摘要:

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

ISSN:0368-1769    

DOI:10.1039/CA8926200126

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

PHY SIOLOQICAL CHEMISTRY. P h y s i o l o g i c a1 C h e m i s t r y . 225 Influence of Nutrition on the Composition of the Blood- ash. By K. LANDSTEINER (Zeit. physioZ. Cliem., 16,13--19).-Verdeil states (Annulen, 69, 89) that the salts of the blood vary with those of the food; an animal fed on flesh has in the blood alkaline phos- phates, which me replaced by carbonates when a vegetable diet is given. Against this view we have the fact (Jarisch, Wiener med. Jahyb., 1871, 435 ; 1877, 1) that the ash of the blood of different animals (men, dogs, horses, oxen) is practically the same, although their diet is different. In the present research, 15 young rabbits were dieted for three months and a half on hay, and another 15 on milk. The ash in the blood was in both cases practically the same, qualita- tively and quantitatively ; such differences as were noticed being ex- plicable by differences in the relation of corpuscles to plasma.In animals with equal amounts of lmmoglobin in their blood, t,he cor- puscular element was probably identical, and here, whatever the diet, the Na20 : K20 quotient and the other analytical details obtained were also identical. W. I). H. Bile during Inanition. By S. 31. LUKJANOW (Zeit. physiol. Chem., 16, 87-142).-The experiments were carried out on guinea pigs, and may be divided into five groups ; the first gronp consisted of normd animals ; the remaining four groups of animals in different stages of226 ABSTRACTS OF OHEMICAL PAPERS, inanition. Very complete analytical tables relating to each experi- ment! are given.The animals were found t o lose on the average 1 per cent. of body weight in four hours four minutes. At; the commencement of inanition, the relative weight of the liver is the smallest ; in the middle period it rises, returning to the normal, and it continnes to rise to the end. I n the initial and middle stages, the liver is poor in water; in the final stage, the amount of water rises, first t o the normal, and then above it. In the blood there is a progressive loss of water. I n the first stage (loss of body weight 5.53 per cent.), the amount of hile per hour per 10 grams of liver substance, and per 1 kilo. of body weight is rather greater than the normal; it then progres- sively sinks, but most rapidly in the middle periods (loss of body weight, 16 to 25 per cent.).This is represented in charts by means of curves. At first the bile is dilut,e, but, later, becomes more con- centrated, soon, however, reaching a maximum at which i t remains ; this increased percentage of solids is chiefly due to the bile salts. The lessening found in the amount of bile secyeted is not solely due to concentration, but also to a, diminution in the solids secreted. The energy of secretion of bile during inanition is thus less .than in normal animals ; but the diminution in energy is most marked during the first half of the hunger period. W. D. H. Carbohydrates of Putrefying Human Urine. Bg G. TREUPEL (Zeit. physiol. Chem., 16, 47--67).-The formation of fatty acids in normal urine when putrefaction sets in is due to the decomposition of its carbohydrates (dextrose and animal gum).In the present research, the furfuraldehyde and a-naphthol reaction was employed for the estimation of sugar (see Abstr., 1891, 1559), the results being con- trolled, in some cases, by Raumann's benzoic chloride method. It was found, that a.s putrefaction advanced the carbohydrate in the urine diminished, but a small quantity always remained, even after very prolonged periods (30 to 47 days). If the urine was exposed to the air, putrefaction and the diminution of carbohydrate occurred more rapidly than in closed vessels. Increase of the temperature to 35" also hastened the process. W. D. H. Ethereal Hydrogen Sulphates in the Urine, and Disinfec- tion of the Alimentary Canal. By A. ROVIGHI (Zeit. physiol.Chem., 16, 20-46) .--Prom experiments on the author's person, 011 various patients, and on clogs, the following conclusions are drawn :- 1. The quantitative estimation of the ethereal hydrogen sulphates in the urine is a trustworthy criterion of the amount of putrefactive change in the intestine. 2. The amount of these substances passed varies with the time of day, so that it is necessary to examine a specimen of the mixed 24 hours' voidings. 3. In children, the amount passed is less than in adults. 4. Oil of turpentine and camphor in large doses lessen the putrefac-PHYSIOLOaIOAL CREMISTRY. 227 tion in the dog's intestine, and, consequently, the output of ethereal sulphntes in the urine. 5. In the human being, given either by mouth or rectum, these drugs have not the same efficacy.6. Tannin clyst,ers lessened, but only very slightly, the ethereal hydrogen sulphate of the urine in a case of enteroperitonitis, where their amount was excessive. 7. A saturated solution of boric acid injected into the intestine is more effective; but the absorption of the acid by the intestinal ~nucous membrane is dangerous. 8. The use of Carlsbad salts and Marienbad water is followed by an increased oiitput of ethereal hydrogen sulphates for the first few days ; this is followed by a very marked diminution. 9. Kephir (l-& litres per diem) is an excellent means of lessening intestinal putrefaction. Its action depends, in part at least, on the lactic acid it contains. TV. D. H. Physiological Action of Strontium Salts. By J. V.LABORDE (Compt. rend. Soc. Biol., 1890, 708-716 ; 1891, 562-566 ; compare Abstr., 1891, 99).--The action of the snlphate? normal tartrate, and orthophosphate of strontium was compared experimentally with that of the corresponding salts of potassium. The results again showed the innocuity of the strontium compounds ; the lactate and tartrate have a slight diuretic action. Elimination takes place chiefly through the faeces. It is partly assimilated, being found in the liver and bones, and, t o a small exteut, is climinated in the urine. Further experiments with the bromide were confirmatory of the foregoing. W. D. H. Physiological Action of Camphors, and of their Compounds with Chloral. By SCHUITT (Colnpt. rend. ~Soc. B i d , 1890, 678- 683).-1n a warm-blooded animal, camphor causes excitation of the central nervous system leading to general convulsions, an increase in the depth of respiration, a, slowing of the heart, with increased force of its beats, and a marked elevation of blood pressure.Borneol and menthol, on the other hand, produce a sedative action on the nerve centres, borneol being the more powerful. Borneol, however, di- minishes the frequency and depth of respiration, the number and force of the heart beats, and produces a fall of blood pressure ; whilst menthcl increases respiratory and cardiac activity, leading to a heightened intravascular pressure. In experiments on rabbits, it was found that by giving borneol after chloral hydrate, the depressing action of the chloral was augmented by that of the borneol, whereas menthol in part counteracted this depression. Starting from this, the physiological action of com- pounds of chloral with the camphors was investigated.Camphor dissolves in anhydrous chloral, but does not form definite compounds with it, whereas borneol and menthol do. The mixture of camphor and chloral produces the same effects as i f the drugs were given successively, the convulsive effects of the camphor being masked by the sedative action of the chloral.228 ABSTRAOTS OF CHEXIOAL PAPERS. Chloral bomiylute, CCI,-CH(OK)*OCloH,,, forms white crystals in- soliible in water, and melts at 45-55". It is very toxic, producing a lowering of blood pressure and temperature to a greater extent than can be accounted for by the amount of chloral i t contains.C7zZoraE menthylate, CCl&H( OH) .OC,,,H,,, is a transparent, yellow- ish liquid, of the consist,ence of glycerol, insoluble in water, soluble in alcohol of go", and in oil. When distilled with water, i t dissociates into menthol and chloral hydrate ; an analogous dissocia- tion in t,he body probably accounts for its physiological mtion. It irritates the mucous membranes when applied locally. Given snbcu- taneously or by the mouth, it leads to paralysis of the posterior limbs, and then to sleep ; the soporific action is the same in its strength and duration as that produced by a corresponding dose of chloral hydrate, although its onset is somewhat delayed. The paralytic effects and lessening of reflex action are due to the menthol. The movements of respiration and of t4he heart are effected in the same way as witli chloral ; the depression of temperature is, however, not so marked.Blood pressure is first lowered, then rises, remaining stationary at a lower level than the original. Thus, to some extent, the menthol corrects the depression due to the chloral. w. I). H. Toxic Action of Blood andof Various Tissues. By J. H ~ R I - COURT and c. RICHET (Compt. rend. A%. Bid., 1890, 695--696).-The blood of one animal is poisonous to that of another species; thus the toxic dose of dogs' blood, as tested in the rabbit, is 40-45 grams per kilo. of body weight. Birds' blood is more poisonous, its toxic dose being 7 grams. Mosso has previously shown, particularly with fishes' blood, that the poisonous effects of the serum are due to its protejids (ichthptoxin) ; and the present experiments confirm this conclusion, as the alcoholic extracts of the blood and spleen, which are, of course, free from prote'id, have lost their toxicity.The alcoholic extract of the muscles of some dogs was, however, poisonous, of others not. W. D. 1". Toxicity of Serum. By A. CHABRIN (Compt. rend. SOC. BioE., 1890, 697).-A preliminary note regarding the toxicity of the serum from cases of urlleniis, confirmatory of the coaclusions in the preceding abstract. W. U. H.PHY SIOLOQICAL CHEMISTRY.P h y s i o l o g i c a1 C h e m i s t r y .225Influence of Nutrition on the Composition of the Blood-ash. By K. LANDSTEINER (Zeit. physioZ. Cliem., 16,13--19).-Verdeilstates (Annulen, 69, 89) that the salts of the blood vary with thoseof the food; an animal fed on flesh has in the blood alkaline phos-phates, which me replaced by carbonates when a vegetable diet isgiven.Against this view we have the fact (Jarisch, Wiener med.Jahyb., 1871, 435 ; 1877, 1) that the ash of the blood of differentanimals (men, dogs, horses, oxen) is practically the same, althoughtheir diet is different. In the present research, 15 young rabbits weredieted for three months and a half on hay, and another 15 on milk.The ash in the blood was in both cases practically the same, qualita-tively and quantitatively ; such differences as were noticed being ex-plicable by differences in the relation of corpuscles to plasma. Inanimals with equal amounts of lmmoglobin in their blood, t,he cor-puscular element was probably identical, and here, whatever the diet,the Na20 : K20 quotient and the other analytical details obtained werealso identical.W. I). H.Bile during Inanition. By S. 31. LUKJANOW (Zeit. physiol. Chem.,16, 87-142).-The experiments were carried out on guinea pigs, andmay be divided into five groups ; the first gronp consisted of normdanimals ; the remaining four groups of animals in different stages o226 ABSTRACTS OF OHEMICAL PAPERS,inanition. Very complete analytical tables relating to each experi-ment! are given.The animals were found t o lose on the average 1 per cent. ofbody weight in four hours four minutes. At; the commencement ofinanition, the relative weight of the liver is the smallest ; in themiddle period it rises, returning to the normal, and it continnes torise to the end. I n the initial and middle stages, the liver is poorin water; in the final stage, the amount of water rises, first t o thenormal, and then above it. In the blood there is a progressive lossof water.I n the first stage (loss of body weight 5.53 per cent.), the amountof hile per hour per 10 grams of liver substance, and per 1 kilo.ofbody weight is rather greater than the normal; it then progres-sively sinks, but most rapidly in the middle periods (loss of bodyweight, 16 to 25 per cent.). This is represented in charts by meansof curves. At first the bile is dilut,e, but, later, becomes more con-centrated, soon, however, reaching a maximum at which i t remains ;this increased percentage of solids is chiefly due to the bile salts.The lessening found in the amount of bile secyeted is not solely dueto concentration, but also to a, diminution in the solids secreted.The energy of secretion of bile during inanition is thus less .than innormal animals ; but the diminution in energy is most marked duringthe first half of the hunger period.W. D. H.Carbohydrates of Putrefying Human Urine. Bg G. TREUPEL(Zeit. physiol. Chem., 16, 47--67).-The formation of fatty acids innormal urine when putrefaction sets in is due to the decomposition ofits carbohydrates (dextrose and animal gum). In the present research,the furfuraldehyde and a-naphthol reaction was employed for theestimation of sugar (see Abstr., 1891, 1559), the results being con-trolled, in some cases, by Raumann's benzoic chloride method.It wasfound, that a.s putrefaction advanced the carbohydrate in the urinediminished, but a small quantity always remained, even after veryprolonged periods (30 to 47 days). If the urine was exposed to theair, putrefaction and the diminution of carbohydrate occurred morerapidly than in closed vessels. Increase of the temperature to 35"also hastened the process. W. D. H.Ethereal Hydrogen Sulphates in the Urine, and Disinfec-tion of the Alimentary Canal. By A. ROVIGHI (Zeit. physiol.Chem., 16, 20-46) .--Prom experiments on the author's person, 011various patients, and on clogs, the following conclusions are drawn :-1. The quantitative estimation of the ethereal hydrogen sulphatesin the urine is a trustworthy criterion of the amount of putrefactivechange in the intestine.2.The amount of these substances passed varies with the time ofday, so that it is necessary to examine a specimen of the mixed 24hours' voidings.3. In children, the amount passed is less than in adults.4. Oil of turpentine and camphor in large doses lessen the putrefacPHYSIOLOaIOAL CREMISTRY. 227tion in the dog's intestine, and, consequently, the output of etherealsulphntes in the urine.5. In the human being, given either by mouth or rectum, thesedrugs have not the same efficacy.6. Tannin clyst,ers lessened, but only very slightly, the etherealhydrogen sulphate of the urine in a case of enteroperitonitis, wheretheir amount was excessive.7.A saturated solution of boric acid injected into the intestine ismore effective; but the absorption of the acid by the intestinal~nucous membrane is dangerous.8. The use of Carlsbad salts and Marienbad water is followed byan increased oiitput of ethereal hydrogen sulphates for the first fewdays ; this is followed by a very marked diminution.9. Kephir (l-& litres per diem) is an excellent means of lesseningintestinal putrefaction. Its action depends, in part at least, on thelactic acid it contains. TV. D. H.Physiological Action of Strontium Salts. By J. V. LABORDE(Compt. rend. Soc. Biol., 1890, 708-716 ; 1891, 562-566 ; compareAbstr., 1891, 99).--The action of the snlphate? normal tartrate, andorthophosphate of strontium was compared experimentally with that ofthe corresponding salts of potassium.The results again showed theinnocuity of the strontium compounds ; the lactate and tartrate havea slight diuretic action. Elimination takes place chiefly through thefaeces. It is partly assimilated, being found in the liver and bones,and, t o a small exteut, is climinated in the urine.Further experiments with the bromide were confirmatory of theforegoing. W. D. H.Physiological Action of Camphors, and of their Compoundswith Chloral. By SCHUITT (Colnpt. rend. ~Soc. B i d , 1890, 678-683).-1n a warm-blooded animal, camphor causes excitation of thecentral nervous system leading to general convulsions, an increase inthe depth of respiration, a, slowing of the heart, with increased forceof its beats, and a marked elevation of blood pressure.Borneol andmenthol, on the other hand, produce a sedative action on the nervecentres, borneol being the more powerful. Borneol, however, di-minishes the frequency and depth of respiration, the number andforce of the heart beats, and produces a fall of blood pressure ; whilstmenthcl increases respiratory and cardiac activity, leading to aheightened intravascular pressure.In experiments on rabbits, it was found that by giving borneol afterchloral hydrate, the depressing action of the chloral was augmentedby that of the borneol, whereas menthol in part counteracted thisdepression. Starting from this, the physiological action of com-pounds of chloral with the camphors was investigated.Camphor dissolves in anhydrous chloral, but does not form definitecompounds with it, whereas borneol and menthol do.The mixtureof camphor and chloral produces the same effects as i f the drugswere given successively, the convulsive effects of the camphor beingmasked by the sedative action of the chloral228 ABSTRAOTS OF CHEXIOAL PAPERS.Chloral bomiylute, CCI,-CH(OK)*OCloH,,, forms white crystals in-soliible in water, and melts at 45-55". It is very toxic, producing alowering of blood pressure and temperature to a greater extent thancan be accounted for by the amount of chloral i t contains.C7zZoraE menthylate, CCl&H( OH) .OC,,,H,,, is a transparent, yellow-ish liquid, of the consist,ence of glycerol, insoluble in water,soluble in alcohol of go", and in oil.When distilled with water, i tdissociates into menthol and chloral hydrate ; an analogous dissocia-tion in t,he body probably accounts for its physiological mtion. Itirritates the mucous membranes when applied locally. Given snbcu-taneously or by the mouth, it leads to paralysis of the posterior limbs,and then to sleep ; the soporific action is the same in its strength andduration as that produced by a corresponding dose of chloral hydrate,although its onset is somewhat delayed. The paralytic effects andlessening of reflex action are due to the menthol. The movements ofrespiration and of t4he heart are effected in the same way as witlichloral ; the depression of temperature is, however, not so marked.Blood pressure is first lowered, then rises, remaining stationary at alower level than the original. Thus, to some extent, the mentholcorrects the depression due to the chloral. w. I). H.Toxic Action of Blood andof Various Tissues. By J. H ~ R I -COURT and c. RICHET (Compt. rend. A%. Bid., 1890, 695--696).-Theblood of one animal is poisonous to that of another species; thusthe toxic dose of dogs' blood, as tested in the rabbit, is 40-45 gramsper kilo. of body weight. Birds' blood is more poisonous, its toxicdose being 7 grams. Mosso has previously shown, particularly withfishes' blood, that the poisonous effects of the serum are due to itsprotejids (ichthptoxin) ; and the present experiments confirm thisconclusion, as the alcoholic extracts of the blood and spleen, whichare, of course, free from prote'id, have lost their toxicity. The alcoholicextract of the muscles of some dogs was, however, poisonous, ofothers not. W. D. 1".Toxicity of Serum. By A. CHABRIN (Compt. rend. SOC. BioE., 1890,697).-A preliminary note regarding the toxicity of the serum fromcases of urlleniis, confirmatory of the coaclusions in the precedingabstract. W. U. H

