulphonic acid( 5 grams) with nitric acid sp. gr. 1.4 (10 c.c.) and adding a saturatedsolution of sodium chloride (40 c.c.) ; it separates in yellow needles,and is crystallised from dilute alcohol ; it is readily soluble in wate196 ABSTRACTS OF CHEMICAL PAPERS.and almost insoluble i n alcohol ; sulphurous acid ccinverts it into thecorresponding quinol-derivative.The quinnne reacts with 1 2-di-amidotoluene forming an azine which crystallises in red needles thnsproving its constitution.Sulphonic Acids of p-Naphthaquinone. By 0. N. WITT (BPT.,24. 3154-315'i).-The amidonaphtholsulphonic acids are very readilyoxidised ; thus in alkaline solution they are converted by the oxygenof the air into greenish-brown compounds which may be derivativesof /!-napht,haquinhydrone ; in acid solution when ferric chloride orpotassium dichromate is nsed as the oxidising agent B-naphtha-quinonesulphonic acids appear to be formed w tiich cannot however,be isolated on account of their great affinity for these metals.Ammonium P-naplLt It aquinonesdphonate C ,,,H5O2-SO3NH4 is obtainedby adding amido-/+-naphthol-/-sulpbonic acid (10 grams) in sma; Iportioiis a t a time to nitric acid sp gr.1.2 (10 c.c.) ; the semi-solidproduct is spread upon a porous tile and finally crystallised from avery small quantity of mater the solution being cooled by ice; in thisway a pyoduct representing 6O-i5 per cent. of the starting material,is obtained i n the form OE golden-yellow needles; i t is dried at100-110". The compound is very soluble in water and somewhatless so in alcohol ; on treating it with sodium hydroxide the sodiumsalt is formed but an excess of the alkali decomposes it; i t reactswith orthodiamines with the forinat ion of azinesulphonic acids.Thecorresponding quinol-derivative is formed when the sal t is reducetiwith aqueous sulphurous acid but it is more conveniently prqmredas follows :-The amidonaphtholsulphonic acid is mixed with waterand the calculated quantity of bromine added ; to the solution of thequinone an excess of snlphurous acid is now added and the ammoniuniquinolsulphonate isolated by evaporating the solution ; it formswhite plates and is very easilg soluble in water ; alkalis colouv itsaqueous solution deepyellow and aminonin in the presence of airdeep-brown ; silver sal6s are immediately reduced and it is notoxidised to the quinone by nitric acid of sp gr.below 1.2. Wlieiioxidised in the presence of pnradiamines violet-red dyes belongingto the group of indoplicnols are produced and it reacts with diazo-compounds with the formation o€ azo-dyes which yield brownish-redto indigo-blue lakes with metallic mordants. It thus furnishes anexception to the observations that orthodihgdroxy-compounds are notcapable of forming azo-dyes. 'P 11 e 0th e r amidonaphtholsul phonicacids yield similar compounds on oxidation.By H. PICTET and H. J. ARKERSMIT (Annnlen.266 1%-1.53 ; compare Abstr. 1891 837).-Attempts to synthesist.phenanthridine by treating orthohydroxybenzylideneaniline,0 H.C,H,*CH:NPh,and benzylideneorthamidophenol OH-C,H,*N:CHPh with dehydrat-i n g agents were unsuccessful ; both compounds seem to yield smallquantities of acridine on distillation over zinc-dust.BenzyIidet2eorthaniiClop7L61101 C13Hl,N0 prepared by the condensa-A.R. L.A. R. L,PhenanthridineORGANIC OHEMISTRT. 197+ion of henxaldehyde and orthamidophenol ciytallises from alcoholi n grej hexagonal plates melts a t 89" and is readily soluble in etherand benzene but insoluble in water. prepared as previously de-scribed (Zoc. cit.) crystallises from alcohol in colourless needles meltsabove 290" and is insoluble in cold water ether benzene and alkalis.Phenanthridilze methyl hydrozide C,aH,N,MeOH prepared by de-composing the metliiodide ( A bstr. 1890 390) with alcoholic soda,crjstallises in colourless needles mslts a t log" arid dissolves freely inalzohol ether and mineral acids yielding fluorescent solutions.HZ is obtained when phenanthridineC6H4.NH 'hydrochloride is treated with tin and hydrocliloric acid ; i t c r p t a l -lises from dilute aicohol i n colourless needles melts at go" and iswlrriost insolnble in wafer but very readily soluble in alcohol andether yielding fluorescent solutions.It is readily oxidised even oncxposure to t3he air being reconverted into phenanthridine. Thenzercurochloride crystallises from hot water in needles and melts at204". The pZatinor:hZoride decomposes a t about 220" but withoutitieltiug. The picrate and the dichromate crystallise from hot wateri i i slender pllow nebdles. The nitroso-derivative is an oil. Theucetyt derivatj ve C,,HlsNO cryst'allises in colourless prisms meltingat 108".F. S. K.YJL*Q (OH)CGH,*N Hydroxyphenanthridiue,D;hydrophenanthri~~~ae,Methylphenanthridine and Chrysidines. By A. PICTET and S.$!RLICH (Annalen 266 153-168 ; compare Abstr. 1891 217).-Paramethy~207~ennnthridine7 (?6H4-EH [N Me = 2 51 is formed,CJ€,Me-Ntogether with benzene toluene.- &c. when the vapour of benzylidene-paratoluidine is passed over red-hot pumice ; it is isolated by meansof its mercurochloride. It crystallises from dilute alcohol in long,colourless needles melts a t 131" and is readily soluble in alcohol,ether benzene chloroform and light petroleum b u t only very spar-ingly i n water; its aqueous and alcoholic solutions show a slight,blue fluorescence.The hydrochloride is readily soluble in water fromwhich it crystallises in yellow needles ; the suZphate and the nitrateare also readily soluble. The plutimcldoride ( C14HllN)2,H2Pt C1 +2H20 crystallises in yellow needles loses its water a t 110" does notmelt below 28P and is decomposed by hot water. The mercurochlondeforms yellow needles melts at 215" and is sparingly soluble in coldwater the solution showing a green flcorescence. The aurochloridecrystalliscs in yellow needles melting at 210" with previous decom-position. The picrate and the diclwomate crystallise in needles. Themethiodide C14H,,N,MeI crystallises from warm alcohol in brownneedles melting a t 180" with decomposition. The methyZ hydroxide,C11H,1N,b4eOH ciytallises from dilute alcohol in colourless needles,melts a t 136" and is almost insoluble in water.The methochzoridecrjstallises in yellow needles and is only sparingly soluble in coldwater198 ABSTRACTS OF ClEEMICAL PAPERS.OrthornothyZ~henai~t~ridi~,e CI,H,,N [N Me = 2 31 is obtainedwhen the vapour of benzylideneorthotoluidine is passed over red-hotpumice. but the principal product is a-phenylindole (compare Ahstr.,1886 711) ; it melts a t about 70". is not easily obtained in crystals,2nd is very readily soluble in alcohol ether chloroform benzene andlight petroleum. The hydrochloride crystallises from water i n slender,yellow needles and dissolves freely i t 1 cold water the dilute solutionsshowing a blue fluorescence. The platlnochloride (C,,H,,N) H2Pt C16 + 2H20 crystallises in yellow needles and does not melt below 275".The rnercurochloride (m.p. 156") aurochloride (m. p. 196-200") andthe picrate (m. p. 220" with decomposition) mystallise i n yellowneedles the d i c h r m a f e crystallises from hot water in shall orange-red needles. The wethiodide C14HI,N,MeI separates from alcohol inbrownish-yollow needles melts a t 187" with decomposition and isreadily soluble in alcohol and water hnt only very sparinglyin ether.a-Chrysidine (Abstr. 1891,217) crystallises from alcohol in needles,melts a t 108" and is readily soluble in ether chloroform and lightFetroleum but insoluble in water. The hydrochloride crystallises fromhot dilute hydrochloric acid in yellow needles and melts a t about 210".The nitlaate forms yellow prisms melting at 155".The platinochloride,(Cl,H,lN)2,H2PtC16 + 2H20 crystallises in long yellow needles anddecomposes a t 255". The mercurochloride (m. p. 240-245") theauroaldoride (m. p. 228") and the picrate (m. p. 240") crystallise inyellow needles ; the dichrornate and the zinc double salt (m. p. aboutfrom alcohol in pale yellow needles. melts at 108" and is insoluble inetlier. The methyl hJydroxide C1,H ,,N,MeOH forms colourless needles,and melts a t 110". The methochloride crystallises from dilute hydro-chloric acid in long slender needles ; its mercurochloride melts at 215",and its platinochloride (C,,H,,N),,Me2PtC1 crystallises in yellowneed1 es .p- Chrysidine (loc. cit.) crystallises from alcohol in lustrous colour-less needles melts a t 131" and resembles the corresponding a-deriva-tive in its properties.The hydrochZor;de crystallises in small yellowprisms and melts at about 220". The nitrate is sparingly soluble,and forms yellow needles melting a t 187". The pZatinochZoride,(C17H,,N)2,H2PtC16 + 2H20 crystallises in yellow needles and meltsa t 245" with decomposition. The dichrornate (C,,H,,N,),,H,Cr,O +2H20 crystallises from hot water in orange needles aud decomposesa t about 200" but without melting. The rnercumchloride (m. p. 272"),CI icrochloride (m. p. 245" with decomposition) picrate and zinc doubles a l t crystallise in yellow needles. The methzodide Cl7HlIN,MeI crys-tallises from alcohol in brown needles melts at 237" and is onlysparingly soluble in cold water and insoluble in ether.The corre-sponding hydroxide forms colourless needles melts a t 133" and isreadily soluble in alcohol and ether but insoluble in water. Theinethochloride crystallises from dilute hydrochloric acid in lustrousneedles ; its platinochloride (C,,H,,N)2,Me2PtCI forms yellow needles.Phenanthridine and the f o u r bases described above have manyproperties in common ; they are feeble bases and their salts are alldecomposed by water. Their methiodides are decomposed by soda in( r 2 ,O C ) are also crystalline. The methiodide C,,H,,N,MeI crystailiseORGAN'C CHEMISTRY. 3 99the cold yielding crjstalline hydroxides these compounds are Rolublein alcohol and ether yielding solutions which show a blue and a violetflnorescence respectively and they form with acids yellow salts theaqueous solutions of which show a green fluorescence.P. S. K.Action of Benzoic Acid on Turpentine. By G. BOUCHARDATand J. LAFONT (Cornpi. rend. 113 551-553).