ISSN:0368-1769    

DOI:10.1039/CA8926200225

出版商:RSC    

年代:1892

数据来源: RSC

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228 ABSTRAOTS OF CHEXIOAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Influence of Vegetable Poisons on the Germination of Seeds. By C. CORNEVIN (Arm. Agyon., 17,433-441).-The author’s experi- ments are arranged under the following heads :- A. Action of a regetable poison on the seeds of the species producing it.-Seeds of Agrostemma githago, immersed for 6, 12, 18, 24, 36, andVEGETABLE PHYSIOLOGY AND AGRICULTURE. 229 48 hours in a solution of saponine, and then sown in sterilised soil, germinated sometimes as well as, and sometimes better than, un- treated seeds. Similar resultls were obtained with seeds of Cytisuus hburnum plunged in a solution of cytisine; in fact, more of the treated seeds germinated than of the untreated. B. Action of a vegetable poison not localised in the seed OTA the seeds of the p l a n t producing it.-Poppy seeds contain no poisonous alkalo'ids, and tobacco seeds no nicotine. Seeds of Nicotiana tabacum, plunged for 38 hours in a concentrated decoction of tobacco, and then sown, did not germinate until 48 hours after untreated seeds. Seeds sown in soil watered with dilute nicotine (1 : 50) had their germination re- tarded by 10-23 days, and some refused to germinate.On the other hand, of 50 poppy seeds soaked for 38 hours in aqueous extract of opium, 48 germinated, whilst only 33 out of 50 untreated seeds ger- minated, and this, 24 hours after the others. Out of 50 poppy seeds sown in soil impregnated with opium, 49 germinated ; out of 50 sown in soil watered with water only, 35 germinated a, day in arrear of the treated lot.To ascertain which of the opium alkalo'ids exercises this stimulating effect on germination, solutions of morphine, narce'ine, codei'ne, papaverine, narcotine, and thebahe were tried separately, with the result that narcotine, codehe, and narce'ine stimulated or hastened the germination, whilst papaverine retarded it by 24 hours, and morphine and theba'ine were without influence. C. Action of a vegetable poison on seeds of species not producing it.- Maceration of 30 hours in solutions of oleandrine and of andromedo. toxin (from azaleas) had no injurious effect on the germination of peas, barley, wheat, and oats ; but, whereas haricots were uninjured by oleandrine, their germination was retarded 9-10 days by andro- medotoxin.Colchicine was without effect on wheat, barley, and oats, but was fatal t o the germination of haricots and very injurious to that of peas. Cytisine prevented the germination of haricots, but was without efiect on wheat, oats, barley, peas, and mustard. Saponine and nicotine prevented the germination of haricots, but were without influence on wheat. Opium appeared to hasten the germination of' oats. D. Injuence of the duration of contact of the poison o n the germina- tion of seeds.-Immersion of wheat in nicotine solution for 30 houm was without influence, but if the action was continued for 60 hours only a few seeds germinated, and that after a retardation of 7-8 dayg. Three hours immersion of haricots in cytisine was without influence ; 6 hours accelerated the germination; 9 hours prevented half the seeds from germinating; 12 hours immersion was fatal to all.Nicotine and saponine take 24 hours to destroy the germinating power of haricots. Wheat is more susceptible t o injury from nicotine than from cytisine or saponine ; the reverse is the case with haricots. J. M. H. M. Direct Absorption of Amrnoniacal Salts by Plants. By A. B. GRIPPITHS (Chenz. News, 64, 147 ; compare Muntz, Abstr., 1890,230 ABSTRACTS OF CECEMIOAL PAPERS. i9,287) .-Bean seedlings, after immersion in copper sulphate solution t o destroy nitrifying microbes, and washing with sterilised water, were allowed to grow under antiseptic conditions in a sterilised solution containing 0.1 per cent. of potassium chloride, 0.003 per cent. of ferrous carbonate, and 0.05 per cent. of sodium chloride, ammonium, calcium, and magnesium sulphates, and tricalcium phosphate.At the end of four weeks, the ammonia in the culture solution had diminished to an amount corresponding with 0.027 per cent. of am- monium sulphate. There had been no direct absorption of atmospheric nitrogen, for nodules were not formed on the root,s or rootlets, and there had been no nitrification, f o r ' a t no time could any traces of nitric nitrogen be found in the culture solutions ; hence the ammonium salts must have been directly absorbed by the plant. JN. VT. Mineral Substance in Teak. Ry D. HOOPER (&it. R?-yst. Nin., 19, 485, from Nature, 37, 523).-The inorganic matt,er of teak (Tectona grandis) was formerly determined as CaHPO,.The author finds that the inclusions of a tree from Nilambur have the following composition :- CaC03. Ca3(P0J2. Quartz. Organic matter. H20. 70.05 2.89 9.76 14-33 3.00 Composition of the Ash of Achyranthes aspera, Linn. By C. J. H. WARDEN (Chern. News, 64, 161).-The ash, which is used in India as an alkali, for washing, dyeing, and medicinal purposes, con- tains potassium salts equivalent t o 21.5 per cent. of potassium oxide i n the leaves, to 38.0 per cent. in the stems, and t o 28% per cent. in the roots. The author suggests the use of the plant as a cheap green manure. JN. W. B. H. B. Starch in the Fungus Boletus pachypus, Fr. By E. BOUR- QUELOT (J. Pharm. [ 51, 24,197-199).--The occurrence of starch has been very rarely detected in fungi. Thin sections of the foot and cap of B.pachypus stained with iodine solution give a blue colora- tion, due to the presence of starch in the tissue. The liquid pressed out of the fungus does not give the starch reaction. On boiling the fungus with water, the filtered solution gives a precipitate with alcohol, which, when redissolved in water, gives a blue coloration with iodine solution ; a second portion mixed with fresh saliva (diastase solution) loses its property of becoming blue with iodine solution after a short time, whilst a third portion, treated with saliva, and kept a t the laboratory temperature for 10 hours, acquires the power of reduc- ing alkaline copper solution. Formation and Physiological Significance of Oxalic Acid in Fungi. By C. WEHMER (Ann. Agron., 17,462464 ; from Bot.Zeit., 1891, 15) .-The author has experimented with pure cultivations of fungi in nutritive solutions. In doses of 1 per cent., oxalic acid is fatal to the growth of fungi, but in smaller quantities it is assimilated and decomposed by some as carbonaceous aliment in default of any J. T.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 231 more suitable, Fungi form oxalic acid from any sort of carbonaceous compound which they can assimilate ; its formation depends less on the nourishing medium and the species grown than on the degree of development which the fungus attains; it is, however, directly promoted by the presence of bases in the solution with which it can com- bine. The quantity formed is often many times greater than that of the fungus itself, and the weight of oxalic acidpZus fungus corresponds nearly with that of the sugar consumed when sugar is used as nutri- tive medium.The author looks on oxalic acid as the product of in- complete respiration, and its persistence is, to a great degree, deter- mined by the presence of bases. It is destroyed by further oxidation, with production of carbonic anhydride and water. J. M. H. M. Organic Acids in Beet Juice. By E. 0. v. LIPPMAXN (Bey., 24, 3299--3306).-The presence of malic and tartaric acids in beet juice, hitherto asserted without proof by the text-books, has been proved. The chalk precipitate formed when unripe beets are treated in the evaporating apparatus contains, besides oxalic and citric acids, small quantities of I~evomalic, dextrotartaric, and gliitaric acids.Some deposits were also examined which had been formed in the preliminary warming of the juice after its treatment with chalk. One contained, besides oxalic acid, ordinary succinic and normal adipic: acids. Another contained, besides oxalic, glycollic acid ; about the same time as this was deposited, i t was noticed in the factory that a white powder fiometimes separated out during the filtration of the juice; this powder was shown to contain a polymeride of glyoxal. The author bas once succeeded in obtaining glyoxylic acid from quito young beet plants. The presence in beet juice of the first five members of the oxnlic acid series has IIOW been proved, and also of glycollic, glyoxylic, malic, tartaric, and citric acids. C. F. B. Constituents of Henbane Seed.By F. RANSOM (Pharm. J. Trans. [3], 22, 215--216).-The author obtained from the dried seeds of biennial plants of Hyoscyanzus niger, grown at Hitchin, only 0.058 per cent. of nlkaloi'd. The seed is, therefore, not so rich in alkalo'id as some have asserted, and as it contains also much fixed oil, in which the alkaloid is to some extent soluble, its use for galenical preparations seems undesirable. R. R. AlkaloYds of the Solanaceae. By W. ScHi;'wE (Arch. Pharni,., 229, 492-531) .-The author summarises the conclusioiis to be drawn from his paper, thus:- (1.) The younger roots of wild belladonna contain only hyoscy- a,mine, whilst the older roots contain atropine as well as hyoscyaniine, but only in small proportion ; the same was observed t o be the case in the older cultivated roots.(2.) The ripe berries of cultivated Atropa belladotinu nigra contain atropine and hyoscyamine ; those of the wild plant contain atropine only ; the ripe fruit of Atropa belladoma Eutea contains only atropine, and another base, perhaps identical with atropamine. The unripe2 32 ABSTRACTS OF OHEMICAL PAPERS. fruit of wild Atropu belladonnix raigya contains hyoscyamine with only a small quantity of atropine. (3.) The leaves of the yellow and black fruited, wild Atropa beZEa- donna contain hyoscyamine and atropine, the latter being in small quantity o~ily. (4,) Fresh and old seeds of Datura strarnonium contain chiefly hyoscyamine ; small quantities of atropine and scopolamine are also present. (5.) SoZanunz tuberosum contains, besides beta'ine, an alkalo'id which causes mydriasis.(6.) The niydriatic alkaloid contained in Lycium barbarzm and SoZanum wigrum exists only in small quantities, and appears to be identical with the base contained in Solanzbm tuberosum. (7.) The leaves of Nicotiana tabacunz also contain traces of mydriatic alkaloids. (8.) In the seeds, leaves, and root of Afiisodus Zuridus, gathered in autumn, h yoscyamine only has a pre-existence. A. G. B. Toxic Principles of Amanita pantherina, D.C. By IKOKO (J. Pharm. [ 5 ] , 24, 261-4262 ; afterpharm. Post, 24,1891, 581 ; compere R. Bohm, Abstr., 1885, 1008).--The fungus, when dried, loses a, portion of its poisonous activity, A dried sample yielded 0.1 per cent. of alkaloids, consisting of cholinc with a little muscarine. J. T.Cicuta maculata, Linn. By R. GLENK (Pha~nz. J. Trans. [3], 22, 69-70).-This paper contains the results of a complete analysis of the fruit of Cicuta maculata, with the chemical reactions of the volatile oil, resins, an aqueous extract, and the constituents of the ash. The author obtained an alkalo'id which, however, does not occur in the root also, but was unable to determine whet,her or no this was coniine, owing to insufficiency of material. At one stage of the operations a strong coniine-like odonr was noticed. By K. KRESLING (Arch. P ~ u ~ w z . , 229, 3 8 9 4 2 5 ; compare von Planta, Abstr., 1886, 91) .-The methods adopted in the analysis of the pollen were those recommended by Dragendorf. Full details are given in the original paper; the results are summarised as follows :- R.R. Pollen of Pinus Sylvestris. Noisture, 8.73 per cent. Ash, crude ash, 5-51 per cent.; pure ash, 3.0 per cent., contain- ing :- K20. NGO. MgO. CaO. Pz05. SO3. C1. Fe20,. A1,0,. Si02. Mn203. 37-16 1.62 4.94 4.63 28.70 4.38 1.35 4.08 1.86 10.51 trace. (Compare Famintzin and Przybytek, BzdZ. Acad. Imp. Sci. St. P6tersbourg, 30, 358.) Fat, 11-12 per cent., melting about 40°, and containing:- glycerol, 6.24 per cent. ; alcohols, chiefly cholesterol axrd myricyl alcohol, 6.16 per cent. ; fatty acids, 87.85 per cent., of which 77.35 per cent, is olek acid, and 22.65 per cent. solid acids, chiefly palmitic.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 233 Lecithin, 0.895 per cent. Cane sugar, 12.75 per cent. Starch, 7.4 per cent. Total glucose, obtained by boiling with seminormal acid, 33.1 per cent., which i R 11.7 per cent.more than can be accounted f o r by the cane sugar and starch; this remainder must be derived from the carbohydrates of the cell well. Cellulose, 19.06 per cent. Mucilage, 0.196 per cent. Organic Acids.-Tartaric and malic acids were isolated. Five grams of pollen gave sufficient acid to neutralise 1 7 C.C. of decinormal sodium hydroxide solution. Nitrugeizo us Com~ozciz~s.-Globulin, nuclein, peptone, albumin, amines, and ammonia (0.094 per cent.) were detected. No peptonisirlg ferments were found. Prote'ids, soluble in water and precipitated bp tannin, 1.61 per cent. By extraction with dilute hydrochloric acid and sodium hydroxide, 1.595 per cent. of prote'ids was dissolved and precipitated by tannin.After this extraction there is still 0.681 per cent. of nitrogen, calculated on the original pollen, in the residue, and about half the total of nitrogen, namely, 1.34 per cent., remains in the extract, not being precipitated by tannin. Of bases, there were isolated : xanthine, 0.015 per cent. ; guanine, 0.021 per cent. ; hypoxanthine, 0.085 per cent., and a small quantity of a substance rich in nitrogen, vernine. A. G. B. Rain as a Source of Nitrogen for Vegetation. By C. F. A. TUXEN (Fursch. Gebiete Agr. Phys., 14, 367-368 ; from Tidsskr. f. Landokon., 1890, 325-350) .-In connection with the question of the nitrogen compounds at the disposal of plants, the nitrogen compounds of rain in Denmark were investigated. The tables on the next page show (I) the amount of rain (from 1880 to 1885) and the ammonia and nitric acid per million ; and (11) the amount of nitrogen as ammonia and as nitric acid in kilograms per hectare.The ammonia is chiefly due t o the decomposition of organic matter. The results are considered t o be high, as the rain was collected near a rather large village, where the product.ion of ammonia and nitric acid would probably be greater than in other parts oE the country. N. H. M The Phosphoric Acid of the Soil. By P. P. DFH~RAIN (Ann. Agron., 17, 445-454) .-The author discusses the assimilation of phosphoric acid by different crops in the light of facts furnished by the experimental plots at Grignon. The plots left unmanured since 1875 gave, of late years, very poor crops, and the author has attributed this result, in great measure, to the impoverishment of the soil in humus.As regards the direct elements of fertility, he has shown that the nitrogen is still easily nitrifiable, and that the total phosphoric acid is as much as 0.1 per cent. Yet a dressing of 200 kilos. mineral superphosphate on this plot raised the yield of wheat in 1890 from 8 to 22 metric quintals per hectare, whilst 200 kilos. of superphosphate with 200 kilos. of potas- sium chloride gave 24 metric quintals. Even then, as regards wheat, YOL. LSII. Tf. I' Ammo- nia. ------ 0.85 2-53 1-71 1.05 0.58 I Summer. Nitric acid, -- 0'46 0.15 0.13 0.04 1-26 I Rain- fall. mm. '56 103 47 98 88 Rain- full. Amnio- nia. ---- 1.80 3-07 9.90 3'63 4.35 1960-1 .............. im-2 ..............1882-3 .............. 1883-4 .............. 1884-5 .............. Ammo- nia. mm. 14 1 178 215 179 146 Nitric acid. 1880-1 ................... 1881-2 ................... 1882-3 ................... 1883-4 ................... 1884-5 ................... 7-96 12-33 13'47 10-33 11.42 Ammo- nia. 0 -75 0 -70 0 '81 1 -50 0 '92 -- 2 .80 1-28 0.98 i-97 6.07 Nitric acid. 2.38 4-02 2.91 2-21 0.98 0 -40 0 '45 0.31 0 -44 0.85 1'27 2.71 0.62 1.31 0'35 Om%d 3.14 1 0.02 3.13 0.16 0.22 4'81 0.03 3.96 0.05 O W 3 1.78 , 0.53 3-63 0.56 2.15 5-60 1.11 5-46 , 1.61 Rain- fall. mm. 287 184 165 ' 205 1 1 i 3 11. Bummcr. 1-06 1 0.56 1.24 0.82 1-79 1 0.68 2.71 0.80 1.38 I 1-20 Rain- fall. .- m m. 78 74 61 173 114 Winter. Ammo- nia. I_- 3 -38 4.36 7 -98 1.05 5 '10 Nitric acid. 0 -80 0 -03 0.04 0.31 1 -09 Spring.I Win tcr. I Autumn - I I I I I Ammo- Nitric Ammo- Nitric Ammo- Nitric nia. I acid. 1 nia. I acid. 1 nia. I acid. Spring. E3 w 6 Nitric acid. -- 9m s 0.16 g 2'01 g 0'50 !aj 0'12 0.56 im ci W w Y E 0 b- cd 9 r Whole year. I cd m Ammo. Nitric Tohl D nin. 1 acid. i nitrogen. --- lo -26 13 -61 14 -45 12'30 17 -49VEQETABLE PHYSIOLOGY AND AGRICULTURE. 235 the sterility is largely due t o exhaustion of assimilable phosphoric acid, the total phosphoric acid, nevertcheless, remaining abundant. The author long since proposed to treat samples of soil with acetic acid in order to distinguish the assimilable from the non-assimilable phosph- ates, on the assumption that the calcium phosphate of the soil is assimilable and entirely soluble in acetic acid, the ferric and aluminium phosphates being non-assimilable and insoluble.I n point of fact, the soil of the unmanured plots yields only traces of phosphate soluble in acetic acid, whilst that of the manured plots yields notable quantities, as do other soils on which dressings of superphosphate produce no increase of crop. The Roil of the unmanured plots con- tained, in 18i9, 0.03 per cent. of P,O, soluble in acetic acid, to-day, only traces; in 10 years, therefore, a layer of soil weighing 4000 tonnes per hectare has lost 1200 kilos. of assimilable P,O,. The crops removed during *his time certainly contained less than 400 kilos. of P,05 altogether, so that two-thirds of the assimilable P,O, must have been washed out of the soil or converted into inert forms.The former alteimative is improbable, drainage watera, especially from unmanured soils, containing mere traces of phosphoric acid. As regards the second alternative, Thenard concluded long ago, that a dressing of calcium phosphate (bone black) was converted, after a time, into ferric and aluminium phosphahes by reaction with Roil, and the same thing may be proved by a laboratory experiment. If a little calcium phosphate be mixed with soil and treated with carbonic acid water in a seltzogene, after a few days it is found that no phosphate is dissolved, although calcium phosphate by itself is soluble in carbonic acid water. The soil may be replaced by oxide of iron or alumina with the same result. Although ferric and aluminium phosphates may be non-assimilable by wheat, they appear to fitand 011 a different footing as regards oats, for whereas the plots manured every year gave, in 1888, 37.8 metric quintals of oats per hectare, the plots unmanured since 1875 gave as much as 31.1 metric quintals. Moreover, in 1891, whilst the manured plots gaye 36 metric quintals of oats, and the unmanured plots 28, the addition of 200 kilos.of superphosphate to the latter only raised the yield to 30 quintals. The author suggests, as a possible explanation, that the acid in the juice of the roots is carbonic acid, that the roots of oats may be more charged with this than those of wheat, and that the carbonic acid may withdraw alkali carbonate from its association with the clay of the soil to form bicarbonate, which is capable of dissolving the phosphates of iron and alumina, althuugh carbonic acid itself will not do so.Even calcium carbonate, in conjunction with carbonic acid wat8er, is capable of causing the solution of ferric phosphate. It is probable that dressings of farmyard manure, containing as it does alkali carbonates, assist in the solution of these phosphates, and so render them assirnilable by crops, and also liable to be washed out of the soil. J. M. H. M.228 ABSTRAOTS OF CHEXIOAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Influence of Vegetable Poisons on the Germination of Seeds.By C. CORNEVIN (Arm. Agyon., 17,433-441).-The author’s experi-ments are arranged under the following heads :-A. Action of a regetable poison on the seeds of the species producingit.-Seeds of Agrostemma githago, immersed for 6, 12, 18, 24, 36, anVEGETABLE PHYSIOLOGY AND AGRICULTURE.22948 hours in a solution of saponine, and then sown in sterilised soil,germinated sometimes as well as, and sometimes better than, un-treated seeds. Similar resultls were obtained with seeds of Cytisuushburnum plunged in a solution of cytisine; in fact, more of thetreated seeds germinated than of the untreated.B. Action of a vegetable poison not localised in the seed OTA the seedsof the p l a n t producing it.-Poppy seeds contain no poisonous alkalo'ids,and tobacco seeds no nicotine. Seeds of Nicotiana tabacum, plungedfor 38 hours in a concentrated decoction of tobacco, and then sown,did not germinate until 48 hours after untreated seeds.Seeds sownin soil watered with dilute nicotine (1 : 50) had their germination re-tarded by 10-23 days, and some refused to germinate. On the otherhand, of 50 poppy seeds soaked for 38 hours in aqueous extract ofopium, 48 germinated, whilst only 33 out of 50 untreated seeds ger-minated, and this, 24 hours after the others. Out of 50 poppy seedssown in soil impregnated with opium, 49 germinated ; out of 50 sownin soil watered with water only, 35 germinated a, day in arrear of thetreated lot. To ascertain which of the opium alkalo'ids exercises thisstimulating effect on germination, solutions of morphine, narce'ine,codei'ne, papaverine, narcotine, and thebahe were tried separately,with the result that narcotine, codehe, and narce'ine stimulated orhastened the germination, whilst papaverine retarded it by 24 hours,and morphine and theba'ine were without influence.C.Action of a vegetable poison on seeds of species not producing it.-Maceration of 30 hours in solutions of oleandrine and of andromedo.toxin (from azaleas) had no injurious effect on the germination ofpeas, barley, wheat, and oats ; but, whereas haricots were uninjuredby oleandrine, their germination was retarded 9-10 days by andro-medotoxin.Colchicine was without effect on wheat, barley, and oats, but wasfatal t o the germination of haricots and very injurious to that ofpeas.Cytisine prevented the germination of haricots, but was withoutefiect on wheat, oats, barley, peas, and mustard.Saponine and nicotine prevented the germination of haricots, butwere without influence on wheat.Opium appeared to hasten thegermination of' oats.D. Injuence of the duration of contact of the poison o n the germina-tion of seeds.-Immersion of wheat in nicotine solution for 30 houmwas without influence, but if the action was continued for 60 hoursonly a few seeds germinated, and that after a retardation of 7-8 dayg.Three hours immersion of haricots in cytisine was without influence ;6 hours accelerated the germination; 9 hours prevented half theseeds from germinating; 12 hours immersion was fatal to all.Nicotine and saponine take 24 hours to destroy the germinatingpower of haricots. Wheat is more susceptible t o injury fromnicotine than from cytisine or saponine ; the reverse is the case withharicots. J.M. H. M.Direct Absorption of Amrnoniacal Salts by Plants. By A.B. GRIPPITHS (Chenz. News, 64, 147 ; compare Muntz, Abstr., 1890230 ABSTRACTS OF CECEMIOAL PAPERS.i9,287) .-Bean seedlings, after immersion in copper sulphate solutiont o destroy nitrifying microbes, and washing with sterilised water, wereallowed to grow under antiseptic conditions in a sterilised solutioncontaining 0.1 per cent. of potassium chloride, 0.003 per cent. offerrous carbonate, and 0.05 per cent. of sodium chloride, ammonium,calcium, and magnesium sulphates, and tricalcium phosphate.At the end of four weeks, the ammonia in the culture solution haddiminished to an amount corresponding with 0.027 per cent. of am-monium sulphate.There had been no direct absorption of atmosphericnitrogen, for nodules were not formed on the root,s or rootlets, and therehad been no nitrification, f o r ' a t no time could any traces of nitricnitrogen be found in the culture solutions ; hence the ammonium saltsmust have been directly absorbed by the plant. JN. VT.Mineral Substance in Teak. Ry D. HOOPER (&it. R?-yst. Nin.,19, 485, from Nature, 37, 523).-The inorganic matt,er of teak(Tectona grandis) was formerly determined as CaHPO,. The authorfinds that the inclusions of a tree from Nilambur have the followingcomposition :-CaC03. Ca3(P0J2. Quartz. Organic matter. H20.70.05 2.89 9.76 14-33 3.00Composition of the Ash of Achyranthes aspera, Linn. ByC. J. H. WARDEN (Chern.News, 64, 161).-The ash, which is used inIndia as an alkali, for washing, dyeing, and medicinal purposes, con-tains potassium salts equivalent t o 21.5 per cent. of potassium oxidei n the leaves, to 38.0 per cent. in the stems, and t o 28% per cent. inthe roots. The author suggests the use of the plant as a cheap greenmanure. JN. W.B. H. B.Starch in the Fungus Boletus pachypus, Fr. By E. BOUR-QUELOT (J. Pharm. [ 51, 24,197-199).--The occurrence of starch hasbeen very rarely detected in fungi. Thin sections of the foot andcap of B. pachypus stained with iodine solution give a blue colora-tion, due to the presence of starch in the tissue. The liquid pressedout of the fungus does not give the starch reaction. On boiling thefungus with water, the filtered solution gives a precipitate withalcohol, which, when redissolved in water, gives a blue coloration withiodine solution ; a second portion mixed with fresh saliva (diastasesolution) loses its property of becoming blue with iodine solution aftera short time, whilst a third portion, treated with saliva, and kept a tthe laboratory temperature for 10 hours, acquires the power of reduc-ing alkaline copper solution.Formation and Physiological Significance of Oxalic Acid inFungi.By C. WEHMER (Ann. Agron., 17,462464 ; from Bot. Zeit.,1891, 15) .-The author has experimented with pure cultivations offungi in nutritive solutions. In doses of 1 per cent., oxalic acid isfatal to the growth of fungi, but in smaller quantities it is assimilatedand decomposed by some as carbonaceous aliment in default of anyJ. TVEGETABLE PHYSIOLOGY AND AGRICULTURE.231more suitable, Fungi form oxalic acid from any sort of carbonaceouscompound which they can assimilate ; its formation depends less onthe nourishing medium and the species grown than on the degreeof development which the fungus attains; it is, however, directlypromoted by the presence of bases in the solution with which it can com-bine. The quantity formed is often many times greater than that ofthe fungus itself, and the weight of oxalic acidpZus fungus correspondsnearly with that of the sugar consumed when sugar is used as nutri-tive medium. The author looks on oxalic acid as the product of in-complete respiration, and its persistence is, to a great degree, deter-mined by the presence of bases.It is destroyed by further oxidation,with production of carbonic anhydride and water. J. M. H. M.Organic Acids in Beet Juice. By E. 0. v. LIPPMAXN (Bey., 24,3299--3306).-The presence of malic and tartaric acids in beet juice,hitherto asserted without proof by the text-books, has been proved.The chalk precipitate formed when unripe beets are treated in theevaporating apparatus contains, besides oxalic and citric acids,small quantities of I~evomalic, dextrotartaric, and gliitaric acids.Some deposits were also examined which had been formed in thepreliminary warming of the juice after its treatment with chalk. Onecontained, besides oxalic acid, ordinary succinic and normal adipic:acids. Another contained, besides oxalic, glycollic acid ; about thesame time as this was deposited, i t was noticed in the factory that awhite powder fiometimes separated out during the filtration of thejuice; this powder was shown to contain a polymeride of glyoxal.The author bas once succeeded in obtaining glyoxylic acid from quitoyoung beet plants.The presence in beet juice of the first fivemembers of the oxnlic acid series has IIOW been proved, and also ofglycollic, glyoxylic, malic, tartaric, and citric acids. C. F. B.Constituents of Henbane Seed. By F. RANSOM (Pharm. J. Trans.[3], 22, 215--216).-The author obtained from the dried seeds ofbiennial plants of Hyoscyanzus niger, grown at Hitchin, only 0.058 percent. of nlkaloi'd.The seed is, therefore, not so rich in alkalo'id assome have asserted, and as it contains also much fixed oil, in whichthe alkaloid is to some extent soluble, its use for galenical preparationsseems undesirable. R. R.AlkaloYds of the Solanaceae. By W. ScHi;'wE (Arch. Pharni,.,229, 492-531) .-The author summarises the conclusioiis to bedrawn from his paper, thus:-(1.) The younger roots of wild belladonna contain only hyoscy-a,mine, whilst the older roots contain atropine as well as hyoscyaniine,but only in small proportion ; the same was observed t o be the casein the older cultivated roots.(2.) The ripe berries of cultivated Atropa belladotinu nigra containatropine and hyoscyamine ; those of the wild plant contain atropineonly ; the ripe fruit of Atropa belladoma Eutea contains only atropine,and another base, perhaps identical with atropamine.The unrip2 32 ABSTRACTS OF OHEMICAL PAPERS.fruit of wild Atropu belladonnix raigya contains hyoscyamine with onlya small quantity of atropine.(3.) The leaves of the yellow and black fruited, wild Atropa beZEa-donna contain hyoscyamine and atropine, the latter being in smallquantity o~ily.(4,) Fresh and old seeds of Datura strarnonium contain chieflyhyoscyamine ; small quantities of atropine and scopolamine are alsopresent.(5.) SoZanunz tuberosum contains, besides beta'ine, an alkalo'id whichcauses mydriasis.(6.) The niydriatic alkaloid contained in Lycium barbarzm andSoZanum wigrum exists only in small quantities, and appears to beidentical with the base contained in Solanzbm tuberosum.(7.) The leaves of Nicotiana tabacunz also contain traces ofmydriatic alkaloids.(8.) In the seeds, leaves, and root of Afiisodus Zuridus, gathered inautumn, h yoscyamine only has a pre-existence. A.G. B.Toxic Principles of Amanita pantherina, D.C. By IKOKO (J.Pharm. [ 5 ] , 24, 261-4262 ; afterpharm. Post, 24,1891, 581 ; compereR. Bohm, Abstr., 1885, 1008).--The fungus, when dried, loses a,portion of its poisonous activity, A dried sample yielded 0.1 percent. of alkaloids, consisting of cholinc with a little muscarine.J. T.Cicuta maculata, Linn. By R. GLENK (Pha~nz. J. Trans. [3], 22,69-70).-This paper contains the results of a complete analysis of thefruit of Cicuta maculata, with the chemical reactions of the volatileoil, resins, an aqueous extract, and the constituents of the ash. Theauthor obtained an alkalo'id which, however, does not occur in theroot also, but was unable to determine whet,her or no this was coniine,owing to insufficiency of material.At one stage of the operations astrong coniine-like odonr was noticed.By K. KRESLING (Arch. P ~ u ~ w z . ,229, 3 8 9 4 2 5 ; compare von Planta, Abstr., 1886, 91) .-Themethods adopted in the analysis of the pollen were those recommendedby Dragendorf. Full details are given in the original paper; theresults are summarised as follows :-R. R.Pollen of Pinus Sylvestris.Noisture, 8.73 per cent.Ash, crude ash, 5-51 per cent.; pure ash, 3.0 per cent., contain-ing :-K20.NGO. MgO. CaO. Pz05. SO3. C1. Fe20,. A1,0,. Si02. Mn203.37-16 1.62 4.94 4.63 28.70 4.38 1.35 4.08 1.86 10.51 trace.(Compare Famintzin and Przybytek, BzdZ. Acad. Imp. Sci. St.P6tersbourg, 30, 358.)Fat, 11-12 per cent., melting about 40°, and containing:-glycerol, 6.24 per cent. ; alcohols, chiefly cholesterol axrd myricylalcohol, 6.16 per cent. ; fatty acids, 87.85 per cent., of which 77.35 percent, is olek acid, and 22.65 per cent. solid acids, chiefly palmiticVEGETABLE PHYSIOLOGY AND AGRICULTURE. 233Lecithin, 0.895 per cent.Cane sugar, 12.75 per cent.Starch, 7.4 per cent.Total glucose, obtained by boiling with seminormal acid, 33.1 percent., which i R 11.7 per cent. more than can be accounted f o r by thecane sugar and starch; this remainder must be derived from thecarbohydrates of the cell well.Cellulose, 19.06 per cent.Mucilage, 0.196 per cent.Organic Acids.-Tartaric and malic acids were isolated.Five gramsof pollen gave sufficient acid to neutralise 1 7 C.C. of decinormalsodium hydroxide solution.Nitrugeizo us Com~ozciz~s.-Globulin, nuclein, peptone, albumin,amines, and ammonia (0.094 per cent.) were detected. No peptonisirlgferments were found. Prote'ids, soluble in water and precipitated bptannin, 1.61 per cent. By extraction with dilute hydrochloric acidand sodium hydroxide, 1.595 per cent. of prote'ids was dissolved andprecipitated by tannin. After this extraction there is still 0.681 percent. of nitrogen, calculated on the original pollen, in the residue,and about half the total of nitrogen, namely, 1.34 per cent., remainsin the extract, not being precipitated by tannin. Of bases, therewere isolated : xanthine, 0.015 per cent.; guanine, 0.021 per cent. ;hypoxanthine, 0.085 per cent., and a small quantity of a substancerich in nitrogen, vernine. A. G. B.Rain as a Source of Nitrogen for Vegetation. By C. F. A.TUXEN (Fursch. Gebiete Agr. Phys., 14, 367-368 ; from Tidsskr. f.Landokon., 1890, 325-350) .-In connection with the question of thenitrogen compounds at the disposal of plants, the nitrogen compoundsof rain in Denmark were investigated. The tables on the next pageshow (I) the amount of rain (from 1880 to 1885) and the ammonia andnitric acid per million ; and (11) the amount of nitrogen as ammoniaand as nitric acid in kilograms per hectare.The ammonia is chiefly due t o the decomposition of organic matter.The results are considered t o be high, as the rain was collected neara rather large village, where the product.ion of ammonia and nitricacid would probably be greater than in other parts oE the country.N.H. MThe Phosphoric Acid of the Soil. By P. P. DFH~RAIN (Ann.Agron., 17, 445-454) .-The author discusses the assimilation ofphosphoric acid by different crops in the light of facts furnished bythe experimental plots at Grignon.The plots left unmanured since 1875 gave, of late years, very poorcrops, and the author has attributed this result, in great measure, tothe impoverishment of the soil in humus. As regards the directelements of fertility, he has shown that the nitrogen is still easilynitrifiable, and that the total phosphoric acid is as much as 0.1 percent.Yet a dressing of 200 kilos. mineral superphosphate on thisplot raised the yield of wheat in 1890 from 8 to 22 metric quintals perhectare, whilst 200 kilos. of superphosphate with 200 kilos. of potas-sium chloride gave 24 metric quintals. Even then, as regards wheat,YOL. LSII. f.I'Ammo-nia.------0.852-531-711.050.58I Summer.Nitricacid,--0'460.150.130.041-26IRain-full.1960-1 ..............im-2 ..............1882-3 ..............1883-4 ..............1884-5 ..............Ammo-nia.mm.14 1178215179146Nitricacid.1880-1 ...................1881-2 ...................1882-3 ...................1883-4 ...................1884-5 ...................Ammo-nia.0 -750 -700 '811 -500 '92Nitricacid.2.384-022.912-210.980 -400 '450.310 -440.851'27 2.71 0.62Om%d 3.14 1 0.020.22 4'81 0.03O W 3 1.78 , 0.532.15 5-60 1.11Rain-fall.mm.287184165 ' 205 1 1 i 311.Bummcr.1-06 1 0.561.24 0.821-79 1 0.682.71 0.801.38 I 1-20Rain-fall..-m m.787461173114I Win tcr.I Autumn -II I IAmmo- Nitric Ammo- Nitricnia. I acid. 1 nia. I acid. VEQETABLE PHYSIOLOGY AND AGRICULTURE. 235the sterility is largely due t o exhaustion of assimilable phosphoric acid,the total phosphoric acid, nevertcheless, remaining abundant. Theauthor long since proposed to treat samples of soil with acetic acid inorder to distinguish the assimilable from the non-assimilable phosph-ates, on the assumption that the calcium phosphate of the soil isassimilable and entirely soluble in acetic acid, the ferric and aluminiumphosphates being non-assimilable and insoluble.I n point of fact,the soil of the unmanured plots yields only traces of phosphatesoluble in acetic acid, whilst that of the manured plots yields notablequantities, as do other soils on which dressings of superphosphateproduce no increase of crop. The Roil of the unmanured plots con-tained, in 18i9, 0.03 per cent. of P,O, soluble in acetic acid, to-day,only traces; in 10 years, therefore, a layer of soil weighing4000 tonnes per hectare has lost 1200 kilos.of assimilable P,O,.The crops removed during *his time certainly contained less than400 kilos. of P,05 altogether, so that two-thirds of the assimilableP,O, must have been washed out of the soil or converted into inertforms. The former alteimative is improbable, drainage watera,especially from unmanured soils, containing mere traces of phosphoricacid. As regards the second alternative, Thenard concluded longago, that a dressing of calcium phosphate (bone black) was converted,after a time, into ferric and aluminium phosphahes by reaction withRoil, and the same thing may be proved by a laboratory experiment.If a little calcium phosphate be mixed with soil and treated withcarbonic acid water in a seltzogene, after a few days it is found thatno phosphate is dissolved, although calcium phosphate by itself issoluble in carbonic acid water. The soil may be replaced by oxide ofiron or alumina with the same result.Although ferric and aluminium phosphates may be non-assimilableby wheat, they appear to fitand 011 a different footing as regards oats,for whereas the plots manured every year gave, in 1888, 37.8 metricquintals of oats per hectare, the plots unmanured since 1875 gave asmuch as 31.1 metric quintals. Moreover, in 1891, whilst the manuredplots gaye 36 metric quintals of oats, and the unmanured plots 28,the addition of 200 kilos. of superphosphate to the latter only raisedthe yield to 30 quintals.The author suggests, as a possible explanation, that the acid in thejuice of the roots is carbonic acid, that the roots of oats may be morecharged with this than those of wheat, and that the carbonic acidmay withdraw alkali carbonate from its association with the clayof the soil to form bicarbonate, which is capable of dissolving thephosphates of iron and alumina, althuugh carbonic acid itself willnot do so. Even calcium carbonate, in conjunction with carbonicacid wat8er, is capable of causing the solution of ferric phosphate.It is probable that dressings of farmyard manure, containing as itdoes alkali carbonates, assist in the solution of these phosphates,and so render them assirnilable by crops, and also liable to be washedout of the soil. J. M. H. M