-Renzoic acid appearst o unite with French turpentine slowly in the cold ; at 150° employ-ing equal weights of acid and turpentine the act>ion is rapid after50 hours' heating all the turpentine is taken up. The uncombinedacid is removed from the product by treatment with an alkali. Theportions volatile below 200" separate iuto solid camphene boiling at 157",[alD = -3" 30' and an isomeric liquid terpilene boiling a t 175-180",[a] = -3"to -4" 30'. The production of almost inactive carnpheneatid terpilene is accounted for by the formation of turpentine andterpilene benzoates which under the prolonged influence of a tem-perature of lFiO' yield acid and camphene and terpilene respectively,hydrocarbons losing their rotatory power rapidly under these con-ditions.Camphene has been isolated to the extent of l / l O t h andterpilene of 1/3rd of the weight of the turpentine. The residue lefton distilling at 220" forms nearly half the weight of the turpentine.It decomposes on distillation into henzoic acid and camphene hydro-carbons. It may be distilled at 190-19.5" under a pressure of 30 mm.when a small residue of polyterpilenes rpmains consisting principallyof colophene volatile at about 31.5". The portion passing over at190" is an oily mixture of camphenol and isocamphenol benzoates,which are hardly affected by boiling aqueous alkalis but are hydrolysedi i i the cold by alcoholic potash ; the product of hydrolysis when washedwith tepid water is partly crystalline.On fractional distillation laevo-camphenol and dextroisocamphenol are separated.Camphenol purified by recrystallisation from light petroleum meItsat 193" and distils a t 212"; its rotatory power is [a]n = -332" 10' to-32" 20'. The derived camphor is solid and has a rotatory powerof 38" to 38" 10'. These rotatory powers of the camphenol andcamphor are of the same sign. but inferior to those of lawoborneolfrom Ngai and feverfew camphor. The differences obtain probablyowing to the turpentine not being an optically single compound a d ,according to the authors' experiments to the production from thecamphene benzoate of inactive or raceniic camphenols not separableby solvents from the l~evocnmphenol.Isocamphenol purified in thesame way melts a t 47" and boils at 198-199" ; its rotatory power is[a! = + 10" 40' and does not vary under Dhe prolonged action ofacids or high temperatures. Phosphorus pentachloride converts iso-c.impheno1 dissolved in light petroleum into a liquid chloride whichdoes not solidify even at -60" boils from 100" to 105" a t 40 mm. and:s nearly inactive. Nitric acid converts isocamphenol into a liquidsubstance having the odour oE camphor which at -60" forms crys-talline plates melting a t -20". This compound of the same formulaa s camphor boils a t 13" lower that is a t abont 191" ; it is stronglyI~vorotatory.It forms st crystalline compound with hydroxylamine.The properties of this isocarnphor assimilate it to the natura200 ABSTRAOTS OF CHEMTOAL PAPERS.com pound fenolone obtained by Wallach from essence of fennel andisocampheriol to the fenolic alcohol derived fi om it.The action of henzoic acid at 150" on the turpentines gives apractical method of reproducing camphenols and isocamphenols.Terpenes and their Derivatives. By J. W. B R ~ H L (Ber. 24,3373- 3416 j.-The present comniunication deals exclusively withthe constitution and properties of vhrious cmnphene derivatives.Menthol is readily converted into cymene by heating it withanhydrons cupric sulphate in sealed tubes for several hours a t250-280". It is not advisable to use potassium dichromate orpotassium permanganate in place of cupric sulphnte since a t lowtemperatures the action of these substances is very feeble and athigher temperatures violent explosions occur.MelzthyZ ethyZ ether C,,H,,OEt is prepared by boiling menthol(50 grams) dissolved in anhydrous toluene (30 grams) with sodium(8 grams) for 15 hours. The solution is separated from the excessof sodiuni and heated with ethyl iodide in excess ; the sodium iodideand toluene are removed and the residue dried and fractionated oversodium in a vacuum.The ether boils a t 211.5-212" under a pres-snre of 750 mm. and is a colourless liquid with a slight menthol-like odour.BoriayZ ethyZ ether C,,H,,OEt is obtninod in a manner similar tothe preceding compound xylene being used as a solvent in place oftoluene ; it is a clear colourless viscid liquid which boils at 97" undera pressure of 'LO rnm.and a t 204-204.5" under a pressure of 750 mm.The yield is 98 per cent. of the borneol employed. All attempts toprepare dibornyl ether were unsuccessful.BomyZ meth!yZene ether CH,(C,,H,70)2 is formed by thc action ofmethylene iodide on sodium bornyloxide ; it crystallises from light1 etroleum in colourless rhornbic prisms melts at 167-168" and boilsunder reduced pressure without decomposition ; when molten itexhibits a bluish-yellow fluorescence.Bornyl methyl ether is formed during the preparation of the pre-ceding compound and is separated by fractionation.All attempts to obtain pure sodiun~ camphor have been fruitless.Nthyl camphor prepared according to Baubigny's method combineswith one atomic proportion of sodium if heated with it in xyleneEolntion and on treatment with ethyl iodide and subsequent rectifica-tion a viscid liquid is formed which boils at 156-168" under apressure of 10 mm.and is probably diethyl! cumphor; it could not becompletely purified from lack of material.The act.ion of sodium on camphor is stated by Baubigny to proceedaccording to the equatlon 2C,,H,,O + 2Na = C,,H,,NaO + C&I,,ONa;the yield of borneol is however considerably less than is indicatedby this equation; a portion of the camphor is always recoverednnahered ; these facts as well as the behaviour of the ethereal saltsof camphorcarboxylic acid (see below) seem to show that Baubigny'sconclusions are incorrect ; apparently camphor comlnines with 2 atomscf sodium and the rgnction which takes place is redlg represented bythe equation 3C,oB160 + 4Na = CioHL4Na,O + 2CloHI70Na.W.TORGANIC CHEMISTRY. 201Camphocarboxylic acid is readily prepared by dissolving camphor(228 grams) in ether (1-1.5 litres) and adding sodium (46 grams)in the form of fine wire ; the flask is fitted with a reflux apparatus,and a current of dry carbonic anhydride is passed through the solu-tion; there is considerable development of heat and the sodium israpidly dissolved. As soon as the reaction is completed powderedice (1 kilo.) is addcd the ether separated and the aqueous solutionallowed to remain f o r 24 hours when a portion of the borneol sepa-rates in crystals and the remainder is thrown down on heating thofiltrate to 50" ; the precipitated borneol after recrystallisation fromtight petroleum melts a t 208-208.5" ; the yield is theoretical.Onacidifying the aqueous solution camphocarboxylic acid is precipi-tated as a snow-white mass which on crystallisation from warm (notboiling) water yields the pure acid in colourless needles ; the yield isalmost quantitative. This reaction niay be explained by assumingthat a disodium salt CBHIA<ll C*CooNa is first formed and this on C*O.COONstreatment with water is decomposed yielding the compoundCBH14< B:EFNa which then by intramolecular change gives sodiumcarnphocarboxylate C,H,a< CH*CooNa.I I In proof of the foregoingCOtheory it is fonnd that ethyl camphocarboxj-late reacts with sodiumand ethyl chlorocarbonate to form a compound C8H14<~.o.cooEt'which on hydrolysis yields camphocarboxylic acid ; further on treat-ing ethyl camphocarboxylate in toluene sohition with sodium andcarbonic anhydride and subsequently adding water the ethereal saltis recovered unchanged showing thatf ethyl sodiocamphocarboxylatedoes not react with carbonic anhydride or that the compound if anyis formed is decomposed by water.Camphocarboxylic acid melt8s a t 127-128" with evolution ofcarbonic anhydride. The sodium salt forms a crystalline powderreadily soluble in water or dilute alcohol insoluble in acetone ether,and carbon bisulphide.The caZcium salt (ClIHl5O,),Ca crystallisesfrom water or alcohol in needles; the potassium lithium andammonium salts resemble the sodium salt. The ethyl salt is preparedby dissolving the acid in absolute alcohol and saturating the solutionwith hydrogen chloride ; it is a colourless viscid liquid and boils at166%-167%" under a pressure of 21 mm. ; the yield is t'heoretical.Sodium acts on ethyl camphocarboxylate hydrogen being evolved,and on treating the product with ethyl chlorocarbonate a pale-yellow,viscid liquid with an odour of pine-apple is produced; this afterDurification. boils a t 1796-181.5" under a pressure of 20 mm. ItsC-COOEtbhysical arid chemical properties prove tgat it has the formulaCJ314<8 C'CooEt 0.C 0 OEt (see above). The author suggests that the'' ethyl me thrlcamphocarboxylate," C,H < co recently$Me.CO OEtTOL. LXII. 202 AUSTRAG'l'S OF CHEMICAL PAPERS.prepared by Minguin by the mutual act'ion of ethyl cainphocarb-oxylate methyl iodide and sodium methoxide is in reality ethylC-COOEtcamphocarboxylate methyl ether C6H1,<80.Me .Ethyl camphocarboxylate readily combines with phenylhgdrazinewhen the two are heated together at 100" ; the product after beingwashed with light petroleum and crystallised from dilute alcohol isdeposited in colourless slender needles which melt at 132". It isreadily soluble in benzene and chloroform and the solutions turn redeven in the dark ; ferric chloride ammonia and soda produce a similarchange.The substance has the formula CliH,oN,O + H,O andappears to he a pyrazolone C,Hl4< CH* I Yo - it loses 1 n i o ~ H ~ O w1ienheated a t 100".Me~zthodicarboxybic acid C,,H160 ( COOH)2 is prepared in a similarmanner to camphocarboxylic acid by the action of carbonic anhydrideon menthone (3 mols.) and sodium (4 atoms) ; the product is treatedwith ice in order t o decompose the sodium mentholcarbonate,C,,,H,,O*COONa the menthol is extracted with ether and the aqueoussolution after saturation with sodium chloride is acidified and againshaken with ether. On allowing the ethereal solution to evaporatespontaneously the dicarboxylic acid is obtained in small colourlessprisms ; it melts at 128.5" with evolution of carbonic anhydride.Itis very unstable readily dissolves in methyl a,lcohol and acetone butonly very sparingly in water chloroform benzene or carbon bi-sulphide. The salts of the alkali metals are exceedingly unstable ;the silver salt is sparingly soluble and readily decomposes on exposuret o light.The author discusses the camphor formula proposed by Kekul6 andby Bredt and points out that according to the former of these,camphor contains an asymmetric carbon atom ; this fact appears tohave been generally overlooked although clearly stated by Van'tHoff.The formation of a dicarboxylic acid by menthone and of a mono-carboxylic acid by camphor is probably owing t,o the presence ofthe group -CH,=CO*CHMe- in the former compound whilst thecarbonjl group of camphor is only linked to a CH group ; mentho-dicarboxylic acid is therefore represented by the formulaC:N.NPh 'CH,-CH,-$IMe-C 0 OHCH( COO€I).COCHPrp< .Camphoric acid must be regarded as a-methyl-6-isopropyl-AaS-~ ~ ~ Y O W U C O ~ ~ C acid CO OHGHPrfl.CH,*CH:CMe*COOH or as a methyl-~so~~opyltetranzethylenedica~Z,ox~lic acid $IH,.$IP,S-CO OH accordingCH2aCMe*COOH 't o whether camphor is represented as having an etliylene linking(Kekulk) or a para-linking. Camphoric acid which melts a t 187 ,is not oxidised by potamium permanganate and is unaffected whenheated with anhydrous cupric sulpliate undcr pressure ; it is known tobe equally stable towards reducing agents and halogen hrdrides. ThORGANIC CHEMISTRY. 