ISSN:0368-1769    

DOI:10.1039/CA8926200228

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

236 ABSTRACTS OF OHEMICAL PAPERS. An a l y t i c a1 C h e m i s t r y. The Application of Capillary Phenomena to the Analysis of Liquids. By E. GossARrr (Compt. rejid., ll3,537--540).-Everyliquid may be caused to roll in drops upon itself, the drops being separated from the main body of the liquid by a thin stratum of vapour. A drop is allowed to fall from a height of 1 mm. upon the concave meniscus at the edge of the vessel containing the liquid. It is con- venient to use a vessel with sloping sides, giving a meniscus of hyperbolic section. The liquid is rendered viscous by the addition of such substances as citric acid or glycerol. Using two pure liquids, the drops of the one never roll upon the other, owing to the immediate absorption of the fieparating film of vapour. If the supporting liquid contains an impurity, test drops of the same liquid will roll upon the supporting liquid, provided that they contain the same percentage of the same impurity, o r that this per- centage only varies within fixed limits.These limits can, with care, be reduced so far that it becomes possible t o find the amount of im- purity present within & of the total. Each impurity behaves as if it alone were present. A general method for the detection and estimation of impurities in liquids hence becomes possible ; it is particularly serviceable in the case of spirituous liquors. W. T. Estimation of Free Hydrochloric Acid in the Stomach. By L. GRAFFENBERGER (Landw. VersucAs-Stat., 39, 4 5 5 4 5 9 ) .-The best method for the estimation of the free hydrochloric acid in the contents of the stomach is that of Sjoquist (Abstr., 1889,302), as modified by v.Jaksch ; this modification consists in estimating the barium gravi- metrically as barium sulphate. In the present research, the applicability of the method was tried with various arti6cial mixtures, to which a known amount of hydro- chloric acid was added ; the mixtiires contained chlorides ; organic acids ; organic acids and chlorides ; peptone ; peptone, chlorides and organic acids ; starch ; and lafitly starch, peptone, pepsin, organic acids, and chlorides. The result in all cases was the same, or at least the error never exceeded 0.01 per cent. The method is thus an admirable one. Protejids other than peptones in the mixture give rise to a loss of acid of from 3 to 4 per cent.Estimation of Chlorates. By F. A. GOOCH and C. G. SMITH (Amer. J. Sci. [3], 42, 220--223).-The authors communicate a, rapid and easy but indirect process for the estimation of chloric acid, which is briefly as follows :-An accurately measured solution con- taining potassium iodide, sodium hydrogen arsenate, and dilute sulphuric acid is boiled in an Erlenmeyer’s flask until the liberated iodine is expelled. The residue, after cooling, is first neutralised with soda, then mixed with excess of solution of sodium hydrogen carbonate, W. D. H.ANALYTICAL CHXMISTRY. 231 and finally titivated with N/10 iodine. The experiment i R now repeated, this time with the addition of a definite amount of a chlorate. As there is no reaction between hydriodic acid and arsenic acid, as long as there is a chlorate present, the amount of iodine used to reoxidise the arsenious acid will be considerably less.The amount of chioric acid may, therefore, be readily calculated. It is of great importance to have a good excess of potassium iodide. The test analyses are satis- factory. L. I)E K. Microscopic Detection of Sulphurous Anhydride. By G. DENIGOS (J. Pharm. [5], 24, 289--290).-A saturated solution of cadmium nitrate is diluted with 20 vols. of an aniline solution con- taining 20 to 25 grams per litre. Immediately before use a little of this is acidified with about 1 per cent. of acetic acid, taken up on the end of a glass rod: and held over the mouth of the vessel from which sulphurous anhydride is supposed to be escaping.I n presence of this compound, a white film rapidly forms, which, under the micro- scope, is clearly seen to consist of regular, hexagonal plates. If the cadmium solution is not acidified, the test appears to be more sen- sitive, but, under the microscope, the hexagonal crystah are found to be almost completely replaced by far less characteristic radiating crystals. J. T. New Method of EBtimating Nitrogen. By E. BOYER (COWZ..~. vend., 113: 503).-The method is founded on the complete reduction of nitric nitrogen t o ammonia by oxalates and sulphur in presence o€ soda-lime. A reducing mixture is made, consisting of 1 part of sulphur, 2 parts of calcium oxalate, and 6 parts of soda-lime. A quantity of the dry substance containing not more than 0.5 gram of nitrate is intimately mixed with 50 grams of the reducing mixture.A combustion-tube, 55 cm. long and 1.7 cm. in diameter, is closed at one end, and is then charged by the successive introduction of 2 grams of calcium oxalate, 10 grams of powdered soda-lime, 10 grams of the reducing mixture, the substance mixed as above, 10 grams of the reducing mixture, 10 grams of powdered soda-lime, and a plug of asbestos. The combustion is carried on just as in an ordinary soda- lime: combustion, and occupies about 40 minutes. It is necessary to boil the staiidard sulphuric acid, before titration, to expel the sulphur- etted hydrogen and carbonic anhydride formed during the combustion. The method may be employed t o determine total nitrogen existing in the three states of organic: ammoniacal, and nitric nitrogen, and yields good results ; for instance, an analysis of sodium nitrate gave 16-45 of nitrogen for 16.47 present; a mixture containing 0.1284 gram of organic and aminoniacal nitrogen yielded 0.1281 gram; a, mixture containing burnt leather, ammonium sulphate, and sodium nitrate gave 0.1161 gram nitrogen out of 0.11655 gram; a similar mixture containing dried blood yielded 0.1624 gram out of 0.1627 gram of nitrogen present.Estimation of Carbon in Steel. By A. A. BLAIR (Chem. News, 64, 66-69 ; from J. Anal. and AppZ. Chem.., 5, 3).-A continuation W. T.238 ABSTRACTS Ol!’ CHEMICAL PAPERS. of the work of the International Steel Standards Committee ; certain modifications are recommended’ in the ordinary combustion process. The double chloride of copper and potassium is to be preferred to the analogous ammonium salt., as the lather is liable to contain organic impurities derived from the manufacture of the ammonia.The air used €or the combustion is best supplied from a pressure- cylinder, as the use of an aspirator facilitates the introduction of im- purities from the atmosphere of the laboratory. The products of combustion are best purified by cuprous chloride and anhydrous copper sulphate, the former absorbing the free chlor- ine, the latter the hydrogen chloride ; the cuprous chloride, which is converted into a convenient granular form by heating the moistened powder and stirring until dry, is placed in the anterior limb of a Marchand U-tube, the posterior limb of which is occupied by the copper sulphate, guarded by a plug of asbestos. As anhydrous copper sulphate is a more efficient desiccating agent than the granular cal- cium chloride used in the guard-tube of the potash bulb, it is necessary t o moisten the gases as they leave the purifying apparatus, and dry them again over calcium chloride before they enter the absorptioi t apparatus. For this purpose, n plug of cotton woo1 placed in the bulb of a Marchand U -tube containing the calcium chloride is moistened at the commencement of each combustion.I n weighing the potash-bulbs, the use of capillary stoppers is recommended, as they allow the equalisation of pressure without per- mitting the introduction of any sensible amount of moisture. J?;. W. Estimation of Thallium. By H. BAUBIGNY (Compt.rend., 113, 544-547) .-The estimation of this metal by precipitation as thallous iodide admits of accurabe results, notwithstailding the remarks of previous observers. The inaccuracy of the method alleged by Willm is due to the final washing with distilled water. Werther’s asser- tion that thallous iodide is insoluble in ammoniacal water is not borne out by the facts, but its solubility in dilute alcohol is less than that author indicates. T h e most accurate modification of the process is carried out as follows :-Tha thallous iodide is precipitated at 80-go”, it then collects together well without to any extent adhering to the glass. The whole is cooled; the orange precipitate, a t first very finely divided, forms a dense, crystalline, yellow powder which may be readily filtered.The precipitate is washed with a 1 per cent. solution of potassium iodide, in which it is insoluble, until free from foreign salts; finally the potassium iodide is washed out by 82” alcohol, which, while readily dissolving potassium iodide, does not dis- solve enough thallous iodide t o yield even a coloration with ammonium sulphide after concentration of the washings to one-fifth their bulk. The precipitate is dried and detached as completely as possible from the filter, and in order to avoid the use of a tared filter, the thallous iodide adhering to the paper is dissolved by the aid of a little dilute nitric acid, and received in a tared porcelain crucible; the solution is then gently evaporated with a, few drops of hydrochloric acid, precipitated by the addition of a drop of concentrated hydriodic acid, dried, the main quan- tity of the precipitate added, the whole heated for some hours at 170”,ANALYTICAL CHEMISTRY.239 and weighed. Although thallium and its salts are too volatile to allow of the incineration of the paper without loss, thallons iodide does not volatilise at 170". Test analyses gave accurate results. (Compare Long, Abstr., 1891, 1295.) W. T. Oxidation of Copper-glance by the Electric Current. By E. F. SMITH and 1). L. WALLACE (Ber., 24, 2938-2939; see also Ber., 23, 2276).-It has been shown that metallic sulphides in alkaline solutions are decomposed by the electric current in such a way that the whole of the sulphur is oxidised to sulphuric acid. Copper-glance was the only exception.The authors have now succeeded in completely decomposing this mineral by the electric current. Finely powdered copper-glance (0.1066 gram) and potassium hydroxide (35 grams) are mixed in a nickel crucible and submitted for 40 minutes to the action of an electriccurrent producing 1 ampere of electrolytic gas per minute. Before stopping the current, it is reversed for a few minutes. The contents of the crucible are then washed out with water, filtered from the insoluble oxide, acidified with hydrochloric acid, and precipitated with barium chloride. The reAnlts are good : 20.80 and 20.91 per cent. of sulphur being obtained, as against 21.00 per cent. obtained by oxidation with nitric acid. The essential conditions for success are the employment of a large quantity of potassium hydroxide and the prolonged action of the electric current. E.C. R. Electrolytic Separation of mercury from Copper. By E. F. SMITH and A. W. MACCAULEY (Bey., 24, 2936--2938).-The authors have found that by carefully regulating the current, the separation of mercury from copper is complete, even when t,he latter is present in twice as large a quantity as the former. Moreover, the presence of zinc, nickel, or other metals in no way hinders the separation. A table of the results obtained is given. A Reaction for Cerous Oxide. By P. C. PLUGGE (Arch. Pharm., 229, 558-561).-The most delicate reagent for cerous oxide is a solution of 1 part of strychnine in 1000 parts of concentrated sulphuric acid. The suspected solution is made alkaline with sodium hydroxide, evaporated on a piece of porcelain, and the dry residue brought in contact with 2 or 3 drops of the strychnine solution ; in the presence of cerium, a bright-blue colour is developed wbich rapidly fades and gives place to a cherry-red or pale-red, according to the quantity of cerium present.As little as 0.01 milligram of cerous oxide can be detected in this way, the colour being a pale blue-violet which rapidly disappears. This test was devised for the detection of cerium in the contents of a stomach, where the cerium was present in the form of oxalate, which is officinal in some pharmacopmias as a remedy for vomiting, dyspepsia, &c. ; in euch a case, the presence of sodium hydroxide is necessary t o decompose the cerium oxalate. The t8est may also be applied directly to a precipitate produced by ammonia and contain- E.C. R.240 ABSTRAOTS OF 0HE;M'IOAL PAPERS, ing zinc and aluminium as well, only ammonium sulphide or zinc sulphide must not be present. Separation of Manganese and Nickel, Manganese and Cobalt, and of Manganese, Nickel, and Cobalt. By P. JAN- NASCH and C. J. FI~ANZEK (Rer., 24, 3204--3205).-1t has been previously shown by Jannasch and McGregory (Abstr., 1891, 963) that zinc and manganese may be quantitatively separated by means of hydrogen peroxide in strong ammoniacal solution and in presence of a large quantity of ammonium chloride. The separation of manga- nese from nickel may be readily carried out under similar conditions, but not that of manganese and cobalt. If, however, the hydrogen peroxide is added to these metals when in the form of double alkali cyanides, the manganese precipitate is completely free from cobalt ; in the same way manganese may be separated from nickel, or, as would be expected, from a mixture of both thet;e metals.The precautions neceesary to ensure success will be published later. Volumetric Estimation of Iron by Potassium Dichromate and Stannous Chloride. By R. NAMIAS (Gazaetta, 21, 473-476). --The author considera the ordinary method of estimating iron by dichromate, using potassium ferricyanide as an indicator, to be in- convenient and somewhat inexact. He finds the following method to give good results :-An excess of standard dichromate solution is run into the solution of the ferrous salt, acidified with hydrochloric acid ; a few drops of iodine and starch solution are added, and the excess of dichromate determined by titration with standard stannous chloride solution.I t is convenient to use a potassium dichromate solution containing about 5 grams of the salt per litre ; the stannous solution should be Colorimetric Estimation of Iron. By L. LAPICQUE (Compt. revLd. HOG. Biol., 1890, 669-671).-1n view of certain observations by Kriiss and Morath (Abstr., 1889, 124), in which they found the colorimetric estimation of iron led to variable results, the author has re-examined his former method (Abstr., 1890, 297) of estimating t,he iron in blood. He also finds certain variable factors, but by using a large excess of alkali thiocyanate in constant proportion, and then acidifying strongly with sulphuric acid, these are reduced t o a minimum.Among the circumsta,nces leading to variation, tempera- ture must be mentioned ; t o obviate this, it is suggested that every time a series of estimations is to be made, the thiocyanate should be previously titrated with a ferric salt in order to determine fhe constant I(. W. D. H. A. G. B. H. G. C. equivalent to this. w. J. P. Decomposition of Chrome-Iron Ore by Hydrochloric Acid under Pressure. By P. JANNASCH and H. VOGTHERR (Ber., 24, 3206-3208) .-The method already recommended by one of the authors for decomposing silicates, namely, by heating with hydro- chloric acid under pressure in a platinum apparatus (Abstr., 1891,ANALYTICAL CHEMISTRY. 241 619), may also be adopted with advantage in decomposing chrome- iron ore for quantitative analysis.The most suitable acid is a mix- ture of 4 vols. of concentrated acid of sp. gr. 1.119 and 1 vol. of water, and it, should be saturated with ammonium chloride ; the tubes must be heated for 8-10 hours at about 250", the decomposition being then a t least as complete as with the methods usually adopted. Estimation of Molybdic and Tungstic Acids. Ey E. F. SMITH and R. H. BRADRURY (Ber., 24, 2930-2936).-The authors have made experiments to determine if molybdic arid tungstic acids can be estimated by means of their barium, calcium, strontium, lead, silver, cobalt, bismuth, or cadmium salts. The following results were obtained :- Barium molybdate' is precipitated on adding barium chloride t o a cold solution of so$urn molybdate.It dissolves completely in acids, is more soluble in a dilute solution of ammonium nitrate than in water, and dissolves in 17,ZOU parts of water at 23". The quantita- tive estimation was carried out as follows :-A measured quantity of sodium molybdate solution containing 0.1 144 gram of molybdenum was made up to 200 c.c., heated to boiling, precipitated with a boiling solution of barium chloride, allowed to remaic until cold, filtered, washed with cold water, and the precipitate separated from the filter-paper, and ignited. The results obtained were good. I f the precipitate be filtered while the soliltion is hot, a small quantity of molybdenum will be found in the filtrate. Barium tungstate is a heavy, white precipitate, which is decomposed by warm acids with formation of yellow tungstic acid, and is more soluble in dilute ammonium nitrate than in water.The quantitattive eetimation, which gives good results, is carried out in a similar way to the molgbdate, but in this case the precipitate is collected while hot, and washed with hot water. Strontium molybdate resembles the barium salt in appearance, is practically insoluble in water, dissolving in 9600 part's a t 17". It is easily decomposed on heating, and is, therefore, not suitable for quantitative estimations. Strontium tungstate behaves in the same mray as the molybdate. Calcium Mo1ybdate.-The addition of calcium chloride to a cold, dilute solution of sodium moljbdatc does not cause a precipitate. On adding alcohol, or on heating the solution to boiling, a white, granular precipitate is at once obtained, which is somewhat soluble in water, and insoluble in alcohol.The quantitative estimation was carried out in the same way as for the barium salt, but although the filtrate contained molybdenum, the results were always too high. The following method was then employed :-The calcium molybdate waB precipitated in boiling solution, and boiled until the precipitate became granular, cooled, one-third the volume of alcohol added, the mixture allowed to remain for some time, filtered, and the pre- cipitate washed with dilute alcohol (1 : 3). The filtrate cont'aiaed no moljbdenum. On heatzing the precipitate in a platinum crucible to a strong, yellow beat, it loses weight, and, unless the heating is sufficient, high results are obtained.H. G. C.242 ABSTRACTS OF CHEMICAL PAPERS. Calcium tungstate resembles the preceding salt, but the quantita- tive results varied considerably. Lead molybdate is a white, granular precipitate, in a moist condi- tion soluble in nitric acid and sodium hydroxide; on heating, i t acquires a yellow colour, and then is not attacked by the above reagents. With regard to the quantitative results, the authors con- firm the results of previous observers. Lead tungst,ate is a white, flocculent, finely-divided precipitate, extremely hard to filter, and insoluble in water. It is quite insoluble in ammonium nitrate, and the addition of this salt renders the filtra- tion much easier. Silver tungstate and molybdate are at once precipitated on adding silver nitrate to solutions of the sodium salts.Silver tnngstate iR more finely divided and more difficult to filter than the molybdate. The latter is a white precipitate resembling silver chloride, distinctly soluble in water, easily soluble in nitric acid, potassium cyanide, and sodium bydroxicl-e; on heating, it turns purple, and melts at a low temperature to a clear, yellow liquid. Silver tungstate is yellow, less soluble in water, melts at a higher temperature, and, on heat- ing, t.urns dark-purple. These salts are not suitable for quantita- tive exFeriments, as they are soluble in water, and decompose on heating. Cadmium molybdate is a heavy, granular salt, insoluble in water, and, when moist, soluble in ammonia, acids, and potassium cyanide, and, after heating, is still soluble in acids.G.ood quantitative results are obtained as follows :--The solution is precipitated with cadmium nitrate, collected on a Gooch's porcelain crucible, and, after drying, carefully heated. Cadmium tnngstate is obtained in a fine state of division, but is not ditficnlt t o filter. It resembles the molybdate, but, after heating, is not soluble in acids. The quantitative estimation is carried out in the same way as for the molybdate. The authors point out that probably an estimation of molybdic and tungstic acids when mixed could be obtained by dividing the solution into two parts: in one part estimating the mixed acids a5 cadmium salts, and in the other part also precipitating as cadmium salts, then dissolving in potassium cyanide, and determining t h e cadmium electrolytically.The quantitative results were good. The bismuth salt's are insoluble in water. Cobalt molybdate is not formed either i n cold dilute or concen- trated solutions. By heating a concentrated solution of sodium molybdate with cobal t nitrate, a small quantity of a bluish-white precipitate is formed, which dissolves again on cooling. Cobalt tungstate is violet-red, and is at once formed on adding cobalt nitrate to a solution of sodium tungstate. Estimation of Antimony and its Condition of Oxidation. By P. A. GOOCH and H. W. GRUKKER (Amer. J. Sci. [3], 42, 213- 220).-When antimonious oxide is treated with iodine in an alkaline solution, it passes into the higher state of oxidation. If, on the other hand, an acid solution of autimonic oxide is boiled with hydriodic E.C. R.ANALYTICAL CHEMISTRY, 243 acid, iodine is liberated, and thc antimony is reduced to the lowcr state of oxidation. On these principles the authors have based the following process €or the determination of antimony :-A weighed quantity of the antimony salt, corresponding with about 0.2 gram of Sb,O,, is titrated in presence of 1 gram of sodium tartrate and 20 C.C. of a saturated solution of' sodium hydrogen carbonate, with N/10 iodine solution standardised against tartar emetic. The result of this titration gives the amount of Sb,O,. 4 grams of tartaric acid is then added to the liqnid, and, if still alkaline, dilute sulphuric acid is added until the mixture is neutral. 10 C.C. of 50 per cent. sulphuric acid is now added, and also a little over a gram of potassium iodide.The liquid is diluted t o 100 c.c., and boiled in an Erlenmeyer flask until the volume is reduced to 50 C.C. In order to prevent bumping, a, platinum spiral is introduced, and to obviate mechanical loss, also a trap made of a two-bulb drying tube, cut short, and hung, large eud downward, in the mouth of the flask. The faint colour still remain- ing after coilcentration is bleached by means of centi-normal sulph- urous acid, and the solution nearly neutrnlised with sodium hydroxide ; 20 C.C. of solution of sodium hydrogen carbonate is again added, and the liquid once more titrated with the standard iodine solution in the presence of starch. This titration gives, of course, the entire amonnt of antimony present.The difference between the indications of the two titrations gives the antimony in the higher state of oxidation. The process is accurate and rapid, as shown by many test analyses, and also extremely simple as regards manipulation. L. DE K. Carbazole Method for Estimating Nitrates in Water Analysis. Bv W. P. MASON (Chem. News, 64, 197).-The author, who is dightly disappointed with the delicacy and uniformity of results ob- tained by this process, points out the fact that cold solutions darken much more slowly than the warmer ones. In applying the process, the same precaution must be taken as when nesslerising for ammonia, namely, the standards and the solutions of unknown strength must be operated on at the same temperature. After the addition of atrong sulphuric acid, the tube may be cooled immediately, or gradually, before the carbazole solution is added.The latter solution, which in a stoppered flask keeps for about 48 hours, acts best when its colour has changed to an olive-green. Estimation of Nitrates in Water. By A. HAZEN and H. W. CLARK (CYhem. News, 64, 121-122, and 162-1644 .-The authors have examined the phenolsulphonic acid process of Grandral and Lajoux (Abstr., 1885, 1093), and find that it is not trustworthy, as the various nitrophenols which may be formed have colouring powers differing in intensity. The aluminium process, however, yields more satisfactory results. 50 C.C. of' the water is treated with 2 C.C. of 40 per cent. sodium hydroxide solution and 0.4 gram of aluminium foil, 0.12 mm.thick, and the whole is allowed to remain at the ordinary temperature for 24 hours. If the free ammonia is high, i t must be distilled off before L. UE K.244 ABSTRACTS OF CHEMIOAL PAPERS. adding the aluminium. A portion of the solution? varying from 1 to 25 c.c., according to the amount of nitrates present. is now diluted to 500 C.C. with water free from carbonic anhydride (prepared by passing steam through distilled water), and nesslerised in the usual way. It is found unnecessary, in most cases, to distil before nesslerising, as the water is sufficiently decolorised and clarified by the action of the hydrogen. The diluent water must be free from carbonic anhydride, a8 otherwise the liquid will become turbid with precipitated aluminium hydroxide.A correction is made for the volume of the sodium hydroxide solution, the ammonia carried off by the hydrogen, and the ammonia converted into nitrogen, the factor being 0.88 when the above quantities are used. The authors have experimentally det,er- mined the amount of ammonia carried off by the hydrogen, and find i t to agree with the amount calculated from the gaseous laws. Albumino'id matter is attacked by the hydrogen, part of it being converted into an amount of ammonia varying from 2 to 4 per cent. of the albuminoid ammonia, but the quantity is negligible unless the latter is very high. Estimation of Volatile Oil in Copaiba. By R. A. CRIPPS (Pharnz. J. Trans. [3], 22, 195--194).-In a small weighed flask, 0 3 gram of copaiba is placed with about 5 C.C. of water.A regulated jet of steam is sent through the mixture, and, as the exit titbe from the flask leads into a test tube immersed in cold water, any turpentine present can be immediately recognised by its odour. The exit tube is provided with a bulb, in which any resin mechanically carried over is arrested. I n half an hour, the loss of weight, after drying the flask at loo", represents all the volatile oil. Examination of Spirits for Secondary Constituents. By A. H. ALLEN and W. CHATTAWAY (Anatyst, 1891,10%--115).-The authors (have devised the following process (a modification of Marquardt's method) for the estimation of fusel oil in commercial spirits, sach as whisky:-As a preliminary step, any fixed matters must be removed, and any ethers and furfuraldehyde destroyed.100 C.C. of the spirit is taken, 20 C.C. N/10 soda added, and the whole heated in a reilux apparatus for an hour. The contents of the flask are then distilled in the followiug manner:-A volume of 90 C.C. is allowed to pass over, the flame is then removed, and 30 C.C. of water is intro- duced into the distilling flask. The distillation is conducted until 20 C.C. more has been collected. The flask is allowed to cool, and 10 grams of sodium sulphate washed into i t with 20 C.C. morc water. If now the distillation be continued until another 20 C.C. has passed over, all the amyl alcohol will have been volatilised. The entire distillate is now diluted with brine until the density of the liquid is about 1.1, when i t is shaken four times successively with carbon tetrachloride, using 40 C.C.the first time, then 20 c.c., and lastly, 10 C.C. The carbon tetrachloride now contains the nmyl alcohol (and other fusel constituents), and, probably, some ethyl alcohol, which may be removed by agitation, first with brine, afterwards with a strong solution of sodium sulphate. The oxidation of the fusel oil may be Jx. W. R. R.ANALYTICAL CHEMISTRY, 245 conducted in a closed bottle, or, more convenientJy, using a reflux condenser. The oxidising mixture consists of 5 grams of potassium dichromate, ‘t grams of strong sulphuric acid, and 10 C.C. of water. When a flask is used attached to a reflux condenser, the carbon tetra- chloride should be kept in active ebullition for eight hours, thesource of heat being a water-bath. After oxidising, the product is diluted with 30 C.C.of water and distilled over a naked flame until only 20 C.C. remains in the flask. 80 C.C. of water is now added, and the distil- lation continued until only 5 C.C. remains in the flask. The distillate will now contain the whole of the valeric acid, a portion being dis- solved in the carbon tetrachloride, and the remainder in the aqueous fluid. The entire distillate is now titrated with N/10 barium hydr- oxide, using methyl orange as an indicator, and shaking tborouqhly after each addition. If the carbon tetrachloride has, before use, been well puriEed by treatment with the oxidising mixture and redistil- lation, no more than 2 C.C. of the baryta solution ought to be required. Phenolphthale’in is now added, and tbe titration continued, with frequent shaking, until the neutral point is again reached.Each C.C. of N/10 alkali used in the second stage of the titration corresponds with 0.0102 gram of valeric acid or 0.0088 gram of arnyl alcohol. The neutralised aqueous fluid is now carefully separated from the carbon tetrachloride (which can be used again), evaporated to dryness at 1;30”, and the residual barium salt is weighed. After allowing for any barium chloride, which may he calculated from the alkali used in the first stage of the titration, the mean combining weights of the organic acids can be found as follows :- Milligrams of organic barium salt C.C. of N barium hydroxide x 67.5 = combining weight of organic acid. The process gives very accurate results, providing the following points are rigidly observed :- 1.The carbon tetrachloride must be previously purified by treat- ment with chromic acid mixture and subsequent diatillaticn over barium carbonate, and must be free from chloroform. 2. All corks used in distilling the spirit must be kept distinct from those employed in the distillation of the products of oxidation. They must be always carefully covered with tin-foil. 3. ,4 few small fragments of pumice-stone should be added, in each case, to the contents of the distilling flasks. They should be treated with the chromic: mixture before use. 4. The brine should be made from clean table salt, and rendered distinctly acid with sulphuric acid. Qualitative and Quantitative Estimation of E’urfu1.aldeity~e.--Furfur- aldehyde in spirits can be detected, and its proportion roughly guessed at, by the reaction of the sample with a solution of aniline in glacial acetic acid.Ten drops of aniline are dissolved in 2 C.C. of the acid, and the mixture added to 10 C.C. of the spirit to be tested. A red coloration, which increases in intensity after a time, shows the presence of furfuraldehyde. If a quantitative estimation is required, the authors proceed as follows :-246 ABSTRACTS OF CHEMTOAL PAPERS. 200 C.O. is distilled to about 20 c.c., when 50 C.C. of water is added, and the distillation continued until all but 10 C.C. has passed over. The distillates are mixed and divided into t,wo equal parts, A and B. One portion, A, is titrated with N/10 soda, using phenolphthalein as indicator, and the free acid thus found calcu- lated to acetic acid.The neutral liquid is treated with 20 C.C. of N/10 soda and boiled in a reflux apparatus for one hour, when the excess of alkali is ascertained by titrating with N/10 hydrochloric acid. The other portion, B, is treated with 1 C.C. of aniline and 1 C.C. of phosphoric acid of 1.442 sp. gr., and boiled in a reflox ap- paratus for at least two hours. It is then distilled t o a low bulk, and the distillate neutralised and treated with 20 C.C. of NllO soda, exactly as was done with the other portion. The difference between the alkali added and that found by titration represents that consumed by the saponification of the ether in 100 C.C. of t,he spirit; each C.C. represents 0-0088 gram of ethylic acetate. The difference between the amounts of alkali required for the saponification of portions A and B represents the alkali which has reacted with furfuraldehyde, acetaldehyde, &c.Assuming, only the first t o be present, 1 C.C. of N/lO soda represents 0,0192 gram of furfuraldehyde. One of the authors very much questions whether the presence of even an excess of amjl alcohol in whisky constitutes a danger to health. L. DE K. Estimation of Glycerol, Astringent Acids, and Colouring Matter in Wine. By I?. JEAN (Analyst, 18131, 56--57).-Estin,zation of the GZyceroZ.-250 C.C. of the sample is evaporated to the volumeof 100 c.c., agitated with lead oxide, and then rendered slightly alkaline with baryta-water. The filtrate is neutralised with dilute sulphuric acid, concentrated to about 50 C.C.in a flat porcelain dish, and mixed with 5 grams of lead oxide, 10 grams of sand, and 20 grams of barium sulphate. The mass is cautiously dried at loo", and the powdered residue extracted with a mixture of equal parts of alcohol and ether until the liquid measures 60 C.C. 30 C.C. is placed in a tared glass capsule, and 210 grams of dry litharge having been added, the whole is evaporated on the water-bath, and then dried to a constant weight at 105-106". The other 30 C.C. is evaporated i n a tared glass capsule of 6 cm. diameter, and finally dried in an air-bath at 160-170". The difference in weight between residue No. 1 (after allowing for the litharge) and No. 2, multiplied by 8, and divided by 1.243, gives the number of C.C. of glycerol in 1 litre of wine.Estimation of Astimingent Acids.-(a.) anontannin. 250 c c. of the sample is concentrated down to 100 c.c., shaken with excess of freshly precipitated arsenious sulphide, and then filtered. The filtrate is concentrated to 50 c.c.? mixed with 10 grams of silica and 20 grams of barium sulphate, and finally dried at 100". The residue is pow- dered and extracted with warm ether ; the latter is evaporated, and the residue is dissolved in a little alcohol. Into this solution is now introduced a weighed quantity of dry, prepared, powdered hide, which will take up all the tannin in about half an hour. AfterANALYTICAL CHEMISTRY. 247 washing it with spirit, it is dried at 100" and reweighed. The increase in weight, multiplied by four, equal8 the cenontanniii i n 1 litre of the wine.( b . ) CTnogaZZic Acid. The alcoholic filtrate is diluted with dis- tilled water up to 100 c.c.,and in 20 c . ~ . of this, the acid is estimated by means of a solution of iodine, previously standardised with gallic acid, as follows :-Two solutions are prepared, one containing 0.2 gram of iodine per litre, the other 0.125 gram of gallic acid in 250 C.C. of' distilled water. Into a beaker, marked 50 o.c., is put 10 C.C. of the gallic acid solution and 3 C.C. of a saturated solution of sodium hydrogen carbonate. Iodine solution is now added from ?; burette until a drop of the mixture, tested on thick filter-paper dressed with powdered starch, leaves n stain surrounded by blue. Water is now added up to the mark, and iodine again added until R similar stain is obtained.Having thus standardised the iodine, it is used in a similar manner on the 20 C.C. of the alcoholic liquid, mixed with 3 C.C. of solution of sodium hydrogen carbonate. ( c . ) Colouring matter. 250 C.C. of the sample is slowly evaporated down to 100 c.c., rendered alkaline with ammonia, and shaken up with freshly-precipitated arsenious sulphide. After filtering, a slight excess of acetic acid is added, and the liquid once more filtered. The two filters containing the arsenious sulphide are, after washing, heated with spirit slightly acidified with acetic acid, which gradually dissolves out the colouring matter. The alcoholic solution is evaporated in a tared capsule, desiccated at 1 0 5 O , and the residual colouring matter. is weighed. L.DE K. Estimation of Pentoses in Vegetables. By W. E. Srrom (Ber., 24, 3019-3021).-The material under examination is heated in a retort with hydrochloric acid (sp. gr. 1.06) so that not more than 10 C.C. of dist,illate is obtained in five minutes, fresh acid being added from time to time. As soon as the distillate ceases t o react with aniline acetate, the heating is suspended, and the distillate neutralised with soda, slight excess of acetic acid added, and the liquid diluted with water to a known volume. Portions of 25 C.C. are then mixed with phenylhydrazine solution, quickly boiled, rapidly cooled, arid filtered, the filtrate being tested with alkaline copper solution; if it contains excess of phenylhydrazine, less is added in subsequent titrations ; after three or four experiments, it is possible to determine the exact quantity of pheilylhydrazine required, within 0.1 C.C.The phenylhydrazine solution is made by dissolving 1 gram of phenylhydrazine hydrochloride, and 3 grams of sodium acetate in 500 C.C. of water, a,nd is standardised by titration with a solution containing 1 gram. of pure furfuramide and a little acetic acid in 1 litre of water. The phenylhjdrazine solution changes after 24 honra. Although this method does not give residts which are theoretically correct, since part of the material ie decomposed during distillation with the acid, the numbers obtained for the same substance are uniform, and the percentages of pentoses contained in different alimentary sub- stances can be readily compared. J. B. T.248 ABSTRACTS OF CHEMICAL PAPERS.Estimation of Mixtures of Saccharose, Invert Sugar, and Dextrose or Levulose. By G. W~GCHMANK (Analyst, 1891, 15-33).-A direct estimation of saccharose in presence of dextrose and IevuIose has been proposed by Winter. This process, t h e accuracy of which is much doubted by the a,uthor (but which want,s further investigation), is carried out as follows :-The sugar solution is mixed with a solution of lead acetate, to which ammonia has been added until a permanent precipitate threatens to form. An abundant white precipitate is formed, which is then digested with a large amount of water. The filtrate contains the sugar as a lead compound, from which the lead may be readily separated by a current of carhonic anhydride. The insoluble portion is suspended in water, and also treated with carbonic anhydride to liberate the dextrose. The insoluble mass, which still contains the levulose, will yield the latter on treatment with hydrogen sulphide.Indirect processes, based on polarisation, do not always yield accurate results, a s the polarimetric observations are too much in- fluenced by a small change in temperature. The author, who has made a large number of test analyses (with- out making any important alteration in the process), has proved the accuracy OF the method proposed by Sieben, which is based on the following principle :- The saccharose and dextrose + levulose are calculated from the copper-reducing power before and after inversion. Any levulose, whether naturally present, or formed from half the quantity of the saccharoso during inversion, may be readily destroyed by prolonged boiling with excess of hydrochloric acid, and subequently determined from the diminished copper-reducing power.L. DE K. Estimation of Maltose, Dextrose, and Dextrin in Beer-wort and Beer by means of Ferment Organisms. By H. ELIOX (Chent. Centr., 1891, ii, 281 ; from C‘entr. Bakteriologie u. Parasitenkunde, 9, 525--528).--The author refers again t o this method (Abstr., 1x91, 368), and in proof of its validity, he points out that tho re- ducing power of the sugar which disappears during fermenta- tion and the amount of dextrose formed by hydrochloric acid from the same, almost exactly corresponds with the amount of maltose. At the same time, he admits that under the term “maltose” he includes also any other sugar which may have undergone ferments- tion, still the result is sufficiently exact for technical purposes.The author also objects to the use, as in Bau’s experiments (Zoc. cit.), of Saccharomyces apiculatzcs, since its nature and fermenting qualities have not as yet been sufficiently examined. Estimation of Cholesterol. By I(. O B E m C r , L m (Zeit. physio~. Chem., 16, 143-151) .-In the estimation of cholesterol in mixtures containing neutral fats, the sodium ethoxide method of saponification (Abstr., 1890, 1474) is found to cause no loss of cholesterol. J. W. L. W. D. H. Carbohydrates. Ry B. TOLLENS and others (Landw. Versuchs-Xtat., 39, 401-453).-1n the analysis of vegetable products by the usualANALYTICAL CHEMISTRY.249 method, the fat, prote’ids, insoluble fibre, and ash are estimated directly, and the difference between the sum of these components and 100 is returned as “ extract,ive matter free from nitrogen.” This extractive matter consists for the most part of carbobydrat*es, which can be estimated directly by means of Pehling’s solution, after pre- vious treatment with dilute acids; it contains, however, in many cases, il considerable proportion of suttstances which cannot be esti- mated in this manner, and for the detection and estimation of which suitable methods are greatly needed. I n the present paper, the author reviews the most important reac- tions of various carbohydrates, with reference to the analysis of vegetable products in general. The levulinic acid reaction is first discussed, and it is stated that the formation of this acid, on boiling a substance with hydrochloric acid of sp.gr. 1.09-la10 for 20 hours, map be considered as strong eyidence of t>he presence of a true carbohydrate* (compare Wehmer and Tollens, AnnaZen, 243, 315 ; Abstr., 1888, 535). The following substances give the levulinic acid reaction :-Cane sugar, dextrose, levulose, inuliii , gum-arabic, filter-paper, fir-wood, st arch, Carragheen moss, levulin, lactose, galactose, raffinose, irisin, mannose, sorbin, the gliicosides salicin and amygdalin, potato-juice, and chondrin. It must be borne in mind that even in the case of a true carbohydrate only a small quantity of lerulinic acid is formed, and that the isola- tion of the acid is by no means an easy matter; consequently an unsuccessful attempt to obtain the levulinic acid reaction only shows the absence of any considerable quantity of a true carbohydrate.Having ascertained in this way the presence of a true carbohydrate, its isolation and identification have next, to be considered. I n the case of dextrose, or of substances such as lactose, raffinose, salep-juice, &c.. which yield dextrose, the presence of this sugar can be easily proved by oxidising the suhstance with nitric acid (comparo Gans a i d Tollens, Annalen, 245, 215 ; Abstr., 1888, 1059); the for- mation of saccharic acid under theee conditions is a proof of the presence of dextrose, or of dextrose-groups. Inulin, sorbin, arabinose, galactose, mannose, and quince-juice+ do not give the saccharic acid reaction.The formation of mucic acid on oxidation with nitric acid (compare Creydt and Tollens, Abstr., 1886, 582) may be taken as a proof that a substance contains galactose or galactose groups ; i t has been shown that this acid is obtained from galactose, lactose, raffinose, and Car- ragheen moss, and also from the “ sulphite-liquors ” of the wood- cellulose process (compare Weld, Lindsay, Schnelle, and Tollens, Abet,r., 1891, 43). The quantity of raffinose in molasses can, in fact, be determined by estimatixig the muck acid produced on oxidation (compare Creydt, Abstr., 1887, 307). There is no reaction by which the presence of levulose, or of levulose groups, in a vegetable product Note by Ahtractor.-The term “ true carbohydrate” seems to apply only to the hexoses, and to compounds such as starch, inulin, &c., which yield hexoses on hydrolysis.t Note by Abstractor.-Quince-juice, according to Baucr (see p. 428), yields dextrose on hydrolysis. VOL. LXII. 8250 ABSTRACTS OF CHEMICAL PAPERS. can be satisfactorily determined ; the readiness with which this sugar undergoes decomposition on heating with sulphuric acid, or dilute hydrochloric acid, yielding brown Rolutions, may, however, serve as a means of distinguishing i t from dextrose ; Seliwanoff's colour re- action (Abstr., 1887, 459) is also to be recommended in particular cases. Mannose can be readily detected by warming a dilute solution OE the substance under investigation with phenylhydrazine acetate ; its presence is shown by the formation of a crystalline hydrazone (m.p. about 188'). As this sugar is usually present in vegetable products in a combined form, the substance must first be heated with 3 per cent. hydrochloric acid for some hours. The presence of mannose in the " sulphite-liquors " from the wood-cellulose process is easily proved by means of the phenylhydrazine reaction ; the sugar can be conveniently prepared by decomposing the hydrazone with concen- trated hydrochloric acid. The pentoses, arabinose, and xylose, although closely related to the hexoses, differ from the latter in possessing certain characteristic properties by which their presence in a given vegetable product can be easily proved. They do not give the levulinic acid reaction, but when distilled with hydrochloric 01- sulphuric acid they yield a dis- tillate which contains furfuraldehyde ; the presence of this compound can be easily ascertained by the red coloration which is produced on the addition of aniline or xylidine (compare Schiff, Abstr., 1887,571).As, however, the hexoses give traces of furfuraldehyde under the same conditions, the presence o€ pentoses must not be regarded as definitely established unless the reaction is very marked, or unless the furfuraldehyde is determined quantitatively by means of phenyl- hydrazine (compare Chalmot and Tollens, Abstr., 1891: 768). The pentoses also give a characteristic red colour with phloroglucinol and with orcinol, in presence of hydrochloric acid. It must be borne in mind that glycuronic acid aiid its derivatives give all the reactions of the pentoses.A very complete account of the occurrence, properties, and methods of estimation of'the pentoses is given, but all the principal facts dealt with have formed the subject of previous papers by the author and others (compare Abstr., 1891, 43, 659, 768). F. S. I(. Valuation of Oil of Cloves. By H. THOMS (Phurm. J. Tmns. [:3], 22, 450, 451).-Assuming that the quantity of eugenol in oil of cloves can be taken as a measure of the value, the author pro- poses to separate the eugenol directly from the oil in the form of benzoyleugenol, by mixing the oil with solution of sodium or potas- fiium hydroxide, and t h m adding an equivalent of benzoic chloride. Crystalline benzoyleugenol separates as the mixture becomes cold, is recrystallised several times from hot alcohol, washed with alcohol a t 17", and weighed dry on a filter, allowouce being made for its solu- bility (0.55 gram in 2.5 C.C.of 90 per cent. alcohol). From the weight of benzoyleagenol, the quantity of eugeiiol present in the oil can be calc dated. R. R.ANALYTICAL CHEMISTRP. 251 Examination of Vinegar. By W. J. SYKES (AnaZyst, 1891, 83--87).-The author thinks that considerahle iriformation may be gathered from an examination of the ni tz-ogenous constituents of a vinegar, as to whet,her it is genuine or not; but the fixing of limits must naturally be rewerred until a long series of experiments have been performed in this particular direction. Albumoses may be estimated by precipitation with a saturated fiolntion of ammonium sulphate.Peptone may be precipitated in the filtrate by the cautious addition of a solution containing 4 grams of tannin in 190 C.C. of proof spirit mixed with 8 C.C. of dilute acetic acid. Pure malt vinegar should also give a turbidity with phospho- tungstic acid, or potassium bismuthoiodide, or potassium mercuro- iodide. L. DE K. Adulteration of Beeswax. By A. and P. BUISINE (BUZZ. SOC. Chim. [3], 5, 65$-660).-Arnongst the substances used to adulterate beeswax, the most conspicuous and common are those indicated in the accompanying table. Although the influence of some of these on the physical character of the wax is extremely marked, others, by judiciors selection, can be so combined as to imitate it, not only in it,s physical characteristics, b u t also in its behaviour under the methods of analysis a t present in use.The authors propose, in addition t o the usual estimation of free and combined fatty acids, to determine the unsaturated fatty acids, the free hydrocarbons, and the alcohols present in the sample, as well as it,s melting point and density. The sample, dried a t 110", at which temperature i t should not lose more than 1 per cent. of its weight, should leave no residue of mineral adulterant's on treatment with hot chloroform or turpentine. The melting point and density of the ori,pina,l sample should corre- spond with those of beeswax. Any serioiis adulteration will be rendered evident by this procedure, and will necessitate further examination to determine its nature and amount. To estimate the soluble fatty acids, an excess of which indicates the presence of vegetable waxes, and to detect soluble colouring matter such as turmeric and annatto, 20 grams of the sample is extracted with hob water.The dried residue is utilised for the determination of t,he fkee and total fatty acids, the unsaturated acids (by iodine absorption), the alcohols (by the amount o l hydrogen liberated by alkalis), and the free hydrocarbons. The nature and approximate amount of the adulterants are then determined, in the manner already indicatel, by reference to the appended table (see next page;, which embodies the results obtained by the examination of the various adulterants known to be in use. Jx. W.---- Japanese wax , . . . . . . . . . Chinese wax. . . . . . . . . .. . Vegetable waxes , . . . . . , . Carnauba wax . . . . . . . . . . Mineral waxes.. . . . . . . . . Paraffins, .. . . . . . . . . . . . . Suint wax.. .. .. .. .. .. .. Fatty acids of suint.. . . . . Tallow .. . . .. . . .. .. .. . . Steario acid . . . . . . , . . . . . Resin.. .. , . .. . .. ... .. .. Yellow beeswax. . . . . . . . . White beeswax . . . . . . . . . Melting point. --. 47-a0 53 *5 47-54 83-85 60-80 38--74 62 - 66 50 --ca 4-50 ' 5 55.5 - 62.