203author confirms Nenschutjkin's observations on t.he low etherificationvalue of camphoric acid.Diethyl camphorate is not acted on bybromine at the ordinary temperature but yields ethyl bromide andcamphoric anhydride when heated at 120". Camphoric anhydride,ethyl chloride and acetic acid are formed by the action of aceticchloride on ethyl hydrogen camphorate at 100". All these observa-tions point to camphoric acid as being a tetramethylene derivative,whilst the ease with which it forms the anhydride also tells in favourof its being regarded as a tetra-substituted succinic acid. Further,the hydromuconic acid formula only indicates the existence of threeoptically isomeric camphoric acids ; four however are known withcertainty and two others are said t o have been isolated ; the tetra-methylene formula requires six isomerides four optically active andtwo inactive.The author concludes that camphor can only be accurately repre-sented by the diagonal formula ; in other words he considers that itis derived from a double tetramethylene ring,Q H2.Q Ha 7 H,CH2*CH*CH2J.B. T.German and Turkish Rose-oil. By U. ECKART ( A d . Pharnb.,229 355-389) .-Rose-oil consists of ethyl alcohol which is distilledoff below- 100" and constitutes 5 per cent. of the oil the ehoptene,which constitutes practically the whole of the liquid portion of the oil,and the stearoptene which is the solid portion. The two latter areseparated by dissolving the oil in 75 per cent. alcohol at i0-80" andcooling to 0" when the stearoptene separates ; the alcoholic solutionis then evaporated in a vacuum to obtain the elaoptene.The ehoptene from both Turkish and German rose-oil has a com-position corresponding with the formula CloHl,O.Its physical constantsvary according to its source between the following limits :-Boilingpoint 216-217" ; refractive index 1.4710-1.4725 ; refraction equi-valent 48.97-49-28 ; dispersion 11.1-12.5 ; specific rotation,-2.7 to -2.8. The vapour density corresponds with the molecularweight 142.43 (CloHlsO == 154). Evidence of Markovnikoff's com-pound C,,H,,O (Abstr. 1891 219) was not obtained.The author proposes the name rhodinol for the compound CloHl,O.The following derivatives of it are described :-The sodium derivative,not prepared perfectly pure ; the chloride ClOHI7CI a yellowish- brownliquid which does not distil without decomposition ; the iodide,CloH171 a brown liquid with an odour of turpentine ; the cyanide ayellow oil.The ether C,oH3,0 was obtained by acting on rhodinolwith carbanil whereby x crystalline carbanilide melting at 235" wasformed ; this was subsequently decomposed by water when the etherseparated as a yellow liquid. The benzoate PhC00*CloH17 is a pale-yellow neutral liquid ; the acetate MeC00*CloH17 and the thio-alcohol,C,oH17*SH were also obtained.By oxidising rhodinol with potassium dichromate and sul phuricacid the corresponding rhodinuldehyde C1,HI6O and the silver saltof the acid Cl,H,,O2 !rhodinolio acid were prepared. When alka-line permangnnate was used as the oxidising agent a pentahydric2 3 204 ABSTRACTS OF CHEMICAL PAPERS.alcohol C,H,405 and the following acids were obtained :-Valeric,butyric acetic formic oxalic and carbonic.When hydrogen peroxidewas used a monobasic acid C6H1206 was formed of which theBarium salt (C6H,,02)2Ba was analysed.Strong dehydrating agents act on rhodinol to form a hydrocarbonof the limonene group namely dipentene C,,H, and a polyterpene,The stearoptene is colourless and odourless ; its quantity varies inrose-oil between 20 and 68 per cent. and its melting point between33.5" and 36.5".The author regards rhodinol as an unsaturated monhydric primaryalcohol with an open-chain structure. Its optical activity shows thepresence of an asymmetrical carbon atom and by applying Briihl'smethod to the refraction equivalent i t would appear to contain twoethylenic linkings ; the author therefore attributes to it the formulaCH,:CPr.CH:CH.CHPr.CH~*OH which would also account for itseasy conversion into closed- chain compounds (compare Semmler,Abstr. 1890 951).Natural Resins.By M. BAMBERGEK (Monatsk. 12 441-463) .-The resin from Pinus Znricio (Poir) dissolves in alcohol ether methylalcohol amyl alcohol acetone and acetic acid ; is partly soluble inbenzene chloroform and turpentine and is insoluble in light petr-oleum. It melt's at about 100"; has a yellow colour which onexposure to light becomes red gives the phloroglucinol reaction,and on distillation in a vacuum furnishes a viscid brown mass.Asdetermined by Schmidt and Erban's method (Monats7~. 7 655),the specimens examined had an acid equivalent of 116.6 and aniodine number of 51.9. The methoxyl number obtained by Benedikt,and Griiesner's process varied from 49.6 t o 54.8.On boiling with water for a long titne or on blowing steam throughan alcoholic solution and exhausting with ether the ethereal solutionobtained gave on evaporation a crystalline mass which had an iodinennmber of 60.4. This was dissolved in alcohol and allowed to crys-tallise. The first separation consisted of caffe'ic acid the diacetylderivative of which formed slender white needles melted at 189",and agreed in properties with the compound obtained by l'iemannand Nagai (Ber. 11 656) who however give a slightly highermelting point namely 190-191".On reduction of the acid withsodinm amalgam hydrocaff e'ic acid C9HI0O4 identical in crystalline[ a ZI c form = 2.5604 1 1.9676 71 = 108"] and optical proper-ties with the acid obtained by Hlasiwetz (AnnaZen 142 354) WRSformed. The second separation was recrystallised from chloro-form and from hot water and proved to be ferulic acid. Themother liquor was then evaporated t o dryness dissolved in ether,the solution shaken with bisulphite and finally treated in the wayrecommended by Tiemann (Be?.. 8 115) whereby vanillin wasobtained.On heating the resin (500 grams) left after boiling with water withpotash (2 kilos.) in an iron dish a mixture of catechol and proto-catechuic acid was obtained.Of these substances the former is(CsHt3)n.A. G. BORGANIC 0 KEMISTRP. 205probably derived from the latter and the latter from ferulic acid bythe action of potash.The resin from Picea vulgaris (Link) melts at about loo" and thesamples examined had an acid equivalent of 125-127-7 an iodinenumber of 61.2 and a methoxyl number of 33-34.9. The resin wastreated in the same way as that obtained from Pinuus Zaricio and gavean aqueous extract which contained paracoumaric (naringenic) acidand vanillin. The resin after boiling with water had an acid equi-valent of 99 and a methoxyl number of 34.8; andgave on fusion withpotash a mixture of protocatechuic and parahydroxybenzoic acids.G. T. 31.Substances contained in the Petals of Gentiana verna.By G.GOLDSCHMIEDT and 8. J ~ H O D A (Monatsh. 12 479-485).-0nevaporation of an alcoholic extract of 1 kilo. of the air-dried petals ofGentiana rema a dark-red viscid mass containing solid greenish-yellow resinous lumps is obtained. Water dissolves a reddish-violet colouring matter dextrose levulose and another substancefrom the product and leaves the resinous lumps unchanged. Theresin dissolves in alcohol and after treatment with charcoal forms ztcolourless solution from which three compounds may be separated byfractional crptallisation. That formed in greatest quantity is anamorphous granular white powder which melts at 215-219".Elementary analysis and a determination of it)s effect in lowering thefreezing point of phenol show that it has the fornzula C,,H,,O,. It iswithout action on hydroxylamine and phenylhydrazine but forms atriacetyl derivative C,H4,(OAc) which is readily soluble in coldalcohol and melts at 175-HOG and consequently contains threehydroxyl groups and has been named gentiol by the authors.It isreadily soluble in hot alcohol dissolves sparingly in ether and benzene,is insoluble in potash and on oxidation with chromic acid in aceticacid solution gives a crystalline acid which melts at 127". Thetwo other fractions are only obtained in small quantity ; one is solublein alcohol ether and benzene crystallises in beailtiful white plates,melts at 1 1 5 - - 1 1 7 O and has the formula C,,H,O,; the other is ayellowish powder which melts a t about 240".Rind of Garcinia Mangostana.By P. R. LIECHTI (dmh. Pharm.,229 426-439) .-The author fully describes his method of preparingmangostin from the rind of GarcirLia rnaiagostana; it does not mate-rially differ frbm that adopted by Schmid (Annalen 93,83 ; J. Chem.SOC. 1856 190).Pure mangostin C20H2205 crystallises in bright-yellow slenderlaminae melts at 173" (uncorr.) not at 190" (Schmid loc. c i f . ) and istasteless and odourless ; it dissolves with a yellow colour in alcohol,ether chloroform glacial acetic acid carbon bisulphide xylene,acetone strong sulphuric acid and alkalis ; i t is sparingly soluble i nbenzene and solution of tannin but not at all in light petroleum.Solutions of mangostin give a greenish-black d o u r with ferricchloride. Alkaline solutions of it fluoresce greenish dissolve ferrichydroxide with a deep red-brown colour and give an orange preci-G. T.M206 ABSTRACTS OF CHEJIICAL PAPERS.pitate with alkaline potassium iodide. Gold silver and platinumare reduced from their solutions by mangostin.When it isheated with potassium hydroxide and a little water until the melthas a clear brown colour and the melt subsequently dissolved inwater acidified and extracted with ether a small quantity of acid,resembling valeric acid in its odour and in its zinc salt is obtained;if the melt is more strongly heated carbonic anhydride and oxalicacid are produced.When mangostin is reduced in alcoholic solution with sodiumamalgam and the solution filtered and acidified a brick-red amorph-ous precipitate is obtained which dissolves in alcohol; the solutiongives a briliiant green fluorescence when mixed with a little alkali.The absorption spectrum of t,his fluorescent solution contains a strongband between E and b and a feeble band at I?.This reductionproduct has the same percentage composition as mangostin and iscalled isonaangostin by the author who regards it as R polymeride.It melts with partial decomposition at 127" (uncorr.) ; its solutions inalcohol and in ether are yellowish-brown and are not 'furthelcoloured by ferric chlolaide nor will they reduce amrnoniacal silveisolution.Schmid (Zoc. cit.) found that gamboge yielded a substance closelyresembling mangostin when oxidised by nitric acid. The authorprepared pure gambodic acid from gamboge by dissolving in absolutealcohol filtering precipitating with water washing dissolving indilute ammonia and precipitating with hydrochloric acid ; it melts a t92-96' (uncorr.). Tbis preparation was oxidised with nitric acid,and the product analysed ; but in its composition and properties itbore no resemblance t o mangostin.Mangostin gives a white crystalline acetate with acetic anhydrideand sodium acetate which is being investigated.Some remarks on the anatomy of the yind of Garcinia rnangostanaconclude this paper.Nicotenylamidoxime.By L. MICHAELIS (Ber. 24 3439-3446).