- 64 63-64 Density. Soluble acids in milligrams of KHO per gram of sample. 0 0 0 0 0 0 0 0 0-1 0-2 ~~ Free acids in milligrams of KHO per gram of sample. --- 18-28 22 17-19 4 4 0 0 95-115 159-185 2 %--5 208 168 19-21 20-23 Total acids n milligrams of KHO per gram of sample. --- 216-222 218 218-220 79--u8 0 0 102-1 19 159-189 196-213 209 178 91-97 93-110 Iodine absorption per 100 parts of sample.-- 6-7 '55 6 *85 6 *G-8 ' 2 7 - 9 0 - 4 '6 1 -7-3 -1 13-18 ' 5 B G--2'8 27- a0 4 133 *If 8-1 1 2-7 C.C. of hydro- gen at O@ and 760 mm. vielded by 1 gr. of sample. -- 69-71 72.3 73-74 78-76 0 0 0 0 52- 60 - 35 58-57 '5 53-57 w cn w Hydrocarb- on8 per 100 parts of sample. 100 100 1 g F 14-18 2 0 a 0 F 0 0 12 5-14 ' 5 11-19.5236 ABSTRACTS OF OHEMICAL PAPERS.An a l y t i c a1 C h e m i s t r y.The Application of Capillary Phenomena to the Analysis ofLiquids. By E. GossARrr (Compt. rejid., ll3,537--540).-Everyliquidmay be caused to roll in drops upon itself, the drops being separatedfrom the main body of the liquid by a thin stratum of vapour. Adrop is allowed to fall from a height of 1 mm.upon the concavemeniscus at the edge of the vessel containing the liquid. It is con-venient to use a vessel with sloping sides, giving a meniscus ofhyperbolic section. The liquid is rendered viscous by the addition ofsuch substances as citric acid or glycerol. Using two pure liquids,the drops of the one never roll upon the other, owing to the immediateabsorption of the fieparating film of vapour.If the supporting liquid contains an impurity, test drops of thesame liquid will roll upon the supporting liquid, provided that theycontain the same percentage of the same impurity, o r that this per-centage only varies within fixed limits. These limits can, with care,be reduced so far that it becomes possible t o find the amount of im-purity present within & of the total.Each impurity behaves as if italone were present.A general method for the detection and estimation of impurities inliquids hence becomes possible ; it is particularly serviceable in thecase of spirituous liquors. W. T.Estimation of Free Hydrochloric Acid in the Stomach. ByL. GRAFFENBERGER (Landw. VersucAs-Stat., 39, 4 5 5 4 5 9 ) .-The bestmethod for the estimation of the free hydrochloric acid in the contentsof the stomach is that of Sjoquist (Abstr., 1889,302), as modified byv. Jaksch ; this modification consists in estimating the barium gravi-metrically as barium sulphate.In the present research, the applicability of the method was triedwith various arti6cial mixtures, to which a known amount of hydro-chloric acid was added ; the mixtiires contained chlorides ; organicacids ; organic acids and chlorides ; peptone ; peptone, chlorides andorganic acids ; starch ; and lafitly starch, peptone, pepsin, organic acids,and chlorides.The result in all cases was the same, or at least the errornever exceeded 0.01 per cent. The method is thus an admirable one.Protejids other than peptones in the mixture give rise to a loss of acidof from 3 to 4 per cent.Estimation of Chlorates. By F. A. GOOCH and C. G. SMITH(Amer. J. Sci. [3], 42, 220--223).-The authors communicate a,rapid and easy but indirect process for the estimation of chloric acid,which is briefly as follows :-An accurately measured solution con-taining potassium iodide, sodium hydrogen arsenate, and dilutesulphuric acid is boiled in an Erlenmeyer’s flask until the liberatediodine is expelled.The residue, after cooling, is first neutralised withsoda, then mixed with excess of solution of sodium hydrogen carbonate,W. D. HANALYTICAL CHXMISTRY. 231and finally titivated with N/10 iodine. The experiment i R now repeated,this time with the addition of a definite amount of a chlorate. Asthere is no reaction between hydriodic acid and arsenic acid, as long asthere is a chlorate present, the amount of iodine used to reoxidise thearsenious acid will be considerably less. The amount of chioric acidmay, therefore, be readily calculated. It is of great importance tohave a good excess of potassium iodide. The test analyses are satis-factory.L. I)E K.Microscopic Detection of Sulphurous Anhydride. By G.DENIGOS (J. Pharm. [5], 24, 289--290).-A saturated solution ofcadmium nitrate is diluted with 20 vols. of an aniline solution con-taining 20 to 25 grams per litre. Immediately before use a little ofthis is acidified with about 1 per cent. of acetic acid, taken up on theend of a glass rod: and held over the mouth of the vessel from whichsulphurous anhydride is supposed to be escaping. I n presence ofthis compound, a white film rapidly forms, which, under the micro-scope, is clearly seen to consist of regular, hexagonal plates. If thecadmium solution is not acidified, the test appears to be more sen-sitive, but, under the microscope, the hexagonal crystah are found tobe almost completely replaced by far less characteristic radiatingcrystals.J. T.New Method of EBtimating Nitrogen. By E. BOYER (COWZ..~.vend., 113: 503).-The method is founded on the complete reductionof nitric nitrogen t o ammonia by oxalates and sulphur in presence o€soda-lime. A reducing mixture is made, consisting of 1 part ofsulphur, 2 parts of calcium oxalate, and 6 parts of soda-lime. Aquantity of the dry substance containing not more than 0.5 gram ofnitrate is intimately mixed with 50 grams of the reducing mixture. Acombustion-tube, 55 cm. long and 1.7 cm. in diameter, is closed at oneend, and is then charged by the successive introduction of 2 grams ofcalcium oxalate, 10 grams of powdered soda-lime, 10 grams of thereducing mixture, the substance mixed as above, 10 grams of thereducing mixture, 10 grams of powdered soda-lime, and a plug ofasbestos.The combustion is carried on just as in an ordinary soda-lime: combustion, and occupies about 40 minutes. It is necessary toboil the staiidard sulphuric acid, before titration, to expel the sulphur-etted hydrogen and carbonic anhydride formed during the combustion.The method may be employed t o determine total nitrogen existingin the three states of organic: ammoniacal, and nitric nitrogen, andyields good results ; for instance, an analysis of sodium nitrate gave16-45 of nitrogen for 16.47 present; a mixture containing 0.1284gram of organic and aminoniacal nitrogen yielded 0.1281 gram; a,mixture containing burnt leather, ammonium sulphate, and sodiumnitrate gave 0.1161 gram nitrogen out of 0.11655 gram; a similarmixture containing dried blood yielded 0.1624 gram out of 0.1627gram of nitrogen present.Estimation of Carbon in Steel.By A. A. BLAIR (Chem. News,64, 66-69 ; from J. Anal. and AppZ. Chem.., 5, 3).-A continuationW. T238 ABSTRACTS Ol!’ CHEMICAL PAPERS.of the work of the International Steel Standards Committee ; certainmodifications are recommended’ in the ordinary combustion process.The double chloride of copper and potassium is to be preferred tothe analogous ammonium salt., as the lather is liable to containorganic impurities derived from the manufacture of the ammonia.The air used €or the combustion is best supplied from a pressure-cylinder, as the use of an aspirator facilitates the introduction of im-purities from the atmosphere of the laboratory.The products of combustion are best purified by cuprous chlorideand anhydrous copper sulphate, the former absorbing the free chlor-ine, the latter the hydrogen chloride ; the cuprous chloride, which isconverted into a convenient granular form by heating the moistenedpowder and stirring until dry, is placed in the anterior limb of aMarchand U-tube, the posterior limb of which is occupied by thecopper sulphate, guarded by a plug of asbestos.As anhydrous coppersulphate is a more efficient desiccating agent than the granular cal-cium chloride used in the guard-tube of the potash bulb, it is necessaryt o moisten the gases as they leave the purifying apparatus, and drythem again over calcium chloride before they enter the absorptioi tapparatus. For this purpose, n plug of cotton woo1 placed in the bulbof a Marchand U -tube containing the calcium chloride is moistenedat the commencement of each combustion.I n weighing the potash-bulbs, the use of capillary stoppers isrecommended, as they allow the equalisation of pressure without per-mitting the introduction of any sensible amount of moisture.J?;.W.Estimation of Thallium. By H. BAUBIGNY (Compt. rend., 113,544-547) .-The estimation of this metal by precipitation as thallousiodide admits of accurabe results, notwithstailding the remarks ofprevious observers. The inaccuracy of the method alleged by Willmis due to the final washing with distilled water.Werther’s asser-tion that thallous iodide is insoluble in ammoniacal water is notborne out by the facts, but its solubility in dilute alcohol is less thanthat author indicates. T h e most accurate modification of the processis carried out as follows :-Tha thallous iodide is precipitated at80-go”, it then collects together well without to any extent adheringto the glass. The whole is cooled; the orange precipitate, a t firstvery finely divided, forms a dense, crystalline, yellow powder whichmay be readily filtered. The precipitate is washed with a 1 per cent.solution of potassium iodide, in which it is insoluble, until free fromforeign salts; finally the potassium iodide is washed out by 82”alcohol, which, while readily dissolving potassium iodide, does not dis-solve enough thallous iodide t o yield even a coloration with ammoniumsulphide after concentration of the washings to one-fifth their bulk.The precipitate is dried and detached as completely as possible from thefilter, and in order to avoid the use of a tared filter, the thallous iodideadhering to the paper is dissolved by the aid of a little dilute nitric acid,and received in a tared porcelain crucible; the solution is then gentlyevaporated with a, few drops of hydrochloric acid, precipitated by theaddition of a drop of concentrated hydriodic acid, dried, the main quan-tity of the precipitate added, the whole heated for some hours at 170”ANALYTICAL CHEMISTRY.239and weighed. Although thallium and its salts are too volatile to allowof the incineration of the paper without loss, thallons iodide does notvolatilise at 170". Test analyses gave accurate results.(CompareLong, Abstr., 1891, 1295.) W. T.Oxidation of Copper-glance by the Electric Current. By E.F. SMITH and 1). L. WALLACE (Ber., 24, 2938-2939; see alsoBer., 23, 2276).-It has been shown that metallic sulphides inalkaline solutions are decomposed by the electric current in such away that the whole of the sulphur is oxidised to sulphuric acid.Copper-glance was the only exception. The authors have nowsucceeded in completely decomposing this mineral by the electriccurrent.Finely powdered copper-glance (0.1066 gram) and potassiumhydroxide (35 grams) are mixed in a nickel crucible and submittedfor 40 minutes to the action of an electriccurrent producing 1 ampereof electrolytic gas per minute.Before stopping the current, it isreversed for a few minutes. The contents of the crucible are thenwashed out with water, filtered from the insoluble oxide, acidifiedwith hydrochloric acid, and precipitated with barium chloride. ThereAnlts are good : 20.80 and 20.91 per cent. of sulphur being obtained,as against 21.00 per cent. obtained by oxidation with nitric acid.The essential conditions for success are the employment of a largequantity of potassium hydroxide and the prolonged action of theelectric current. E. C. R.Electrolytic Separation of mercury from Copper. By E. F.SMITH and A. W. MACCAULEY (Bey., 24, 2936--2938).-The authorshave found that by carefully regulating the current, the separation ofmercury from copper is complete, even when t,he latter is present intwice as large a quantity as the former.Moreover, the presence ofzinc, nickel, or other metals in no way hinders the separation. A tableof the results obtained is given.A Reaction for Cerous Oxide. By P. C. PLUGGE (Arch.Pharm., 229, 558-561).-The most delicate reagent for cerous oxideis a solution of 1 part of strychnine in 1000 parts of concentratedsulphuric acid. The suspected solution is made alkaline with sodiumhydroxide, evaporated on a piece of porcelain, and the dry residuebrought in contact with 2 or 3 drops of the strychnine solution ; inthe presence of cerium, a bright-blue colour is developed wbichrapidly fades and gives place to a cherry-red or pale-red, according tothe quantity of cerium present.As little as 0.01 milligram of cerousoxide can be detected in this way, the colour being a pale blue-violetwhich rapidly disappears.This test was devised for the detection of cerium in the contentsof a stomach, where the cerium was present in the form of oxalate,which is officinal in some pharmacopmias as a remedy for vomiting,dyspepsia, &c. ; in euch a case, the presence of sodium hydroxideis necessary t o decompose the cerium oxalate. The t8est may also beapplied directly to a precipitate produced by ammonia and contain-E. C. R240 ABSTRAOTS OF 0HE;M'IOAL PAPERS,ing zinc and aluminium as well, only ammonium sulphide or zincsulphide must not be present.Separation of Manganese and Nickel, Manganese andCobalt, and of Manganese, Nickel, and Cobalt.By P. JAN-NASCH and C. J. FI~ANZEK (Rer., 24, 3204--3205).-1t has beenpreviously shown by Jannasch and McGregory (Abstr., 1891, 963)that zinc and manganese may be quantitatively separated by meansof hydrogen peroxide in strong ammoniacal solution and in presence ofa large quantity of ammonium chloride. The separation of manga-nese from nickel may be readily carried out under similar conditions,but not that of manganese and cobalt. If, however, the hydrogenperoxide is added to these metals when in the form of double alkalicyanides, the manganese precipitate is completely free from cobalt ;in the same way manganese may be separated from nickel, or, as wouldbe expected, from a mixture of both thet;e metals.The precautionsneceesary to ensure success will be published later.Volumetric Estimation of Iron by Potassium Dichromateand Stannous Chloride. By R. NAMIAS (Gazaetta, 21, 473-476).--The author considera the ordinary method of estimating iron bydichromate, using potassium ferricyanide as an indicator, to be in-convenient and somewhat inexact. He finds the following method togive good results :-An excess of standard dichromate solution is runinto the solution of the ferrous salt, acidified with hydrochloric acid ;a few drops of iodine and starch solution are added, and the excess ofdichromate determined by titration with standard stannous chloridesolution.I t is convenient to use a potassium dichromate solution containingabout 5 grams of the salt per litre ; the stannous solution should beColorimetric Estimation of Iron.By L. LAPICQUE (Compt. revLd.HOG. Biol., 1890, 669-671).-1n view of certain observations byKriiss and Morath (Abstr., 1889, 124), in which they found thecolorimetric estimation of iron led to variable results, the author hasre-examined his former method (Abstr., 1890, 297) of estimating t,heiron in blood. He also finds certain variable factors, but by using alarge excess of alkali thiocyanate in constant proportion, and thenacidifying strongly with sulphuric acid, these are reduced t o aminimum. Among the circumsta,nces leading to variation, tempera-ture must be mentioned ; t o obviate this, it is suggested that everytime a series of estimations is to be made, the thiocyanate shouldbe previously titrated with a ferric salt in order to determine fheconstant I(.W. D. H.A. G. B.H. G. C.equivalent to this. w. J. P.Decomposition of Chrome-Iron Ore by Hydrochloric Acidunder Pressure. By P. JANNASCH and H. VOGTHERR (Ber., 24,3206-3208) .-The method already recommended by one of theauthors for decomposing silicates, namely, by heating with hydro-chloric acid under pressure in a platinum apparatus (Abstr., 1891ANALYTICAL CHEMISTRY. 241619), may also be adopted with advantage in decomposing chrome-iron ore for quantitative analysis. The most suitable acid is a mix-ture of 4 vols. of concentrated acid of sp.gr. 1.119 and 1 vol. of water,and it, should be saturated with ammonium chloride ; the tubes mustbe heated for 8-10 hours at about 250", the decomposition beingthen a t least as complete as with the methods usually adopted.Estimation of Molybdic and Tungstic Acids. Ey E. F.SMITH and R. H. BRADRURY (Ber., 24, 2930-2936).-The authorshave made experiments to determine if molybdic arid tungstic acidscan be estimated by means of their barium, calcium, strontium, lead,silver, cobalt, bismuth, or cadmium salts. The following resultswere obtained :-Barium molybdate' is precipitated on adding barium chloride t o acold solution of so$urn molybdate. It dissolves completely in acids,is more soluble in a dilute solution of ammonium nitrate than inwater, and dissolves in 17,ZOU parts of water at 23".The quantita-tive estimation was carried out as follows :-A measured quantity ofsodium molybdate solution containing 0.1 144 gram of molybdenumwas made up to 200 c.c., heated to boiling, precipitated with a boilingsolution of barium chloride, allowed to remaic until cold, filtered,washed with cold water, and the precipitate separated from thefilter-paper, and ignited. The results obtained were good. I f theprecipitate be filtered while the soliltion is hot, a small quantity ofmolybdenum will be found in the filtrate.Barium tungstate is a heavy, white precipitate, which is decomposedby warm acids with formation of yellow tungstic acid, and is moresoluble in dilute ammonium nitrate than in water.The quantitattiveeetimation, which gives good results, is carried out in a similarway to the molgbdate, but in this case the precipitate is collectedwhile hot, and washed with hot water.Strontium molybdate resembles the barium salt in appearance, ispractically insoluble in water, dissolving in 9600 part's a t 17". It iseasily decomposed on heating, and is, therefore, not suitable forquantitative estimations.Strontium tungstate behaves in the same mray as the molybdate.Calcium Mo1ybdate.-The addition of calcium chloride to a cold,dilute solution of sodium moljbdatc does not cause a precipitate. Onadding alcohol, or on heating the solution to boiling, a white,granular precipitate is at once obtained, which is somewhat solublein water, and insoluble in alcohol.The quantitative estimationwas carried out in the same way as for the barium salt, but althoughthe filtrate contained molybdenum, the results were always too high.The following method was then employed :-The calcium molybdatewaB precipitated in boiling solution, and boiled until the precipitatebecame granular, cooled, one-third the volume of alcohol added,the mixture allowed to remain for some time, filtered, and the pre-cipitate washed with dilute alcohol (1 : 3). The filtrate cont'aiaedno moljbdenum. On heatzing the precipitate in a platinum crucibleto a strong, yellow beat, it loses weight, and, unless the heating issufficient, high results are obtained.H. G. C242 ABSTRACTS OF CHEMICAL PAPERS.Calcium tungstate resembles the preceding salt, but the quantita-tive results varied considerably.Lead molybdate is a white, granular precipitate, in a moist condi-tion soluble in nitric acid and sodium hydroxide; on heating, i tacquires a yellow colour, and then is not attacked by the abovereagents. With regard to the quantitative results, the authors con-firm the results of previous observers.Lead tungst,ate is a white, flocculent, finely-divided precipitate,extremely hard to filter, and insoluble in water.It is quite insolublein ammonium nitrate, and the addition of this salt renders the filtra-tion much easier.Silver tungstate and molybdate are at once precipitated on addingsilver nitrate to solutions of the sodium salts. Silver tnngstate iRmore finely divided and more difficult to filter than the molybdate.The latter is a white precipitate resembling silver chloride, distinctlysoluble in water, easily soluble in nitric acid, potassium cyanide, andsodium bydroxicl-e; on heating, it turns purple, and melts at a lowtemperature to a clear, yellow liquid.Silver tungstate is yellow,less soluble in water, melts at a higher temperature, and, on heat-ing, t.urns dark-purple. These salts are not suitable for quantita-tive exFeriments, as they are soluble in water, and decompose onheating.Cadmium molybdate is a heavy, granular salt, insoluble in water,and, when moist, soluble in ammonia, acids, and potassium cyanide,and, after heating, is still soluble in acids. G.ood quantitativeresults are obtained as follows :--The solution is precipitated withcadmium nitrate, collected on a Gooch's porcelain crucible, and, afterdrying, carefully heated.Cadmium tnngstate is obtained in a fine state of division, but is notditficnlt t o filter.It resembles the molybdate, but, after heating, is notsoluble in acids. The quantitative estimation is carried out in thesame way as for the molybdate.The authors point out that probably an estimation of molybdicand tungstic acids when mixed could be obtained by dividing thesolution into two parts: in one part estimating the mixed acids a5cadmium salts, and in the other part also precipitating as cadmiumsalts, then dissolving in potassium cyanide, and determining t h ecadmium electrolytically.The quantitative results were good.The bismuth salt's are insoluble in water.Cobalt molybdate is not formed either i n cold dilute or concen-trated solutions.By heating a concentrated solution of sodiummolybdate with cobal t nitrate, a small quantity of a bluish-whiteprecipitate is formed, which dissolves again on cooling.Cobalt tungstate is violet-red, and is at once formed on addingcobalt nitrate to a solution of sodium tungstate.Estimation of Antimony and its Condition of Oxidation.By P. A. GOOCH and H. W. GRUKKER (Amer. J. Sci. [3], 42, 213-220).-When antimonious oxide is treated with iodine in an alkalinesolution, it passes into the higher state of oxidation. If, on the otherhand, an acid solution of autimonic oxide is boiled with hydriodicE. C.RANALYTICAL CHEMISTRY, 243acid, iodine is liberated, and thc antimony is reduced to the lowcrstate of oxidation.On these principles the authors have based the following process€or the determination of antimony :-A weighed quantity of theantimony salt, corresponding with about 0.2 gram of Sb,O,, is titratedin presence of 1 gram of sodium tartrate and 20 C.C. of a saturatedsolution of' sodium hydrogen carbonate, with N/10 iodine solutionstandardised against tartar emetic. The result of this titration givesthe amount of Sb,O,. 4 grams of tartaric acid is then added to theliqnid, and, if still alkaline, dilute sulphuric acid is added until themixture is neutral. 10 C.C. of 50 per cent. sulphuric acid is nowadded, and also a little over a gram of potassium iodide.The liquidis diluted t o 100 c.c., and boiled in an Erlenmeyer flask until thevolume is reduced to 50 C.C. In order to prevent bumping, a,platinum spiral is introduced, and to obviate mechanical loss, also atrap made of a two-bulb drying tube, cut short, and hung, large euddownward, in the mouth of the flask. The faint colour still remain-ing after coilcentration is bleached by means of centi-normal sulph-urous acid, and the solution nearly neutrnlised with sodium hydroxide ;20 C.C. of solution of sodium hydrogen carbonate is again added, andthe liquid once more titrated with the standard iodine solution in thepresence of starch. This titration gives, of course, the entire amonntof antimony present.The difference between the indications of thetwo titrations gives the antimony in the higher state of oxidation.The process is accurate and rapid, as shown by many test analyses,and also extremely simple as regards manipulation. L. DE K.Carbazole Method for Estimating Nitrates in Water Analysis.Bv W. P. MASON (Chem. News, 64, 197).-The author, who isdightly disappointed with the delicacy and uniformity of results ob-tained by this process, points out the fact that cold solutions darkenmuch more slowly than the warmer ones. In applying the process, thesame precaution must be taken as when nesslerising for ammonia,namely, the standards and the solutions of unknown strength mustbe operated on at the same temperature. After the addition of atrongsulphuric acid, the tube may be cooled immediately, or gradually,before the carbazole solution is added. The latter solution, which ina stoppered flask keeps for about 48 hours, acts best when its colourhas changed to an olive-green.Estimation of Nitrates in Water.By A. HAZEN and H. W.CLARK (CYhem. News, 64, 121-122, and 162-1644 .-The authorshave examined the phenolsulphonic acid process of Grandral andLajoux (Abstr., 1885, 1093), and find that it is not trustworthy, asthe various nitrophenols which may be formed have colouring powersdiffering in intensity.The aluminium process, however, yields more satisfactory results.50 C.C. of' the water is treated with 2 C.C. of 40 per cent. sodiumhydroxide solution and 0.4 gram of aluminium foil, 0.12 mm.thick,and the whole is allowed to remain at the ordinary temperature for24 hours. If the free ammonia is high, i t must be distilled off beforeL. UE K244 ABSTRACTS OF CHEMIOAL PAPERS.adding the aluminium. A portion of the solution? varying from 1 to25 c.c., according to the amount of nitrates present. is now diluted to500 C.C. with water free from carbonic anhydride (prepared by passingsteam through distilled water), and nesslerised in the usual way. It isfound unnecessary, in most cases, to distil before nesslerising, as thewater is sufficiently decolorised and clarified by the action of thehydrogen. The diluent water must be free from carbonic anhydride,a8 otherwise the liquid will become turbid with precipitated aluminiumhydroxide.A correction is made for the volume of the sodiumhydroxide solution, the ammonia carried off by the hydrogen, and theammonia converted into nitrogen, the factor being 0.88 when theabove quantities are used. The authors have experimentally det,er-mined the amount of ammonia carried off by the hydrogen, and findi t to agree with the amount calculated from the gaseous laws.Albumino'id matter is attacked by the hydrogen, part of it beingconverted into an amount of ammonia varying from 2 to 4 per cent.of the albuminoid ammonia, but the quantity is negligible unlessthe latter is very high.Estimation of Volatile Oil in Copaiba. By R. A. CRIPPS(Pharnz. J. Trans. [3], 22, 195--194).-In a small weighed flask, 0 3gram of copaiba is placed with about 5 C.C.of water. A regulated jetof steam is sent through the mixture, and, as the exit titbe from theflask leads into a test tube immersed in cold water, any turpentinepresent can be immediately recognised by its odour. The exit tubeis provided with a bulb, in which any resin mechanically carriedover is arrested. I n half an hour, the loss of weight, after dryingthe flask at loo", represents all the volatile oil.Examination of Spirits for Secondary Constituents. By A.H. ALLEN and W. CHATTAWAY (Anatyst, 1891,10%--115).-The authors(have devised the following process (a modification of Marquardt'smethod) for the estimation of fusel oil in commercial spirits, sachas whisky:-As a preliminary step, any fixed matters must beremoved, and any ethers and furfuraldehyde destroyed.100 C.C. ofthe spirit is taken, 20 C.C. N/10 soda added, and the whole heatedin a reilux apparatus for an hour. The contents of the flask are thendistilled in the followiug manner:-A volume of 90 C.C. is allowed topass over, the flame is then removed, and 30 C.C. of water is intro-duced into the distilling flask. The distillation is conducted until20 C.C. more has been collected. The flask is allowed to cool, and10 grams of sodium sulphate washed into i t with 20 C.C. morc water. Ifnow the distillation be continued until another 20 C.C. has passed over,all the amyl alcohol will have been volatilised. The entire distillateis now diluted with brine until the density of the liquid is about 1.1,when i t is shaken four times successively with carbon tetrachloride,using 40 C.C.the first time, then 20 c.c., and lastly, 10 C.C. Thecarbon tetrachloride now contains the nmyl alcohol (and other fuselconstituents), and, probably, some ethyl alcohol, which may beremoved by agitation, first with brine, afterwards with a strongsolution of sodium sulphate. The oxidation of the fusel oil may beJx. W.R. RANALYTICAL CHEMISTRY, 245conducted in a closed bottle, or, more convenientJy, using a refluxcondenser. The oxidising mixture consists of 5 grams of potassiumdichromate, ‘t grams of strong sulphuric acid, and 10 C.C. of water.When a flask is used attached to a reflux condenser, the carbon tetra-chloride should be kept in active ebullition for eight hours, thesourceof heat being a water-bath.After oxidising, the product is dilutedwith 30 C.C. of water and distilled over a naked flame until only 20 C.C.remains in the flask. 80 C.C. of water is now added, and the distil-lation continued until only 5 C.C. remains in the flask. The distillatewill now contain the whole of the valeric acid, a portion being dis-solved in the carbon tetrachloride, and the remainder in the aqueousfluid. The entire distillate is now titrated with N/10 barium hydr-oxide, using methyl orange as an indicator, and shaking tborouqhlyafter each addition. If the carbon tetrachloride has, before use, beenwell puriEed by treatment with the oxidising mixture and redistil-lation, no more than 2 C.C. of the baryta solution ought to be required.Phenolphthale’in is now added, and tbe titration continued, withfrequent shaking, until the neutral point is again reached.Each C.C.of N/10 alkali used in the second stage of the titration correspondswith 0.0102 gram of valeric acid or 0.0088 gram of arnyl alcohol. Theneutralised aqueous fluid is now carefully separated from the carbontetrachloride (which can be used again), evaporated to dryness at1;30”, and the residual barium salt is weighed. After allowing forany barium chloride, which may he calculated from the alkali used inthe first stage of the titration, the mean combining weights of theorganic acids can be found as follows :-Milligrams of organic barium saltC.C. of N barium hydroxidex 67.5 = combining weight oforganic acid.The process gives very accurate results, providing the followingpoints are rigidly observed :-1.The carbon tetrachloride must be previously purified by treat-ment with chromic acid mixture and subsequent diatillaticn overbarium carbonate, and must be free from chloroform.2. All corks used in distilling the spirit must be kept distinct fromthose employed in the distillation of the products of oxidation. Theymust be always carefully covered with tin-foil.3. ,4 few small fragments of pumice-stone should be added, in eachcase, to the contents of the distilling flasks. They should be treatedwith the chromic: mixture before use.4. The brine should be made from clean table salt, and rendereddistinctly acid with sulphuric acid.Qualitative and Quantitative Estimation of E’urfu1.aldeity~e.--Furfur-aldehyde in spirits can be detected, and its proportion roughly guessedat, by the reaction of the sample with a solution of aniline in glacialacetic acid.Ten drops of aniline are dissolved in 2 C.C. of the acid,and the mixture added to 10 C.C. of the spirit to be tested. A redcoloration, which increases in intensity after a time, shows thepresence of furfuraldehyde. If a quantitative estimation is required,the authors proceed as follows :246 ABSTRACTS OF CHEMTOAL PAPERS.200 C.O. is distilled to about 20 c.c., when 50 C.C. of water isadded, and the distillation continued until all but 10 C.C. has passedover. The distillates are mixed and divided into t,wo equal parts,A and B.One portion, A, is titrated with N/10 soda, usingphenolphthalein as indicator, and the free acid thus found calcu-lated to acetic acid. The neutral liquid is treated with 20 C.C. ofN/10 soda and boiled in a reflux apparatus for one hour, when theexcess of alkali is ascertained by titrating with N/10 hydrochloricacid. The other portion, B, is treated with 1 C.C. of aniline and1 C.C. of phosphoric acid of 1.442 sp. gr., and boiled in a reflox ap-paratus for at least two hours. It is then distilled t o a low bulk, andthe distillate neutralised and treated with 20 C.C. of NllO soda, exactlyas was done with the other portion. The difference between thealkali added and that found by titration represents that consumed bythe saponification of the ether in 100 C.C.of t,he spirit; each C.C.represents 0-0088 gram of ethylic acetate.The difference between the amounts of alkali required for thesaponification of portions A and B represents the alkali which hasreacted with furfuraldehyde, acetaldehyde, &c. Assuming, only thefirst t o be present, 1 C.C. of N/lO soda represents 0,0192 gram offurfuraldehyde.One of the authors very much questions whether the presence ofeven an excess of amjl alcohol in whisky constitutes a danger tohealth. L. DE K.Estimation of Glycerol, Astringent Acids, and ColouringMatter in Wine. By I?. JEAN (Analyst, 18131, 56--57).-Estin,zationof the GZyceroZ.-250 C.C. of the sample is evaporated to the volumeof100 c.c., agitated with lead oxide, and then rendered slightly alkalinewith baryta-water. The filtrate is neutralised with dilute sulphuricacid, concentrated to about 50 C.C.in a flat porcelain dish, and mixedwith 5 grams of lead oxide, 10 grams of sand, and 20 grams of bariumsulphate. The mass is cautiously dried at loo", and the powderedresidue extracted with a mixture of equal parts of alcohol and etheruntil the liquid measures 60 C.C. 30 C.C. is placed in a tared glasscapsule, and 210 grams of dry litharge having been added, the wholeis evaporated on the water-bath, and then dried to a constantweight at 105-106". The other 30 C.C. is evaporated i n a tared glasscapsule of 6 cm. diameter, and finally dried in an air-bath at 160-170".The difference in weight between residue No.1 (after allowing forthe litharge) and No. 2, multiplied by 8, and divided by 1.243, givesthe number of C.C. of glycerol in 1 litre of wine.Estimation of Astimingent Acids.-(a.) anontannin. 250 c c. of thesample is concentrated down to 100 c.c., shaken with excess of freshlyprecipitated arsenious sulphide, and then filtered. The filtrate isconcentrated to 50 c.c.? mixed with 10 grams of silica and 20 gramsof barium sulphate, and finally dried at 100". The residue is pow-dered and extracted with warm ether ; the latter is evaporated, andthe residue is dissolved in a little alcohol. Into this solution is nowintroduced a weighed quantity of dry, prepared, powdered hide,which will take up all the tannin in about half an hour. AfteANALYTICAL CHEMISTRY.247washing it with spirit, it is dried at 100" and reweighed. The increasein weight, multiplied by four, equal8 the cenontanniii i n 1 litre of thewine. ( b . ) CTnogaZZic Acid. The alcoholic filtrate is diluted with dis-tilled water up to 100 c.c.,and in 20 c . ~ . of this, the acid is estimatedby means of a solution of iodine, previously standardised with gallicacid, as follows :-Two solutions are prepared, one containing 0.2 gramof iodine per litre, the other 0.125 gram of gallic acid in 250 C.C. of'distilled water. Into a beaker, marked 50 o.c., is put 10 C.C. of thegallic acid solution and 3 C.C. of a saturated solution of sodium hydrogencarbonate. Iodine solution is now added from ?; burette until a dropof the mixture, tested on thick filter-paper dressed with powderedstarch, leaves n stain surrounded by blue.Water is now added up tothe mark, and iodine again added until R similar stain is obtained.Having thus standardised the iodine, it is used in a similar manneron the 20 C.C. of the alcoholic liquid, mixed with 3 C.C. of solution ofsodium hydrogen carbonate. ( c . ) Colouring matter. 250 C.C. of thesample is slowly evaporated down to 100 c.c., rendered alkaline withammonia, and shaken up with freshly-precipitated arsenious sulphide.After filtering, a slight excess of acetic acid is added, and the liquidonce more filtered. The two filters containing the arsenious sulphideare, after washing, heated with spirit slightly acidified with acetic acid,which gradually dissolves out the colouring matter.The alcoholicsolution is evaporated in a tared capsule, desiccated at 1 0 5 O , and theresidual colouring matter. is weighed. L. DE K.Estimation of Pentoses in Vegetables. By W. E. Srrom (Ber.,24, 3019-3021).-The material under examination is heated in aretort with hydrochloric acid (sp. gr. 1.06) so that not more than10 C.C. of dist,illate is obtained in five minutes, fresh acid being addedfrom time to time. As soon as the distillate ceases t o react withaniline acetate, the heating is suspended, and the distillate neutralisedwith soda, slight excess of acetic acid added, and the liquid dilutedwith water to a known volume. Portions of 25 C.C. are then mixedwith phenylhydrazine solution, quickly boiled, rapidly cooled, aridfiltered, the filtrate being tested with alkaline copper solution; ifit contains excess of phenylhydrazine, less is added in subsequenttitrations ; after three or four experiments, it is possible to determinethe exact quantity of pheilylhydrazine required, within 0.1 C.C.The phenylhydrazine solution is made by dissolving 1 gram ofphenylhydrazine hydrochloride, and 3 grams of sodium acetate in500 C.C.of water, a,nd is standardised by titration with a solutioncontaining 1 gram. of pure furfuramide and a little acetic acid in1 litre of water. The phenylhjdrazine solution changes after24 honra.Although this method does not give residts which are theoreticallycorrect, since part of the material ie decomposed during distillationwith the acid, the numbers obtained for the same substance are uniform,and the percentages of pentoses contained in different alimentary sub-stances can be readily compared.J. B. T248 ABSTRACTS OF CHEMICAL PAPERS.Estimation of Mixtures of Saccharose, Invert Sugar,and Dextrose or Levulose. By G. W~GCHMANK (Analyst, 1891,15-33).-A direct estimation of saccharose in presence of dextroseand IevuIose has been proposed by Winter. This process, t h eaccuracy of which is much doubted by the a,uthor (but which want,sfurther investigation), is carried out as follows :-The sugar solutionis mixed with a solution of lead acetate, to which ammonia hasbeen added until a permanent precipitate threatens to form. Anabundant white precipitate is formed, which is then digested with alarge amount of water.The filtrate contains the sugar as a leadcompound, from which the lead may be readily separated by a currentof carhonic anhydride. The insoluble portion is suspended in water,and also treated with carbonic anhydride to liberate the dextrose.The insoluble mass, which still contains the levulose, will yield thelatter on treatment with hydrogen sulphide.Indirect processes, based on polarisation, do not always yieldaccurate results, a s the polarimetric observations are too much in-fluenced by a small change in temperature.The author, who has made a large number of test analyses (with-out making any important alteration in the process), has proved theaccuracy OF the method proposed by Sieben, which is based on thefollowing principle :-The saccharose and dextrose + levulose are calculated from thecopper-reducing power before and after inversion.Any levulose,whether naturally present, or formed from half the quantity of thesaccharoso during inversion, may be readily destroyed by prolongedboiling with excess of hydrochloric acid, and subequently determinedfrom the diminished copper-reducing power. L. DE K.Estimation of Maltose, Dextrose, and Dextrin in Beer-wortand Beer by means of Ferment Organisms. By H. ELIOX (Chent.Centr., 1891, ii, 281 ; from C‘entr. Bakteriologie u. Parasitenkunde, 9,525--528).--The author refers again t o this method (Abstr., 1x91,368), and in proof of its validity, he points out that tho re-ducing power of the sugar which disappears during fermenta-tion and the amount of dextrose formed by hydrochloric acid fromthe same, almost exactly corresponds with the amount of maltose.At the same time, he admits that under the term “maltose” heincludes also any other sugar which may have undergone ferments-tion, still the result is sufficiently exact for technical purposes.Theauthor also objects to the use, as in Bau’s experiments (Zoc. cit.),of Saccharomyces apiculatzcs, since its nature and fermenting qualitieshave not as yet been sufficiently examined.Estimation of Cholesterol. By I(. O B E m C r , L m (Zeit. physio~.Chem., 16, 143-151) .-In the estimation of cholesterol in mixturescontaining neutral fats, the sodium ethoxide method of saponification(Abstr., 1890, 1474) is found to cause no loss of cholesterol.J.W. L.W. D. H.Carbohydrates. Ry B. TOLLENS and others (Landw. Versuchs-Xtat.,39, 401-453).-1n the analysis of vegetable products by the usuaANALYTICAL CHEMISTRY. 249method, the fat, prote’ids, insoluble fibre, and ash are estimateddirectly, and the difference between the sum of these components and100 is returned as “ extract,ive matter free from nitrogen.” Thisextractive matter consists for the most part of carbobydrat*es, whichcan be estimated directly by means of Pehling’s solution, after pre-vious treatment with dilute acids; it contains, however, in manycases, il considerable proportion of suttstances which cannot be esti-mated in this manner, and for the detection and estimation of whichsuitable methods are greatly needed.I n the present paper, the author reviews the most important reac-tions of various carbohydrates, with reference to the analysis ofvegetable products in general.The levulinic acid reaction is first discussed, and it is stated that theformation of this acid, on boiling a substance with hydrochloric acid ofsp.gr. 1.09-la10 for 20 hours, map be considered as strong eyidenceof t>he presence of a true carbohydrate* (compare Wehmer and Tollens,AnnaZen, 243, 315 ; Abstr., 1888, 535). The following substancesgive the levulinic acid reaction :-Cane sugar, dextrose, levulose,inuliii , gum-arabic, filter-paper, fir-wood, st arch, Carragheen moss,levulin, lactose, galactose, raffinose, irisin, mannose, sorbin, thegliicosides salicin and amygdalin, potato-juice, and chondrin.Itmust be borne in mind that even in the case of a true carbohydrateonly a small quantity of lerulinic acid is formed, and that the isola-tion of the acid is by no means an easy matter; consequently anunsuccessful attempt to obtain the levulinic acid reaction only showsthe absence of any considerable quantity of a true carbohydrate.Having ascertained in this way the presence of a true carbohydrate,its isolation and identification have next, to be considered.I n the case of dextrose, or of substances such as lactose, raffinose,salep-juice, &c.. which yield dextrose, the presence of this sugar canbe easily proved by oxidising the suhstance with nitric acid (comparoGans a i d Tollens, Annalen, 245, 215 ; Abstr., 1888, 1059); the for-mation of saccharic acid under theee conditions is a proof of thepresence of dextrose, or of dextrose-groups.Inulin, sorbin, arabinose,galactose, mannose, and quince-juice+ do not give the saccharic acidreaction.The formation of mucic acid on oxidation with nitric acid (compareCreydt and Tollens, Abstr., 1886, 582) may be taken as a proof thata substance contains galactose or galactose groups ; i t has been shownthat this acid is obtained from galactose, lactose, raffinose, and Car-ragheen moss, and also from the “ sulphite-liquors ” of the wood-cellulose process (compare Weld, Lindsay, Schnelle, and Tollens,Abet,r., 1891, 43). The quantity of raffinose in molasses can, in fact,be determined by estimatixig the muck acid produced on oxidation(compare Creydt, Abstr., 1887, 307).There is no reaction by whichthe presence of levulose, or of levulose groups, in a vegetable productNote by Ahtractor.-The term “ true carbohydrate” seems to apply only tothe hexoses, and to compounds such as starch, inulin, &c., which yield hexoses onhydrolysis. t Note by Abstractor.-Quince-juice, according to Baucr (see p. 428), yieldsdextrose on hydrolysis.VOL. LXII. 250 ABSTRACTS OF CHEMICAL PAPERS.can be satisfactorily determined ; the readiness with which this sugarundergoes decomposition on heating with sulphuric acid, or dilutehydrochloric acid, yielding brown Rolutions, may, however, serve asa means of distinguishing i t from dextrose ; Seliwanoff's colour re-action (Abstr., 1887, 459) is also to be recommended in particularcases.Mannose can be readily detected by warming a dilute solution OEthe substance under investigation with phenylhydrazine acetate ; itspresence is shown by the formation of a crystalline hydrazone (m.p.about 188'). As this sugar is usually present in vegetable productsin a combined form, the substance must first be heated with 3 percent. hydrochloric acid for some hours. The presence of mannose inthe " sulphite-liquors " from the wood-cellulose process is easilyproved by means of the phenylhydrazine reaction ; the sugar can beconveniently prepared by decomposing the hydrazone with concen-trated hydrochloric acid.The pentoses, arabinose, and xylose, although closely related to thehexoses, differ from the latter in possessing certain characteristicproperties by which their presence in a given vegetable product canbe easily proved. They do not give the levulinic acid reaction, butwhen distilled with hydrochloric 01- sulphuric acid they yield a dis-tillate which contains furfuraldehyde ; the presence of this compoundcan be easily ascertained by the red coloration which is produced onthe addition of aniline or xylidine (compare Schiff, Abstr., 1887,571).As, however, the hexoses give traces of furfuraldehyde under thesame conditions, the presence o€ pentoses must not be regarded asdefinitely established unless the reaction is very marked, or unless thefurfuraldehyde is determined quantitatively by means of phenyl-hydrazine (compare Chalmot and Tollens, Abstr., 1891: 768).Thepentoses also give a characteristic red colour with phloroglucinol andwith orcinol, in presence of hydrochloric acid. It must be borne inmind that glycuronic acid aiid its derivatives give all the reactionsof the pentoses.A very complete account of the occurrence, properties, and methodsof estimation of'the pentoses is given, but all the principal facts dealtwith have formed the subject of previous papers by the author andothers (compare Abstr., 1891, 43, 659, 768). F. S. I(.Valuation of Oil of Cloves. By H. THOMS (Phurm. J. Tmns.[:3], 22, 450, 451).-Assuming that the quantity of eugenol in oilof cloves can be taken as a measure of the value, the author pro-poses to separate the eugenol directly from the oil in the form ofbenzoyleugenol, by mixing the oil with solution of sodium or potas-fiium hydroxide, and t h m adding an equivalent of benzoic chloride.Crystalline benzoyleugenol separates as the mixture becomes cold, isrecrystallised several times from hot alcohol, washed with alcohol a t17", and weighed dry on a filter, allowouce being made for its solu-bility (0.55 gram in 2.5 C.C. of 90 per cent. alcohol). From the weightof benzoyleagenol, the quantity of eugeiiol present in the oil can becalc dated. R. RANALYTICAL CHEMISTRP. 251Examination of Vinegar. By W. J. SYKES (AnaZyst, 1891,83--87).-The author thinks that considerahle iriformation may begathered from an examination of the ni tz-ogenous constituents of avinegar, as to whet,her it is genuine or not; but the fixing of limitsmust naturally be rewerred until a long series of experiments havebeen performed in this particular direction.Albumoses may be estimated by precipitation with a saturatedfiolntion of ammonium sulphate. Peptone may be precipitated inthe filtrate by the cautious addition of a solution containing 4 gramsof tannin in 190 C.C. of proof spirit mixed with 8 C.C. of dilute aceticacid. Pure malt vinegar should also give a turbidity with phospho-tungstic acid, or potassium bismuthoiodide, or potassium mercuro-iodide. L. DE K.Adulteration of Beeswax. By A. and P. BUISINE (BUZZ. SOC.Chim. [3], 5, 65$-660).-Arnongst the substances used to adulteratebeeswax, the most conspicuous and common are those indicated inthe accompanying table. Although the influence of some of these onthe physical character of the wax is extremely marked, others, byjudiciors selection, can be so combined as to imitate it, not only in it,sphysical characteristics, b u t also in its behaviour under the methodsof analysis a t present in use.The authors propose, in addition t o the usual estimation of freeand combined fatty acids, to determine the unsaturated fatty acids,the free hydrocarbons, and the alcohols present in the sample, as wellas it,s melting point and density.The sample, dried a t 110", at which temperature i t should not losemore than 1 per cent. of its weight, should leave no residue ofmineral adulterant's on treatment with hot chloroform or turpentine.The melting point and density of the ori,pina,l sample should corre-spond with those of beeswax. Any serioiis adulteration will berendered evident by this procedure, and will necessitate furtherexamination to determine its nature and amount. To estimate thesoluble fatty acids, an excess of which indicates the presence ofvegetable waxes, and to detect soluble colouring matter such asturmeric and annatto, 20 grams of the sample is extracted with hobwater. The dried residue is utilised for the determination of t,he fkeeand total fatty acids, the unsaturated acids (by iodine absorption), thealcohols (by the amount o l hydrogen liberated by alkalis), and thefree hydrocarbons.The nature and approximate amount of the adulterants are thendetermined, in the manner already indicatel, by reference to theappended table (see next page;, which embodies the results obtainedby the examination of the various adulterants known to be in use.Jx. W----Japanese wax , . . . . . . . . .Chinese wax. . . . . . . . . . . .Vegetable waxes , . . . . . , .Carnauba wax . . . . . . . . . .Mineral waxes.. . . . . . . . .Paraffins, .. . . . . . . . . . . . .Suint wax.. .. .. .. .. .. ..Fatty acids of suint.. . . . .Tallow .. . . .. . . .. .. .. . .Steario acid . . . . . . , . . . . .Resin.. .. , . .. . .. ... .. ..Yellow beeswax. . . . . . . . .White beeswax . . . . . . . . .Meltingpoint.--.47-a053 *547-5483-8560-8038--7462 - 6650 --ca4-50 ' 555.5-62.- 6463-64Density.Soluble acidsin milligramsof KHO pergram ofsample.000000000-10-2~~Free acids inmilligramsof KHO pergram ofsample.---18-282217-194 40095-115159-1852 %--520816819-2120-23Totaln milligramsof KHOgramsample. ---216-222218218-79--u8102-1159-196-20917891-9793-11