-NicotenyZamidorcime C,NH,.C (NH,):N*OH is prepared by digestingequivalent quantities of p-cyanopyridine hydroxylamine hydro-chloride and sodium carbonate in concentrated aqn eous solution foreight hours at 70" in a closed vessel.The mixture is evaporated todryness extracted with absolute alcohol the alcohol distilled off andthe product crystallised from hot chloroform. It melts at 12@"without decomposition is easily soluble in water alcohol acetone,alkalis and acids sparingly so in ether chloroform and benzene andinsoluble in light petroleum. With ferric chloride i t gives a redcoloration ; with Fehling's solution a dirty brownish-green precipitate.The hydrochZoride C6H,N30,2HC1 is prepared by leading dry hydro-gen chloride into a dry ethereal solution of the amidoxime. It formsvery deliquescent needles melts at 171" and is soluble in water andalcohol. The pZatinochZoride obtained by adding platinic chloride toa concentrated solution of the hydi-ochloride crystallises in yellowscales and is solublo in water and alcohol. Stannic chloride andMangostin is oxidised by nitric acid to oxnlic acid.A. G.BORGANIC OHEMISTRY. 207mercuric chloride cause no precipitate when added t o an aqueoussolution of the hydrochloride. The copper salt is obtained by addingcopper acetate to an aqueous solution of the ammonium salt and issoluble in animonia and hydrochloric acid insoluble in water. Thesilver salt is white and blackens in the air.Acetiy Znnicotenylarnidoxirne C5NH*.C (NHJXOAc is formed withdevelopment of heat on mixing finely-powdered nicotenylarnidoximewith acetic anhydride. When the reaction is ended the product isneutralised with sodium carbonate filtered and purified by crystal-lisation from chloroform.It melts a t 143" and is easiIy soluble inbenzene a(lcoho1 acetone chloroform and acids less so in water ether,and light petroleum.Nicotenylazoxirnethenyl C,NH4*C<- N>CMe is obtained as a subli-mate by cautiously heating the preceding compound between watch-glasses on the sand-bath. It melts at logo and is soluble in water,ether alcohol benzene acetone chloroform and acids insoluble inalkalis. The hydrochloride forms small white needles and is solublein water and alcohol. The pZatinochZol.ide is obtained in beautifulyellow needles on adding platinic chloride to a solution of the hydro-chloride and is sparingly soluble in water insoluble in alcohol.Mercuric chloride gives a white precipitate when added to a concen-trated solution of the hydrochloride.Stannic chloride gives noprecipitate.BenzoyZnicoten,yZamidoxime C6NH4*C (NH2):NO-Bz is prepared byadding the calculated quantity of benzoic chloride t o nicotenyl-amidoxi me dissolved in the calculated quantity of sodium hydroxide.The mixture is shaken a s long as the odonr of beiizoic chloride can bedetected a few drops of ammonia added and the compound collected,washed with water and crystallised from alcohol. I t forms colour-less scales melts at 190" is easily soluble in benzene alcohol andchloroform very sparingly in ether and water a i d insoluble inlight petroleum. It dissolves in acids and is reprecipitated byalkalis.NONicoten y Zaxoxinzeberum y 1 C5NH4- CeN:>CPh - is obtained as asublimate by heating the preceding compound between watch-glassesor by boiling it for a long time with watei..It melts at 13!1" and issoluble in ether benzene light petroleum alcohol acetone chloroform,and acids and insoluble in water and alkalis. The hydrochloride isunstable. With platinic chloride and mercuric chloride it yieldssparingly soluble double salts.Nicotenylazoximepropenyl-w-carbonic acid,is obtained by heating a mixture of molecular proportions of nicotenyl-amidoxime and succinic anhydride a t 100" to quiet. fusion. The coldmass is extracted with dilute soda filtered and the filtrate saturatedwith dilute hydrochloric acid. The compound is obtained as avoluminous precipitate and is purified by crystallisation from ho208 ABSTRACTS OF CHENICAL PAPERS.water. It melts a t 178" is soluble i n water acetone alcohol acids,and alkalis sparingly so in ether chloroform and benzene insolublein light petroleum and reacts acid to litmus.The silver salt formsstellate .groups of needles blackens on exposure to light and issoluble in ammonia. The copper salt is green and dissolves inammonia to a blue solution.Nicat~zylpheny Zurami~oxime C,NH,*C( :NOH)*NH.CO*NHPh is ob-tained by mixing finely-divided nicot.enylamidoxime with the calcu-lated quantity of carbanil. It crystallise8 from chloroform i n slendeyneedles melts at 167" is easily soluble in hot water alcohol andchloroform less so in benzene et,her and acetone and insoluble inlight petroleum acids and alkalis.Ethyl Izicotenylil.midozimecarbonate C5NH,.C(NH,):NO-COOEtJ isformed together w i t h nicoteiiylamidoxime hydrochloride by addingethyl chlorocarbonate (2 mols.) drop by drop to B saturated solutionof nicotenylamidoxime (3 m o l ~ .) in absolute ether. It is purified bydissolving i n benzene and precipitating with petroleum melts at 136"and is soluble in water alcohol benzene chloroform acetone andacids insoluble in etlher and light petroleum.Nicotenylazosulphinzecnrbanilicle C5NH,*C<-N>C*NHPh ;NS is ob-tained on gently warming a mixture of finely-powdered nicotenyl-amidoxime and phenylthiocarbimide. The reactmion takes placesuddenly with much frothing and the product is purified by severalcrystallisations from hot benzene.Although the experimental con-ditions were varied the author could iiot obtain a nicotenylthiour-amidoxime but always obtained the condensation product Nicotenyl-azosulphimecarbanilide is also obtained on heating to boiling nicotenyl-amidoxime (1 mol.) and phenylthiocarbimide (2 niols.) dissolved inchloroform. I t crystallises in white needles melts at 241" is insolublein water soluble in alcohol benzene and chloroform less so in etherand acetone and is dissolved by acids and reprecipitnted by alkalis.Nicotenylamidoxime benzyt ether C5NH& (NH,):NO*CH,Ph is ob-tained by gently heating equivalent quantities of nicotenylamidoxime,sodium ethoxide alcohol and benzyl chloride in a reflux apparatus. Itcrystallises from light petroleum in needles melts a t 80° is soluble inether alcohol benzene chloroform and petroleum insoluble in water,and dissolves in acids but not in alkalis.E. C. R.a-Pyridone (a-Hydroxgpyridine). By H. v. PECHMAXN and0. BALTZER (Bey. 24 31.44-3153) .-To prepare a-pyridone (a-hydr-oxypyridine) mnlic acid (500 grams) is converted into cumalic acidby heating it with sulphuric acid and thence iuto the methyl salt;this is dissolved in am.monia and boiled with sodium hydroxide andon then adding hydrochloric acid hydroxynicotiiiic acid is precipitated,which is dried and heated above its melting point until the evolutionof carbonic anhydride slackens when the temperature is raised anda-pyridone passes over. It melts a t 107" boils at 280-281"; theaqueous solution has a neutral reaction ; the colour produced by ferricchloride is quite distinct from that obtained with phenol and theobservation t h a t both the ethyl derivatives (see below) give the samORQANIO CHEMISTSY.209colour stands in harmony with this difference; it does not giveLiebermann's phenyl reaction and does not under any circumstances,reduce permnnganate solution instantaneously ; when mercuric chlor-ide is added to a concentrated solution t h o mems~ochloride separates,and this on crystallisation from water or dilute alcohol forms long,colourless needles and melts at 191-192".Eth yl-a-pyyl-idone is obtained in theoretical yield by heatina a-pyri-done with an excess of ethyl iodide for five hours a t 180' addinghydrochloric acid evaporating on the wat'er-bath redissolving i n alittle water precipitating with an excess of potassium carbonate,extracting with chloroform and recti€y ing.It is a colourless almostodourless oil of strong basic properties boils a t 246-248" is verysparingly volatile with steam is miscible with water and whenheated at 290" in a sealed tube undergoes partial decomposition theresidne being the unaltered compound ; it behaves towards perman-ganate in a manner similar to a-pyridone ; the memwochloride crystal-lises from water or dilute alcohol in prisms and melts a t 112-113" ;the hydrochloride is completely volatilised by protracted heating atthe temperature of the water-bath ; the plutir~cchloride forms yellowneedles sinters st 98" and melts at 105-108".When ethyl-a-pyrid-one is heated in a reflux apparatus with an excess of 4 per cent.sodium amalgam ethylainine is produced ; the authors therefore,believe it to have the constitution CY<Ca:CH>NEt.a-Ethoxypyyidine is formed by shaking silver a-pyridone (preparedby adding the calculated quantity of silver nitrate to a-pyridonedissolved in the equivalent quantity of dilute soda) with ether andethyl iodide at the ordinary temperature until tlie precipitate has thecolour of silver iodide filtering washing the precipitate with alcoholichydrochloric acid distilling off the alcohol and ether mixing theresidue with a little water and precipitating the base with potassiumcarbonate; the yield is equal to the a-pyridoae employed.It is acolourless oil having a strong odoiir of pyridine and more feeblebasic properties than its isomeride ; it boils a t 155-156" is volatilewith steam and is much more stable than its isomeride remainingunchanged when heated in a sealed tube at 230" and being only veryslowly attacked a t the ordinary temperature by permaqanate ; themercuwchloride melts at 141-142". When heated in dilute alcoholicsolution with sodium amalgam ammonia is evolved ; it therefore,CH*C(OEtj probably has the constitution CH<cH-cH>N.Meth y Z-a-pyridone CSNH4Me0 is a colourless almost odourlessliquid boil1 tlg at 240' ; the mwcu.roclzZoride melts a t 127".a-,~eetl~ox?/2~y1.idiaze C5NH4*OMe closely resembles tlie ethyl deriva-tive ; the mercnrochloride melts at 199-200".a-Chloropyridine [Cl = 21 is obtained by moistening a-pyridonewith phctsphorus oxychloride mixing with '28 times the quantity ofphosphorus pentachloride and heating the mixture for 3-4 hours i nan oil-bath at 130" adding water and after rendering alkaline,driving over the new base with steam; it is a colourless oil havinga pyridine-like odour boils a t 166" (714 mm.) and is insoluble inCHC210 ABSTRACTS OF CHEMICAL PAPERS.water ; the platinochloride crystallises in the monosymmetric system,a b c = 1.4348 1 2.0380 ; /3 = 73" 21.4' ; observed forms mP,The concluding portion of the paper is devoted to a discussion onthe constitution of pyridine by v.Pechmann who considers that thegeneral behaviour of pyridine including the tautornerism of itshydroxy-derivatives (see also Haitinger and Lieben Abstr.1885,966) is best explained by assigning to it a centric formula as suggestedby Bamberger. A. R. L.Piperazine. By A. SCHMIDT and G. WICHMANN (Ber. 24 3237-3248) .-Majert and Schmidt (Abstr. 1891 538) have alreadystated that piperazine passes unchanged through the humanorganism. The aut8hors find that with a single dose of 3 grams thebase can be detected in the urine even after 6 days and although thechief portion is voided after a few hours a certain amount remainsin the blood for a long period. To detect piperazine in urine thelatter is rendered free from phosphates of the earth-metals by theaddition of a few drops of sodium hydroxide solution reacidified withhydrochloric acid heated to 40° and filtered after the addition of a soln-tion of potassium bismuthoiodide when crystals of the form alreadydescribed (Zoc.cit.) separate from the filtrate after a time. In thedetection of minute quantities of the base the urine is evaporated,the residue being distilled with solid alkali and sand and the distillateexamined as above. Piperazine undergoes no change when directlyinjected into the blood for example ; by injecting 0.3 gram into theblood of a rabbit the chief portion was found in the wine after2 hours but the presence of the base could still be detected at theend of 1& days.When dry piperazine (1 gram) is heated for 14 hours at 370" withbromobenzene (11 grams) the product filtered from bromide anddistilled until the thermometer registers a temperature of 17@,alcohol extracts diphenylpiperazine (m.p. 160") from the residue.Piperazine (8 grams) and bromobenzene ( 3 grams) heated in asimilar manner give the same compound together with an oily sub-stance probably monophenylpiperazine.Pui.anitrophen2/~ieruzi~~e7 NO2*CsHI.C4H9N2 is obtained whenpiperazine (8 grams) is heated with parachloronitrobenzene (3 grams)at 150" f o r 4 hours ; the melt is triturated with dilute alkali and theresidue extracted with hydrochloric acid when a small quantity ofdinitro-derivative (see below) remains undissolved together withchloronitrobenzene ; the filtrate is freed from chloronitrobenzene byagitating it with ether alkali added and the precipitate which formsis dissolved in benzene ; the pure compound separates from this solu-tion on adding light petroleum; it melts at 129" and is readilysoluble in alcohol chloroform and benzeue but only very sparingly inwater ether and light petroleum ; the hydrochZoride forms yellowish-red lustrous prisms.-Pm OP.Paraclinitr ocliph eny lpiperaziize,cat&( C,H,*NO2)2,is almost exclusively formed when the previously mentioned reORGANIC CHEMISTRY. 2ilagents are heated together in molecdar proportion for 3 hours a t150" ; the product after washing with water is treated with boilingalcohol when the dinitro-compound remains ; it is very sparinglysoluble in all solvents and melts at 248" with decomposition.Dincetyl-piperazine CcH8NzAcz is prepared by heating piperazine acetate withan excess of acetic anhydride in a reflnx apparatus distilling off to300" rectifying the residue in a vacuum and crystallising the solidifieddistillate from benzene when the compound separates in compact,needles ; it melts at 138*5O boils with slight decomposition at 810" andis readily soluble in water and alcohol.Ethyl piperazyloxamate,C4H8N,(C0.COOEt) is formed when piperazine is heated at 100" fora short time with an excess of ethyl oxalate; i t crystallises fromwater in needles melts a t 124" and is readily soluble in solvents.The cowzpozincl C4HloN,,2PhOH which separates on mixing analcoholic solution of piperazine with an ethereal solution of phenol inmolecular proportion crystallises from alcohol in large lustrouspyisms melts at 99-101" and develops the odour of phenol onkeeping ; whilst the compound C4H10N2,C6H602 melting at 295" withdecomposition separates i n compact needles on mixing alcoholic solu -tions of piperazine and quinol.The benzy Zidene derivative C4HBN2:CHPh produced by mixing piper-azine with benzaldedyde heating on the water-bath and treatingwith boiling alcohol is a white amoiaphous substance almost insolublein all solvents and melts at 246-247'; whilst the compoundC4HloN,CS separates as a greenish-white powder on mixing alco-holic solutions of piperazine and carbon bisulphide ; it decomposesat 260".Diazobenzenepiperazine C4H8N,(N,Ph) prepaved by adding piper-azine to an alkaline solution of diazobenxene melts at 129'; acompound is also obtained with quiuone.DickIoropipeTazine C4H8N2C1 is best prepared by adding anaqueous solution of piperazine to one of freshly prepared sodiumhypochlorite collecting the precipitate and crystallising it fromalcoholic ether; it has a sharp tear-exciting odour melts at 71",detonates at 80-85" is sparingly soluble in water but is convertedinto piperazine hydrochloride by it only slightly soluble in ether,aid readily in alcohol.No analogous compound is formed by theaction of sodium hypobromite although the addition of brominewater to an aqueous solution of piperazine seems t o produce it.Dinitrosopiperazine (Ladenburg Abstr. 1891 1333 j decomposeswhen distilled and on reduction with zinc and acetic acid yields t h edihydrasine CaH8N,( NH,) crystallising from alcoholic either in stoutneedles melting at loo" and boiling at 228" ; the latter reducesPehling's solution and ammoniacal silver solution on boiling ; thedibelz~oyl derivafive CaHeN2(NHBz)2 prepared by adding thecalculated quantity of benzoic chloride dissolved in chloroform to asolution of the hydrazine in the same solvent is a white amorphoussubstance which does not melt at 310° and is insoluble in solvents ;whilst the dibenzylidene derivative C4H8N2(N:CHPh) obtained byadding benzaldehyde to a solution of the hydmzine in sodium acetatesolution melts at '205" and is insoluble in water21 2 ABSTRACTS OF CHEMICAL PAPERS.Dimethylpiperazine (Ladenburg Zoc.cit.) boils a t 153-158" anddoes not solidify when cooled to -15" ; the hydrochloride melts at247-250" with decomposition.Diethylpiyerazine C4HgN2Et2 boilsat 165" and does not solidify at -15" ; the hydrochZoride crystallisesfrom dilute alcohol in small white needles melts at 27'7" with de-composition ; the platinochloyide forms small yellow plates.A. R. L.Quinolinehydrazines. Ry E. BOTTJGER (Bey. 24 3276-3277).-A claim for priority. Dufton's researches on orthoquinolinehyclr-azine (Trans. 1891 752) were not published until October whereasthe author had already in august applied for a patent concerning amethod of preparation of quinolinehydrazines. He thinks he has atleast an equal right with Dufton to be regarded as the discoverer ofthese compounds.C. F. B.p-Phenylpentoxazoline. By S. GARRIEL and P. ELFELwr(Eel-. 24 3213- 3218).-The benzoyl derivative of ybromopropyl-amine like the benzoyl derivatives of /3-brometh~lamine and@-bromopropylamine (Abstr. 1890 l267) readily loses hydrogenbromide forming a meso-substitut<ed pentoxazoline,which contains the same nucleus as trimethylenepeeudocarbamide(Abstr. 1890 472). The yhromopropylamine required was preparedaccording to Gabriel and Weiner's method (Abstr. 1868 1292) andwas freed from admixed trimethylenediamine hydrobromide bysolution in absolute alcohol. The crude compound obtained onevaporating t.he solution was dissolved in wa.ter and treated withB mols. of sodium carbonate and 1 mol. of benzoic chloride ; n/-bromo-propy Zhenaamide C HJ3r.C H,*C H,*NHC 0 P h then separates as awhite crystalline compound which is purified by triturating with*dilute soda and recrystallising from benzene.I t forms white fascicu-lar groups of needles melting a t 62". The crystals deliquesce in thecourse of a few weeks and pass into the hydrobromide of p-pheny1-pentoxazoline CH2<CH:,N>CPh ; the free base separates on theaddit,ion of soda. It may be more quickly prepared by dissolvingthe benzamide in hot water adding alkali distilling in a current ofsteam and extracting the distillate with ether. On evaporating thelatter the p-phenylpentoxazoline remains as a yellowish oil havinga peculiar odour and pungent taste ; i t is sparingly soluble in cold,more readily in hot water and cannot be distilled under atrno-apherio pressure without decomposition,CH -0The picrate,forms yellow needles and melts at 151" ; the pZatinochZoTide orange-yellow flat needles melting with decomposition a t 185" ; the dichrom-ate orange needles ; and the fewocyanide a yellowish-green crystallineprecipitateORGANIC CHENISTR T.213Towards hot mineral acids the base behaves in a manner similar tothe oxazoline bases previously described ; with an excess of hydro-bromic acid it is reconverted into y-bromopropylbenzamide and withan excess of hydrochloric acid into y-chloroprop ylbenxawide,CHZCl*CH:,*C H:,*NH.COPh,which crystallises from light petroleum in delicate needles melts at56-57" and is niuch more stable than the bromine derivative. If,however the base be boiled with an equivalent quantity of aqueoushydrobromic acid until the solution no longer forms a sparinglysoluble dichromate it is converted into the hydrobromide of y-amido-propyl benzoate NHz~CHz~CH2~CHz*OBz which separates from aceticacid on the addition of ethyl acetate as a white crystalline powder,melts at 134-135" is readily soluble in water and sparingly in lightpetroleum.The free -pa.nzidopropyE benzoate is a colourless oil easilysoluble in water ; its picrate C1,H,,NO,,C,H3N,O crystallises inyellow needles and melts a t 177-178" and the pZatiizochlo?-ide,(C,,H,,NO,),,H,PtCl~ in yellowish-red needles melting with decom-position a t 204-205".Corresponding with pentoxazoline is the compound pentathiazoline ;this has not yet been prepared but some of its derivatives are alreadyandtrimetliylenepseudothiocarbamide (Abstr.1890 524). Other deriva-tives have been obtained by the action of trimethylene bromide onthioamides and will shortly be described. H. G. C.known namely p-mercaptopenthiazoline C,H,<N>C*SH SOxazolines and Pentoxazolines. By P. ELFELDT (Ber. 24,3218-3228) .-In continuation of the work described in the previousabstract the author has examined other derivatives of bromethyl-amine and bromopropylamine and finds that these like the acetyl andbenzoyl compounds readily yield oxazolines and pentoxazolines.Metanitrobenzoic chloride acts on /%brornethyl,zmine i n presence ofsodium carbonate forming P-bromethylnastanitrobe?zzaiizide,CH2Br*C H2*NH*COgC6H4-No2,which crystallises in needles melting at 116-117" and is almostinsoluble in cold water.It is converted by the calculated quantityof alcoholic potash into ~-naetanitrophsnyZoxasoEine,which crystallises from water or dilute alcohol in long narrow rect-angular plates melting a t 118.5-119.5". Of its salts the picrate,CgH,N,O,,C,H,N,O melts at 145-146" and the platinochloride,(CgH,N20,),,HzPtCI at 195" ; the dichronzate forms a yellowish-redemulsion and the ferrocyanide a yellowish-green crystalline precipi-tate.p-Bromopropylamine hydrobromide (which after recrystallisationfrom acetic acid melts at 156") is readily acted on by rnetanitrobenzoicchloride and alkali with formatiou of P-bromopi.opylmetanitrobenz214 ABSTRACTS OF CHEMIUAL PAPERS.amnide CHMeBr- CH,*NH*C 0.CeH4-NOz which crys tallises frombenzene in small needles melting at 84-85" and is converted byalcoholic potash into P-methyl-~-metanitl.op7tenyloxa~oline,vHMe.0 >C CsH4*N0,.CHZ-NThis crystallises from water or dilute alcohol in long silvery plates,melts at 85-86" and is only slightly volatile in L current of steam ;its picrate C10H10N203,C6H3N307 crystallises in yellow needles andmelts at 152-153" and the y Zatinochloride ( C I O H ~ O ~ ~ O ~ ) ~ H Z P forms flat yellowish-red quadratic crystals melting at 195-196" withdecomposition.ci-Bromopro~y Euminenitrobenzam~de is obtained in a manner similarto the P-compound and crystallises from benzene or chloroform inneedles melting at 89-90'; by the action of alcoholic potash,i t yields p-metanityophenylpentoxazoline C H * < ~ ~ ~ ~ ~ ~ C * C H .N O which separates from dilute alcohol or ether in long silvery platesmelting at 93-94". The picrate C,oHloNz03,C6H3~307 crystallises intufts of needles and melts at 123-124" previously becoming plastic,and the PZatinochZoride ( CloH,,NZ03) ,HZPtC16 forms an orange-red,crystalline powder which melts with decomposition at 196".p- Brometh y Z$phenyZn,cetamide C2H4Br*N H*C O*CH2Ph obtai n ed fromphenylacetic chloride and p-bromethylamine hydrobromide crystal -lises from benzene in small jagged plates and melts at 84-85".When treated with aqueous soda and distilled in a current of steam,it yields p-be?zzyEoxaooiine >C*CH,Ph which may be ex-tracted from the distillate with ether and remains on evaporatingthe solvent as an oil having a feeble penetrating odour.The picrate,CloHl,N0,C6H3N307 melts at 130-131". The larger quantity of thephenylacetamide is however converted into ainidoeth yl phenylacetatehydrobromide NHZ-CzH4~0*CO*CH,Ph,HBr which is isolated byevaporating the solution of the amide to dryness extracting theresidue with water and slowly evaporating the solution. The residueprobably contains hydroxyethylamine hydrobromide and is thereforetreated with Dicric acid. which does not mecipitate the latter butVH2.0CH2*Nyields the pictate of amidoethyl phenylacetaie in ;mall plates mekingat 137-138".Phenylacetic chloride reacts with /3-brornopropylamine much lessreadily than with the corresponding ethyl derivative ; the /I-bromo-propyl phenylacetamide CHMeBr*CH,*NH*CO.CHzPh crystallisesfrom light petroleum in delicate needles melts at 45-46" and whenkept rapidly forms a syrup which is pa.rtially soluble in water.Thesolution gives precipitates with picric acid and platinum chloride theformer having the composition CllHI3NO,C6H3N3O7 ; the solution,therefore in all probability contains /3-methyE-p-Belzzy2oxazolirce,YHMe.0>C*CH2Ph. CHZ- ORGANIC CHEMISTRY. 215y- Bromo~ro~y Zppheny laceta~zi~e C,HGBr*NH*C 0.C H2P h separatesfrom light petroleum in tufts of slender needles melts at 4344",and decomposes if kept or by the action of alkalis forming p-benzyl-pentoxnzoline CH2<CH2.-N>C*CH,Ph which is an oil having apungent taste but no odour in the cold.CH so2The picrate,C11H13NO,CJ%N3oi,crystallises well and melts at 139-140" whilst t h e platinochlorideforms an orange-yellow crystalline powder.obtainedfrom cinnamic chloride and /3-bromethylamine hydrobrom ide crystal-lises from light petroleum in white plates melting at 90-91".Alco-holic potash converts it into ~-cinnamen2/loxazoli~ae,P-Broni eth y Zciiznanty Zamide C2 H4Br.NH.C 0 CHI CH Ph,which crystallises from light petroleum in transparent prisms con-taining light petroleum; this is evolved on exposure to the air orover sulphuric acid and the substance then melts at 52-53' be-coming plastic at 48". The uierate C11H11N0,C6H3N307 forms yellowneedles melting at 188 -IS$' and the platinochloride,( c 11HllNO) ,,H2PtCl6,an orange-yellow crystalline powder melting with decomposition atp.BromopropyZcinnanzyZanzide CHMeBr.CH2*NH*CO-CH:C!HPh,crystallises from benzene 019 light petroleum in white plates meltingat 79-80'.The /%met hyZ-~-cinnnanze~zyloxazoline,193-194'.CHMe.0,yC*CH:CHPh,CHZ- Nobtained from it separates froni light petroleum in crystals containinglight petroleum which is given off on exposure to t'he air the com-pound then melting at S0-Slo. The picrate C~2H13K0,CoH,N,0,,crystallises in delicate needles and melts at 186-183" and theplatinochloride ( C12H13NO)2,H2PtClo melts with frothing atC H2B r- [ C H,] ,*NH*C 0 - C H C HPh,forms hexagonal plates melts at 74" and is converted by alkalis intop- cinnameny lpentoaa,zoline CH2<g2:$>C*CH:CHPhI which alsocontains light petroleum and melts after removal of the latter at55-56".The picl.de Cl2HI3NO,C6H3NYO7 melts at 196" and theplati~~ochloride ( CL,H13N0)2,H&'tC16 at 192 -193" with decomposi-tion. H. G. C.197-198".ry-Bromoprop y lcinnamy lamid e,Thiazole Compounds. By P. SPICA and G. CARRARA (Gazzetta,21 421-433) .-The authors have prepared the following compoundsby Wohler's method :216 ABSTRACT8 OF CEEMlOAL PAPERS.Unsynznzetrical dimethy Ithiocarbamide NH,*CS*NMe is obtained incolourless hard deliquescent crystals melting at 81-82' nnd is verysoluble in water and absolute alcohol.Unsymmetrical dieihyl thiocarbamide NH,. C f3.NEt is a colourless,deliquescent substance which crystallises with difficulty is soluble inwater and absolute alcohol and melts at 169-170".U7 i sy mmet ?mica1 diisoaml y t hiocas.bamide NH,. C S . N ( C,H 1) is ob-tained in colourless scales moderately soluble in water easily solublein absolute alcohol and melts at 208-209". It is very like camphorin appearance and in its behaviour when floating on water.Unsymmetrical diisoamy lselenoca~bamide NH,-CSe*N( C5H1,) isobtained by the action of potassium selenocyanate on diisoamylaminein coloiirless scales melting without decomposition at 171-1 $2'. Byexposure to light or by heating it turns first red and then green. Itcrystallises with 2 mols. H20 which it retains in a vacuum overRulphuric acid but loses on heating at 100" in a current of air.On condensation with halogen derivatives of ketones the unsym-metrical bi- subs ti tu t ed thiocarbamide s should behave ~nalogousl yt o the svmmetrical derivatives and yield thiazole derivatives of the.I S-NR',constitution I CH:CRyN*The authors endeavoured unsuccessfully to prepare these com-pounds by the use of chloracetone and bromacetophenone in thefollowing cases :-A mixture of unsymmetrical dimethylthiocarbamide with chlor-acetone in molecular proportion was heated on a water-bath untfil nofurther odour of chloracetone was observed.The residue was takenup with water made alkaline with caustic soda and the solutionextracted with ether. The ethereal extract contains dimethylamineand an unknown base the platinochloride of which contains 40.02per cent of platinum ; the mother liquor after complete extractionwith ether yields a yellowish precipitate when acidified with hydro-chloric acid.This is partly soluble in alcohol and chloroform,sparingly in light petroleum and sparingly and partially soluble inwater ; i t contains sulphur but no chlorine melts partially at aboutgo" and deconiposes above 100"; it is probably impure a-methyl-hydroxythiazole but the quantity obtained was too small for purifica-tion and analysis.The solution in absolute alcohol of equivalent quantities of un-symmetrical dimethylthiocarbamide and brornacetophenone is evapo-rated to dryness on the water-bath the residue dissolved in absolutealcohol and fractionally crystallised.On recrjstallisation from dilutealcohol long needles melting at 71-72' and agreeing in propertieswith rhodanacetophenone first separate ; the mother liquor containsa deliquescent substance agreeing i n properties with dimethylaminehydrobromide. When unsymmetrical diisozmFlthiocarbamide andbrornacetophenone are treated in the same manner the substancemelting at 71-72' and a white crystalline product which seems tobe diisoamylamine hydrobromide are obtained. When the alcoholicsolution of dibenzilethiocarbamide and chloracetone is treated in themanner indicated above a product is obtained which on solution iORGAN10 OHE MISTRT. 217alcohol and precipitation with light petroleum yields dibenzylammehydrochloride ; the mother liquors contain a yellow substance solublein water and caustic alkalis sparingly soluble in ether insoluble inacids or ammonium carbonate solution and melting a t 96".N oanalyses were made but the substance is supposed to be methylhydr-oxythiazole. Similar results are obtained on heating unsymmetricaldibenzilethiocarbamide with chloracetone on the water-bath withoutany solvent treating with caustic sods and extracting with ether a~3before indicated. Symmetrical diphenylthiocarbamide and chlor-acetone treated in the same manner yield the base melting at 138",prepared by Taumann. Unsymmetrical dibenzilethiocarbamide andbromacetophenone when heated together give benzilsmine hydro-bromide and the substlance melting at 71-72O. To show that thiscompound is really rhodanacetophenone i t was converted into carb-aminethioacetophenone by boiling for a short time with stronghydrochloric acid ; on prolonged ebullition a-phenyl-p-hydroxythiazolewas obtained.The general reaction between unsymmetrical bi-substituted thio-carbamides and halogen derivatives of ketones is best represented bythe following equation :-R*CO*CH,Cl+ S:C(NHz).NR'z = NiC*S*CH,eR*CO + NHR'Z'HCI.W. J.P.Quinazolines. By S. GABRIEL and R. JANSEN'(Ber. 24 3091-3098 ; compare Abstr. 1890 1442) .-Orthamidobenzylncetamide,NHo-CeH4*CH2*NH-COMe [l 21 when distilled yields a substancewhich must be p-methyldihydroquinazoline C,H4<N - hMe forwhen methylated it yields the same &-dimethyldihydroquinazoline,c 6 H 4 < ~ - cH2'rMe C M ~ ' which is obtained by distilling orthamidobenzyl-acetome thylamide NH2.CsH4-CH2*NMe* C OMe.Hence by analogy,the substance formed when orthonitrobenzylformamide,N02*CGHQ*CH2*NH* C OH,is reduced with zinc and hydrochloric acid must be dihydroquin-azoline CsH4<Orthoni trobenzylarnine is best prepared by mixing orthonitro-beiizyl chloride (24.5 grams) with potassium phthalimide (25.5 grams)in benzyl cyanide (35 c.c.) heating the whole on a water-bath untilall the water is expelled and finally keeping it for half an hour at180". The cyanide is then driven over with steam and the residuepurified by boiling with a little alcohol. Nitrobenzylphthalimide(31 grams = 75 per cent. of the theoretical yield) is left behind ; ityields orthonitrobenzylamine when heated (15 grams) with hydro-chloric acid of sp.gr. 1-19 (60 c.c.) for three hours at 185-190".The hydrochloride is obtained by separating the phthalic acid andconcentrating the filtrate. The picrate C7H,N202 C6H3N,0 formssparingly soluble yellow needles and melts at 806-208". Ortho-CHZ-NH--CH2'PHN=CH*VOL. LXII218 ABSTRACT8 OF CHEMIOAL PAPERS.~nitroZ,enzyEcarbamide NH,*C0.NH.CH,.C,H,.N02 is obtained inneedles melting at 150" by concentrating an aqueous solution ofpotassium cyanate and orthonitrobenzylamine hydrochloride.When orthonitrobenzyl chloride (10 grams) is allowed to remainin a closed flask with 10 per cent. alcoholic ammonia (100 c.c.) for10 days at the ordinary temperature crystals of diortl~onitrobenzylamine,NH(CH2*C6H4*NO& (5.5 grams) are deposited.These can be crys-tallised from hot alcohol ; they melt a t 99-100". The hyydrochEoride,C,,H,,N,O,.HCl melts ahove 220° becoming charred. The yZatino-chloride ( C14H,,N30JJ3,P t CL forms small yellow needles verysparingly soluble in water. The nitrosamine (No2*C6H4*CE,),N*NO,is obtained in lustrous needles melting at 120" when nitrous acid isadded to an acetic acid solution of the base. The mother liquorfrom the diamine on concentration leaves a residue (4 grams) fromwhich nitrobenzylamine hydrochloride (2 grams) can be obtained byextracting with alcohol a concentrated filtered aqueous solution ofthe residue.When orthonitrobenzyl chIoride (15 grams) is dissolved in alcohol(150 c.c.) arid warmed for one hour in a stoppered flask in the water-bath with 33 per cent.aqueous methylamine (45 c.c.) and the residueleft after evaporation of the alcohol is treated with water it yieldstliorthonitrobenzyl~ethylamin~ NXe(CHz.C6H4.N0,)z as an insolubleoil which crystallises after a time ; when recrystallised from methylalcohol it forms yellowish prisms melting at 62-64'. The aqueoussolution is concentrated tG a small bulk treated with 33 per cent.aqueous potash and extracted with ether. The brownish oil obtainedon evaporating the ether is mixed with hydrochloric acid and thesolution evaporated. The orthonitrobenz ylrnetlzy lamine hydrochloride,NO2-C6H4-NHMe,HC1 (9.5 grams) thus obtained crystallises from95 per cent. alcohol in tables and melts at 175-176-5".When thissalt (6 grams) is boiled for a quarter of an hour in a reflux apparatuswith dry sodium acetate (3 grams) and acetic anhydride (12 c.c.),the mixture concentrated and treated with water orthonitrobenzyl-acetomethy Zanaide N02.C6H4.CH2*NMe*C OMe separates as an oil,which finally crystallises ; from light petroleum it can be obtainedin small lustrous white crystals melting at 57-58". This substance,finely powdered (I gram) is mixed with water (15 c.c.) and con-centrated hydrochloric acid and treated with zinc. After remainingfor a. time the clear solution is poured off and treated with excess ofaqueous soda ; the ortko.midobenzylacetomethylamide,NH,.C6H,*CH,.NMe.COMe,is extracted with ether and recrystallised from this solvent ; it formsa fine powder melting at 94-95'. This was heated gently in a smalldistillation-flask until no more water was expelled Py-dimethy ldihydro-qwinazoline C6H4< then distils orer at 300-305" as a pale-yellow oil which solidifies on cooling.It crystallises from ether insmall white needles softens at 70° and melts at 75-77". Its solu-tion in water is alkaline and has a bitter taste. I h dissolves also inhydrochloric acid and the solution fornis double salts with platinumCH2-rMeN= CMeORQANIC CHEMISTRY. 219chloride potassium dichromate and picric acid. The picrate softensa t 210" and melts at 215-217".6-Methyldihydroquinazoline unites with methyl iodide forniingcolourless crystals of the methiodide. When these are dissolved inwater and the solution treated with potash a yellow oil separates,which has all the properties of py-dimethylhydroquinazoline describedabove.CH2-PHhas now been obtained crys- N= CH'From benzene it separates in small yellowish crystals whichThe hydrochloride C8H8N2,HCl,Dihydroquinazoline C,H,<talline.soften at 115" and melt at 127'.crystallises from alcohol.C. F. B.Choline. By E. SCHMIDT (Arch. Phnrnz. 229 467-486).-Choline platinochloride melts at 232-233" when heated in a narrowcapillary tube but generally at 240-241" with much frothing ; Bodegives 233-234" (Inaug. Diss. Narburq l889) and Jahns gives 225"(Abstr. 1891 94).Gram (Arch. exp. Path. Pharm. 20 116) says that nenrine andcholine platinochlorides are so similar in crystalline form as to be dis-tinguishable only by their difference in colour.The author findsthat choline platinochloride forms large soluble red tabular rnono-clinic cryst'als arranged like steps ; whilst neurine platinochloridecrystallises in small individual sparingly soluble orange-red regularoctahedra and me1t.s at 211-213".To convert choline into neurine it is heated with fuming hydriodicacid at 140" and the product is treated with moist silver oxide. Toconvert neurine into choline it is heated with hydriodic acid and theproduct then heated with silver nitrate in aqueous solution (compareBode Zoc. cit.).Choline platinochloride is not converted into neurine platinochlor-ide when heated with hydrochloric acid in the water-bath as statedby Gram (Zoc.cit.).Choline lactate is not converted into neurine lactate when heatedin water as stated by Gram but a lactocholine platinochloride,NMe,Cl*CH,*CH,*O~CHMe.COO~CH~*CH2*~~e~Cl,PtCl~,2H~O is ob-tained if after the action has continued for p i x days neutralplatinic chloride is added in considerable quantity and the mixturerapidly evaporated This snl t forms columnar crystals with bevelledends melts with decomposition at 220" and dissolves easily in water,but more sparingly in alcohol.An aqueous solution of choline does not contain any neurine afterit has been kept for four months whether the solutSon be concentratedor dilute. In two experiments with hay infusion the author foundthat under the influence of the organisms contained therein cholineis converted to a small extent into neurine; further experimentsgave somewhat uncertain results.A. G. B.Adenine. By M. KR~~GER (Zeit. physiol. Chern. 16 160-172),-The knowledge of the nucle'in bases derived from nuclejic acid is of!2220 ABSTRAOTS OF OHEMICAL PAPERS.importance as the origin of uric acid in the system may probably bearrived at by their study especially if adenine and hypoxanthine canbe shown to belong t o the uric acid group which includes xanthineand guanine. Adenine was prepared from tea-extract and estimatedby the help of sodium picrate (BruhnR Abstr. 1890 534). It canbe prepared free from water of crystallisation by adding excesg ofammonia to concentrated solutions of its hydrochloride ; four-sidedpyramids are thus obtained.A 0.5 per cent. aqueous solution givesno precipitate with potassium ferrocyanide or ferricyanide until aceticacid is added when thin crystalline plates are obtained. Ferric chloridegives a red coloration unaltered by heat. Copper sulphate producesa greyish-blue amorphous precipitate containing 2 atoms of copper to1 mol. of SO3 ; it is therefore a mixture of copper-adenine and adenine-copper sulphate. With chromic acid it forms a dichromnte,this crystallises as six-sided plates. With chloracetic acid it formsprismatic ciystals of a chloracetate C5N5N5,2C H,C10,. Withhydrochloric acid at 135" it is completely decomposed (Kossel) and itappeared of importance to determine the products formed. On carry-ing out the reaction in sealed tubes it was found that the productswere carbonic anhydi-ide carbonic oxide and ammonium chloride.Fouratoms of its nitrogen appear in the form of ammonia ; consequently nomethylamine group is present in adenine. Glycocine is also formed,and the following equation represents what occurs :-C5H,N5 + 8H20= 4NH3 + GO + 2CH202 + C2H5N02. No formic acid is however,found as such ; the strong acid the pressure and the temperaturebreak it up completely into carbonic oxide and water. Similarlytreated hypoxanthine undergoes the following reaction :-C5H4N,0 + 7H,O = 3NH3 + CO + 2CH202 + C2H5N0,. Comparing theseresults with those obtained by Schmidt (Annalen 217 311) in rela-tion to xanthine (C5H4N402 + 6H20 = 2C02 + CHz02 4- 3NH3 +C2H5N0,) it is seen that xanthine and hypoxanthine yield qualita-tively the same products; the quantitative difference is that therelation of CO CH30 is 1 2 in hypoxanthine and 2 1 in xanthine.Uric acid under the influence of concentrated hydriodic acid at160-170" alga yields glycocine carbonic anhydride and ammonia(Strecker ibid.146 142).Adenine and Hypoxanthine. By G. BRUHKS and A. KOSSEL(Zeit. physiol. Chem. 16 1-12).-By Beckmann's method (Zeit.physikal. Chem. 4 532) the molecular weight of adenine was foundto be sufficiently near 135 to wasrant the author's previous assump-tion that its formula is C5H5N5.On oxidation uric acid xanthine and their derivatives yield pro-ducts which show they contain an alloxan nucleus. Whether hypo-xanthine and adenine contain this is uncertaiu but by bringing acidgroups into their molecule it was hoped to obtain an answer to thisquestion.For this purpose the action of ethyl chlorocarbonnte on hypo-xanthine was investigated ; 4 grams of hypoxanthine hydrochloridewere mixod with 3 grams of sodium hydroxide and 5 grams of ethylW. D. HORQANIC CHEMISTRY. 221chlorocarbonate and after 24 hours the precipitate which formed wascollected and was recrystallised from hot water when tables about7 mm. by 1 mm. were obtained melting at 185-190'. They weresparingly soluble in alcohol ether and cold water but readily in hotwater sodium hydroxide and hydrochloric acid. Their compositionwas found to be C,H3N40*C00Et that is the substauce is the urethaceof hypoxanthine.It was however found unsuitable for experimentson oxidation and attention was then directed to the bromine deriva-tives of adenine. The action of bromine appears to take place in thefollowing stages :-(1.) C5H5N5 + Br = C5H4N6Br + HBr.(2.) C5H4N5Br + HBr = C5H4N5Br,HBr.(3.) C5H4BrN5,HBr + 2Br2 = C5H,BrN5,BrP,HBr.The final product which is red is Etroinadeizine tetrabrowkle h y d mbromide.Bromudenine C5H4BrX5 crystallises in thin plates it is sparinglysolnble i n water but very readily in ammonia and fixed alkalis andfairly soluble in mineral acids with which it forms salts. The sulphate,( C5H4RrN5),,H&3 Oa + 6Hz0 hydrochloride C5H4BrN5,HC1 andnitrate C5H4BrN5,HN03 were prepared. The picrate,C,HABrN CsH,( NO,) 3.OK + H,O,is very similar in its properties to adenine picrate. Bromadenine likeadenine also gives metallic derivatives with silver nitrate mercuricchloride cadmium chloride &c.Attempts to obtain an oxyadenine or ethoxyadenine by t,he methodadopted by tc'ischer i n regard to caffei'ne (Ber. 14 ti37 ; 15 29 453 ;Annalen 215 253) failed. Difficulties were also found in an attemptto prepare chloradenine but at. last it was obtained by heatingadenine with phosphorus pentachloride in a sealed tube at 160-170"for several hours. W. D. El.Behaviour of Cupreine and Quinine with Methyl Iodide.By 0. HESSE (Awnalen 266 240-245).-When quinine is boiledwith excess of methyl iodide in methyl alcoholic solution i t yields themethiodide C20H2,N,0,,MeI + HzO as sole product ; if however thereaction is carried out at 80-loo" the dimethiodide C20H,4N202,2McI + 3H20 is formed. The dinasthochloride prepared from the meth-iodide crystallises in pale-yellow needles and is readily soluble inwater.The pZatinochZoride C20H,4N20,,Me,PtCI + 2Hz0 is a dark-yellow crystalline compound sparingly soluble in cold water. Theaurochloride C,,H,,N,O,,~M~AUC\~~ is a yellow flocculent substance,and decomposes at about 100".When a methyl alcoholic solution of cuprehe is boiled with excessof methyl iodide the methiodide is formed but if the mixture isheated at 80-loo" cupreine dimethiodide C19Hz2Nz02,2MeI + 3H20,is produced. This compound crystallises in prisms melts at about210" with decomposition and is moderately easily soluble in hot water.The corresponding methochloride crystallises in pale-yellow needles,and is moderately easily soluble in water and alcohol ; its pZatino222 ABSTRACTS OF CHEMICAL PAPERS.chloride C19H22N202,MezPtC1 is an orange granular compound verysparingly soluble in cold water.When cup're'ine is heated with methyl iodide and sodium methoxidein methyl alcoholic solution i t is converted int~o a mixture of themono- and di-methiodides of quinine as stated by Grimaux andArnaud (Abstr. 1891 1121).F. S. K.Preparation of Homologues of Quinine. By E. LTPPMANN(Monatsh. 12 512-514) .-The yield of methylquinine obtained byClaus and Mahlmann's process (Ber. 14j is unsatisfactory owing toa large quant'ity of the quinine methiodide escapiug decomposition ;the author finds that the following method gives much better results.The quinine methiodide is boiled with excess of silver oxide thesilver iodide filtered off and the solution treated with a slight excessof dilute sulphuric acid whereby the sparingly soluble sulphate isprecipitated in the form of needles.The crystalline mass is dried ona porous plate and heated in sealed tubes at 140" with excess ofsodium hydroxide solution. Under these conditions the quininemethohydroxide C20H2,N,0,,MeOH loses water and is converted intomethylquinine C20H23MeN20 which can be separated from theproduct by shaking with ether.By 0. HESSE ( A n n u l e n 266 245-248).-Thisarticle is principally controversial ; the author also describes experi-ments which point to the conclusion that commercial cinchoninesulphate may sometimes contain two isomeric alkalo'ids one of whichyields isocinchonine the other cinchoniline.Isocinchonines.By E. JUNGFLEISCH and E. LEGER (Compt. rend.,113 651-654 ; compare Abstr. 2891 1121).-A continuation of thediscussion with Hesse. They find that the isocinchonine of Com-stock and Koenig is identical with cinchoniline.G. T. M.Isocinchonine.F. S. K.C. H. B.Digitaleine. By J. HOUDAS (Compt. rend. 113 648-651) .-Theauthor has shown that the soluble digitalines of Schmiedeberg consistalmost entirely of one glucoside to which he gives Nativelle's namediqitaZeine. I t is characterised by the following properties :-Whenamyl alcohol is.added to an aqueous solution of digitalehe the latteris rapidly precipitated in a crystalline form.If a hot mixture ofamyl arid ethyl alcohols is used the solution on cooling deposits long,nacreous lamellq which contain amyl alcohol and water of crystal-lisation. If these crystals are dissolved in boiling watler the amylalcohol expelled by prolonged ebullition and the liquid mixed withits own volume of ethyl alcohol of 95" long needles separate instellate groups on cooling. The crystals contain ethyl alcohol andwater and are more soluble t,han those containing amyl alcohol.Similar results are obtained with methyl alcohol. It follows thatwhen an alcohol of the ethyl series is added to it solution of digita-leine a crystalline compound of the alcohol and hydrated digitale'ineis obtained and its solubility in water is greater the lower themolecular weight of the alcohol.Phenols seem t o behave in ORGANIC CHEMISTRY. 223similar manner and ordinary phenol gives a well-crystallised com-pound which will be described subsequently. The crystals lose theiralcohol and water at 110". They dissolve somewhat slowly in coldwater but very rapidly i n boiling water. Digitaleine however hasnot yet been crystallised from aqueous solutions. When the liquidevaporates the glucoside is left as a vitreous residue.Digitaleine is very slightly soluble in alcohol and is practically in-soluble in chloroform ether and light petroleum. I n aqueous solution,it has a lmvorotatorypower; [ a J D = -49.25". When heated it showsno distinct melting point but agglomerates at about 250"; intumescesat about 270" and is completely carnmelised at 280'.It seems to beunaffected by exposure to air and its aqueous solution can be keptfor a long time withont undergoing any change. It is precipitatedby tannin or nmmoniacal lead acetate and dissolves in cold hydro-chloric acid without coloration; but if the solution is heated itbecomes violet-red with a slight greenish fluorescence. Sulphuricacid diluted with its own volume of water produces a yellowishcoloration in the cold changing to red and finally to black onheating.The elementary composition is represented by the formulaC,,H',,O, and agrees with that given by Schmiedeberg. Whentreated with very dilute sulphuric acid digitalei'ne yields two crys-tallisable glucosides without any glucose. C. H. B.Hydrastine. By M. FREUND and C . DORMEYER (Ber. 24 3164).-The question as to whether the bromomethylhydrohydrastinine,CI2Hl4NO2Br described by the authors (Abstr. 1891,1518) is relatedt o the compound obtained by Merlin (Abstr. 1884 1385 ; 1887 164)from diinethylpiperidine and bromine and is therefore an ammoniumbromide has yet to be settled. A. R. L.Lupanine the AlkaloYd of the Blue Lupine. By C. SIEBERT(Arch. Pharm. 229 531-546).-Hagen (Abstr. 1886 163) ascribesthe formula C,,H,,N,O t o lupanine ; this formula is contrary to thelaw of even atomicities and should be doubled except that Hagen'sresults do not exclude the formula C15HP1NZ0.The crushed seeds were extracted eight times with two successivequantities of alcohol containing hydrochloric acid ; the extract -wasdistilled t'he residue made alkaline with potassium hydroxide andextracted with ether; the ethereal solution was shaken with dilutehydrochloric acid and tlie aqueous solution of the hydrochloride thusobtained was again treated with potassium hydroxide and ethert,o separate the pure base. The seeds yielded 0.33 per cent. oflupanine ; Hagen obtained 0.19-0.22 per cent.Lupanine is freely soliible in cold water t o a clear solution andalso in cold alcohol (compare Hagen Zoc. cit.). The hydrochloride,C15H24N20,HC1 + 2H20 forms long white needle-shaped crystals,easily soluble in water alcohol and chloroform but not in ether ; whendried a t go" it melts a t 127". The hydriodide C,H24N20,HI + 2H20,forms yellowish crystals and when dried at loo" melts a t 184-18.5".The hydrobromide C15H2dN20,HBr + 2H20 forms large white224 ABSTRAOTS OF OHEMIOAL PAPERS.tabular crystals melts at lll" and is soluble in water and alcohol.The platinochloride forms nodular crystals with 4 mols. H,O. Theaurochloride separates on addition of water to its alcoholic solutionin long prismatic crystals; i t is anhydrous dissolves in alcohol andwater and melts at 198-199'. The methiodide melts at 248-249"(Hagen gives 215").Tmpanine is not changed by heating with fuming hydrochloric acidat 200" or with concentrated aqueous or alcoholic sodium hydroxidesolution at the ordinary pressure. When heated with soda-lime thelupanine molecule is split up 1 atom of nitrogen appearing asammonia and the other as a pyridine ba,se ; an unsaturated hydro-carbon is also obtained and may be taken as evidence of a side chaini n the molecule.By oxidation with potassium permanganate in acid solution,lupanine yielded carbonic anhydride a little ammonia a neutral sub-stance C15H20N203 and a nitrogenous acid. A. G. B.Nuclei'ns. By H. MALFATTI (Zeit. physiol. Chem. 16 68-86).-Nucle'ins may be divided into two groups the true nucle'ins fromcell-nuclei which yield xanthine bases on decomposition and theparanucleins from egg yolk and milk which do not. The questionarises whether the artificial nuclei'n of Liebermann prepared by theaddition of metaphosphoric acid to albumin belongs to the first 01second group. The preparation of nucleic acid from nucle'in byAltmann (Du Bois Reyrnond's Archiv physiol. Abth. 1889 514) givesa further means of distinguishing between the two groups. Anartificial nucle'in containing 6.1 per cent. of phosphorus was preparedfrom serum-albumin ; after dissolving in ammonia aud reprecipitatingby acetic acid several times the percentage of phosphorus sankto 1.6. This is due to the separation of a nucleic acid rich in phos-phorus. This is soluble in ammonia ; from this solutim i t is not pre-cipitable by acetic acid but i t is by hydrochloric acid ; it yields notrace of xanthine derivatives and therefore belongs to the class ofparanuclei'c acids and the nucle'in from which it originates to theclass of paranuclei'ns. The opinion however is advanced that thenucle'ins and paranucleiins are not so distinct as might be supposed,'nut that the true nucleins are either simple additive or substitutionwmpouuds of paraiiuclejina and the xanthine bases in question.After incineration and heating with potassium nitrate phosphorusestimations were made by titration with uranium acetate.New Protei'd from Human Blood Serum. By C. CHABRIE(Compt. rend. 113 557-559).-Serum neutralised by acetic acid iscoagulated and evaporated at 100". The mass is extracted bydistilled water at looo the water being half the original bulk of t h eserum. The filtered liquid is somewhat cloudy ; the addition of 89"alcohol gives a white flocculent precipitate collecting together aftersome hours. The precipitate collect,ed and dried in the air issoluble in water from which it is reprecipitated by alcohol. It con-tains an organic substance resembling albumin arid yields 0.637 percent. of ash consisting of phosphates and not containing calcium orW. D. HPHY SIOLOQICAL CHEMISTRY. 225chlorides. It is proved to be a new substance by the followingreactions:-It is coagulated by alcohol but not by heat even inpresence of acetic acid. Nitric acid gives a precipitate soluble inslightl excess. Potassium ferrocyanide in presence of acetic acidgives a milkiness increasing with time. Phosphotunqstic acid yieldsa precipitate ; ammonium phosphomolybdate gives a white precipi-tate on heating. Acid mercury nitrate gives a yellow precipitate ;Millon’s reagent a white one becoming rose-coloured on heating.The substance yields no sublimate and no biuret reaction. No resultfollows the addition of a saturated solution of magnesium sulphate ;sodium sulphate causes a white precipitate.On account of its analogies with albumin i t is proposed to namethe new substance albumone. It was found to the extent of 1/12,000by weight in the blood of a healthy man. I n t h a t takeu from apatient suffering from nephritis it formed 0.087 per cent.Albumone is strongly lEvorotatory but the opalescence of its solu-tion prevents the determination of the amount of rotation withaccuracy. It does not dialyse.It differs from BBchamp’s nBphrozymase obtained from urine thissubstance saccharifying starch at 60” whereas albumone exerts nosuch action. W. T