ISSN:0368-1769    

DOI:10.1039/CA8926200236

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

253 General a n d Physical Chemistry. Measurement of Light Intensity by the Expansion of Chlorine. By A. RICHARDSOX (Phil. Mag. [ 5 ] , 32, 277--284).-The author has confirmed Budde's observation (PhiZ. Mag., 1871) that when chlorine is exposed to sunlight an expansion of the gas occurs, which is independent of direct heating effects due to the light ; and that the volume to which the gas first expands is maintained during exposure, provided that the intensity of the light remains constant, contraction to the original volume taking place when the gas is shaded. In order to compare the expansion obtained in this way with the light intensity, as determined by means of a Bunsen and Roscoe's pendulum actinometer, a differential apparatus was constructed, con- sisting of two tubes of 55 C.C.capacity and 10 cm. in length, which were connected with a graduated horizontal gauge, provided with a small bulb at each end. The gauge and bulbs contained strong sulphuric acid, a, short column of air serving as index. The tubes to be exposed were suspended in a box, which could be placed at any required angle to face the sun, and when filled with dry air were found to bo equally heated. One tube was then filled with dry chlorine, and the acid, up to the index, was saturated with this gas. The bulbs containing the acid were in all cases protected from the light. When the maximum expansion of the chlorine was reached at any one time, as shown by the index remaining stationary, the light intensity was measured. A comparison of the numbers thus obtained showed that the change in volume of the chlorine is very nearly pro- portional to the actinic intensity of the light, as given by the actino- meter.Experiments were also made with mixture: of chlorine and air. The effect of dilution with air is a t first very marked, diminishing after a time, but finally increasing when only a small proportion of chlorine remains. It was found that the expansion of chlorine by light is unaffected by change of temperatwe within a range of from 14" to 138". The author finally constructed an automatic registering apparatus for measuring light intensity. This was done by suspending a differ- ential apparatus on the beam of a balance in such a manner that the flow of acid from one arm to the other produced a movement of the beam, which was communicated by means of a lever to a pen, and was recorded on a rotating drum. This instrument will record continu- ously the actinic intensity of the light undei.all conditions of weather throughout the year. J. W. The Application of Ketteler's Formulae to Optical Chemistry. By R. Nasixr (Rend. Acad. Lint., 6, ii, 324-331).-!I!he author com- pares Ketteler's formula, N = (12' - l ) ( v - /3) (Abstr., 1889, 3%), VOL. LXII. t254 ABSTRACTS OF CHEMICAL PAPERS. with those of Lorenz and Lorentz, Gladstone and Landolt, and points out that the constants p and M vary much in valne under different conditions of temperature and pressure. Thus, for a-bromonaphthal- ene, the value of p between 16.5" and 28.1" is 0.03226, between 28.1" and 77.6" 0.15966, and the mean value betwecn 16.5' and 77.6" is 0.13620, the numbers being for infinite wave-lengt'h. A small change in the index of refraction makes an enormous difference in the values of p and M, and as the index of a substance varies somewhat with different samples, each as pure as possible, the values calculated for /3 and Ill are very discordant, and hence of little value in optical: chemistry.Ketteler's formulae, although of great theoretical interest from a purely physical point of view, cannot be advantageously applied t o optical chemistry, simply because the experimental data are not sufficiently exact. Rotatory Power of Silk. By 1;. VI(;NOX (Compt. rend., 113, 802-804).-Silk may be expected to act on polarised light, as it readily yields leucine and tyrosine on hydrolysis.Attempts to find a suitable solvent for the material a5 a whole proving unsuccessful, the two chief constituents were examined separately. The colouring matter of the silk of Bombyx nzori having been extracted by repeated treatment with hot alcohol acidified with hydrochloric acid, the skein is plunged into cold 3 per cent. aqueous soda solution, which dissolves the enveloping material, but leaves the matrix or fibrolin untouched. The rotatory power of a yellowish, limpid solution thus obtained was [alj = -39.2". To preparc the fibro'in for examination, the silk is boiled twice wikh 10 per cent. soap solution, the soap being washed away with water after each boiling ; it is then washed with acidified water (0.1 per cent. of hydrochloric acid), and finally with alcohol.The white sub- stance thus obtained is dried and dissolved in moderately strong hydrochloric acid. A clear, dilute solution prepared in this way showed a rotatory power of [a]j = --OD, which was not materially altered by further dilution, or by the addition of excess of ammonia. The rotatory powers of the two chief constituents of silii are, therc- fore, practically identical, and are of the same sign as those of the prot eids. JN. W. W. J. P. Changes of Voltaic Energy of Alloys during Fusion. By G. GORE (Phil. Xag. [ 5 ] , 32, 27--31).-Regnauld (Chem. News, 38, 53) observed that liquid gallium is electropositive t o solid gallium in a neutral solution of gallium sulphate. The author hao made corrc- sponding observations with various alloys.A glass dish and a tobacco pipe with a wide bowl were partially filled with a conducting liquid (solution of hydrogen chloride o r sodium chloride), and con- nected by means of a siphon. A rod of the solid alloy was placed in the cup, and a second portion was melted in the bowl of the pipe. Connection was made through a galvanometer by means of iron wires, The alloy in the bowl was alternately heated and cooled, the galvano- meter being observed in order to ascertain if there was any deflection of unusual inagoitude when the temperature passed the melting pointGENERAL AND PHYSICAL CHEMISTRY. 255 c ~ f the alloy. As most of the alloys employed did not melt sharply, no very sudden deflection was noted, but in the case of an amalgam of 1 part of cadmium aud 4 parts of mercury in a solution of sodium chloride, there was a sudden reversal of the current when the amalgam completely liquefied, the liquid being electronegative i o the Electromotive Forces of Metallic Salts.By C. L. SPEYERS (Arnar. Ohem. J., 13, $72--486).-1n continuation of previous work (Abstr., 1890, 843), the dserence of pot entia: between mercury and copper, iron, and tin has been measured in various electrolytes in ten different states of concentration, varying from molecular propor- tion (gram-litre) to molecular proportion, each solution having one-half the concentration of the preceding. The metals were used in the state of amalgam wherever practicable. In the case of copper, the electrolytes were hydrochloric, nitric, acetic, and sulphuric acids, alone and in pairs ; the copper salts of these acids, with the exception of the chloride, which attacked the mercury; pairs of these salts, iiamely, nitrate with acetate and sulphate, and acetate with sulphate ; mixtures of the salts with acids, namely, the nitrate, acetate, and sulphate with nitric, acetic, and sulphuric acids ; and, finally, the zinc selts of the same acids.In the case of iron, the same series of electrolytes was used, with the addition of the metallic chlorides, ferrous and ferric salts being substituted for copper salts. In the case of tin, the electrolytes used were the above acids, alone or in pairs ; the chlorides, alone, or mixed with acids ; the above-mentioned zinc salts, and the corresponding ferric salts. The general conclusions which tho author deduces from the numerous data thus obtained are : That the electromotive force in- creases, as a rule, with dilution ; that in solutions containing hydro- chloric acid it is lower than in those containing the other acids, and is not materially affected by the admixture of those acids or of metallic salts ; that in solutions containing different pairs of metallic and acid radicles it is only slightly greater than in the solutions of the pair yielding the lower value; and that it is lessened by substituting copper, stannous tin, or, in the case of chlorides, ferrous iron for hydrogen, but is practically unaffected by the substitution of stannic tin.The increase of electromotive force with dilution may be explained by means of the dissociation hypothesis, if the assumption is made that the mean free path of the ions is increased by dilution, so that the ions have less influence on one another, and give up, therefore, more electricity t o their respective electrodes. A theory of chemical affinity, which is proposed, is based on the non- conductivity of the non-metals.The atoms of these are supposed to contain it constant amount of negative electricity, neglecting artificial surface charges, whilst the metallic atoms contain positive, o r both positive and negative, electricity, the total quantity, however, being constant. When an atom of a non-metal comes in contact with a metal, its charge attracts the positive charge of the latter, and, as i t cannot unite with it, a portion of the metal is detached, and a corn- solid a t this point.J. W. t 2256 ABSTRACTS OF CBEMICAL PAPERS. pound formed, the stability of which depends on the completeness of the internal insulation of the negative ion and the magnitude of the positive charge of the positive ion. This explains the weakness of the combinations of metals with metals, and non-metals with non- metals, and the strength of those of metals with non-metals. The lowering effect produced on the electromotive force by stannous tin, and to a less general extent by ferrous iron, may be explained in accordance with the above hypothesis, by supposing that the negative electricity in the non-cond ucting ion is inextricably entangled with the matter. The initial action of the ion on the metal is to dislodge and combine with a portion of the latter containing unit positive charge, and a molecule of an ous compound is formed ; this, however, meets with more negative ions, and gives up part of its positive charge t o one of them, so that 2 moleculels of the ic compound are formed.Siuce the negative electrode is charged with negative electricity by the negative ions, and partially discharged by the positive ions, it follows that when the ic compound is present, the charge removed is less, and the potential of the electrode numerically greater than when the 02~s compound is present. Influence of Boric Acid on the Electrical Conductivity of Aqueous Solutions of Organic Acids. By G. MAGRABIKI (Gazzetta, 21, ii, 215--228).-1t has been previously shown (Guzsetta, 20) that the electrical conductivity of solutions of tartaric acid is sensibly increased by the addition of boric acid and is t o some extent de- pendent on the dilution and the quantity of boric acid used; this behavionr was explained by assuming the formation of a combina- tion of the two compounds which has electrolytic properties and is partially dissociated by water.In the present paper, the results of a series of experiments on the influence of boric acid on the electrical conductivity of aqueous solutions of acetic, benzoic, butyric, succinic, crotonic, salicylic, lactic, glyceric, gallic, amygdalic, and glycollic acids are described. There is a marked difference between the be- hariour of hydroxy- and other acids, the conductivity of solut,ions of the former being materially increased by the addition of boric acid even in very dilute solutions ; this increment rises with the quantity of boric acid added, but falls on dilution ; it varies considerably with the nature of the acid under observation.Solutions of hydroxyiso- butyric, pyrocntechuic, malic, and citric acids similarly show an in- crease of conductivity on the addition of boric acid, whilst pyruvic, dehydracetic, formic, oxah, valeric, monochloracetic, levulinic, camphoric, and aspartic acids, which do not contain the hydroxyl group in their acid radicles, exhibit no such increase. This beliaviour may possibly be of use in deciding as to the presence of an hydroxyl group in organic acids. The electrical conductivity of aqueous solutions of resorcinol, quinol, phenol, ortho- meha- and para-cresol, guaiacol, and phloro- q1ucinol is only very slightly increased by the addition of boric acid; on the other hand, that of solutions of catechol, and more especially of pyrogallol, is considerably increased.The author be- lieves this t o be due t o the presence and position of the hydroxyl JN. W.GENERAL AND PHYSICAL CHEMISTRY. 257 group in these compounds, and proposes to investigate the behaviour of polyhydric phenols containing two hjdroxyl groups in ortho- position i n this respect. S. B. A. A. Some Points on Electrolysis. By J. SWIA-BCRNE (Phil. J h g . [ S ] . 32, l-g).-The author considers a one-fluid reversible cell, with its external circuit closed through a resistance so high that, in corn- prison, the internal refiistance is negligibIe.A coulomb passing through the cell has work done on it numerically equal to the elec- tromotive force E. A t the electrodes p and n there is chemical action, c , and local heating, h, so that as there is assumed to be no work done in overcoming the resistance of the electrolyte, E = Epc + En, + I+,, + E,J~. The seat of E.M.F. is here supposed to be in the cell and not a t the metallic junction outside. Jf the chemical work is assumed to be independent of the tem- perature of the cell, _ _ it can be shown from the above equation that CEE E = E,,, -+ E,, + e de, when 0 is the temperature (Helmholtz’s equation). The author further shows how the Peltier effect a t each eontact in the cell can be obtained sepa~ately. When there is any secondary or “ non-adjuvant ” action, the cell is not reversible. The formation of lead sulphate on both plates of a secondary battery is considered by the author to be a primary reaction (that is, there is 110 intermediate formation of lead monoxide) and the cause of the :Lctirity of the cell.His views of nascent action are as foIlows :-Sodium amalgam in dilute acid gives off hydrogen, and will ’reduce a ferric salt to the ferrous stage. This reduction he does not attribute to the action of “ nascent ” hydrogen. A better explanation would be that the metal can dissolve if it e i t h e ~ reduces the ferric salt or evolves hydrogen. “ Evolution of hydrogen and reduction of the salt are thus alternate, not consecutive, results. Similarly, in an engine, the steam either works the engine 01’ comes out at the safety-valve; it does not begin to lift the safety-valve, and then change its mind and work the engine in a iiascent state.” J.W. Relation of E.M.F. to Latent Heat, Specific Gravity, &c., of Electrolytes. By G. GORE (Phil. Mug. [S], 32, 157--168).-1n order to ascertain whether, in cases where t’he mixture or dilution of electrolytes is attended by a heat-effect, a change in the power of exciting electromotive force occurs, the author took various pairs of solutions (or one solution and pure water) a t the same temperature, measnred the E.M.F. of a, cadmium-platinum couple in each liquid separately, then mixed the liquids, observed the 1,emperat ure of the mixture, and, a8fter allowing the liquid t o acquire the former tem- pel-atnre, measured the EMF.of the couple in it. This E.M.F. he then compared with the mean valae of the E.M. Ir’. in the liquid before mixture. The results are contained in the following table. The solutions of the chlorides of sodium and potassium were nieasured w i t h a zinc-platinum couple :-258 ABSTRACTS OF CIHEMICAL PAPERS. Mixture. Chniige of temperature in degi-ees centigrade. Change iii E.M.F. .......... ! NkSO, solution + dil. H2S0, CH,-COOH + water. ................ Tartaric acid solution + miter ........ I NH,NO, 7 - .......... j NaNO, I . . . . . . . . . . . , S r W " Y . . . . . . . . . . NaCl . . . . . . . . . . I Na2S04 (NH4),S0, ., . . . . . . . . . . Na2C0, I . . . . . . . . . . I KNO:S . . . . . . . . . . ! NHdCl 1 CH,*COONa ,. .. ........' KCl 1 .. . . . . . . . . 1 M g W NaOH . . . . . . . . . . t HCl 9 , . . . . . . . . . . ~ .. ........I I Et.4 I NH, J w 3 , . . . . . . . . . . ,. >, . . . . . . . . . . 9 , . . . . . . . . . . ,, 3 I , . . . . . . . . . . Y l . . . . . . . . . . - 0.66 - 0.9 - 0.16 - 4'44 - 1-42 - 1.08 ? - 0.14 - 0.14 - 0.28 - 0.54 - 0.19 + 0.14 + 0.22 + 0-04 + 7-14 + 2-38 + 11 -00 + 0'02 + 0.10 + Os0$O1 + 0*0'130 + 0 '1923 + 0 '04.00 + 0 '1228 + 0 '0'141 + 0 '0668 + 0 -0359 + 0 -0402 -0 '0445 +0.0'715 + 0 *0345 + 0 -0360 + 0 '0787 + 0 '1219 + 0 -0298 t. 0 '2872 + 0,2375 + 0 -0150 + 0 '0040 Special experiments weye also made on the contractiou of salt solutions and water. The author concludes that " in cases of mere physical mixture, the changes of mean specific gravity and of mean electromotive force of electrolytes are probably related t o each other as concomitant effects of the same cause, change of molecular motion." J.W. Specific Inductive Capacity and Latent Heat of Vaporisa- tion. By E. OBACEI (Phil. Nag. [ 5 ] , 32, 113-127).-From a con- sideration of the specific inductive capacities published by Tereschin (Ann. Phys. Chem. [2], 36, 792) and the heats of vaporisation ob- served by Schiff (Anden, 234, 3:38), the author finds a relation between these two magnitudes for members of vmious homologous series. In any one series, the quotient of the latent heat of vaporisa- tion, X, by the specific inductive capacity, I(, is practically constant. Thus, for the ethered salts of acetic acid the following values of AiK are obtained :- Nethyl.35thjI. l'ropjl. Isobutylyl. Amyl. 12.0 12.8 12.3 1'2.1 12.8 K The mean value of the ratios for the corresponding formates is 9-83, Monatomic alcohols give a mean The relation thus obtained in hornologous series may be combined and that of the benzoates, 10.33. ratio of 7-56, and eOhy1 salts of the acetic series, 12.42. with othei- similar relations. T c3i For example, Trouton gives X =QENERAL AND PHYSTCAL CHEMISTRY. 259 2350 240 a45 S50 255 where T is the boiling point in the absolute scale, 31 the molecular weight, and C a constant. It' we make X = riK and introduce this value in the equation, then rlK = CA,., or KhI = C'T; that is, in any series the boiling points ilz the absolute scale are proportioiial to the molecular inductive capacities. Similarly, by making use of De Heen's results, it follows that the coefficient of expansion at 0" is inversely propoytional to the molecular inductive capacity.The ratio X/K for ethyl oxide is 20.8 ; for carbon tetrachloride, 21.0 ; f o r carbon bisulpliide, 33.0 ; and for oil of turpentine, 31.1. T J. W. 10 248 260" 10 -243 265 10 239 270 10 -233 275 10 -229 280 Chmge of the Empirical and Theoretical Isotherrnals of Mixtures of two Substances with the Temperature. By A. BL~~MCKE (Zeit. physikal. Chem., 8, 554-565).--Y1he method which the author has employed in a former papel- (Abstr., 1891, 375) for tracing the connection between the empirical and theoretical iso- thermals of mixtures is still furthey extended, the effect of changc: of temperature on the relation between the isothermah of mixtures of two substances being here considered.H. C. Thermal Expansion of Liquid Bismuth. By C. CATTANEO (Rend. Acad. Linc., 7, i i , 88--93).--Viiicentini ( A t t i 3. Ac. T o r i n o , 22, 1886) stated that liquid bismuth has a maximum density a t its point of solidification. This was contested by Liideking (Abstr., 1888, 790), who found the temperature of maxiniuni density to be a, few degrees above the melting point. The author confirms Vincentini's statement by observing the expansion of an amalgam of bismuth pi-epaiwl by dissolving the metal in an equal weight of mercury. The experiments were conducted in dilatometers holding about 220 grams of the amalgam, those used by previous experimenters being much smaller. The saturation temperature of the amalgam was 162.7", and the density was measured between 236" and 279".On examining +,he curve obtained b ~ - plotting densities against temperatures, no breaks could be detected, the curye being practically a straight line. The author therefore concludes that liquid bismuth has a maximum density a t its solidifying point. The density of liquid bismuth at various temperatures is given below :- ncnsity of liquid Ri. --I---I-- Dcnsity of liquid Bi. -I--- 10 - 224 10 -219 10 -214 10 -809 10 - 905 W. J. P.260 ABSTRACTS OF CHEMICAL PAPERS. Calculation of the Boiling Points of Normal Isomeric Ethereal Salts of the Fatty Series. By G. HIXKICHS (COW@ rend., 113, 798--800).-The boiling points of the normal fatty ethereal salts having the general formula C,H21,+,*C,H?,-,0, are plotted out in curves, the ordinates of which are proportional to khe logarithms of the maximum momeiits of inertia of the molecules (Conapt.Tend., 76, 1592; 112, 1128), and the abscism proportional to p , that is, to the length of the alkyl chains. Four different curves are thus obtained, corresponding to the four values 6, 7, 8, 9 of p + q, and the actual boiling points fall very fairly on them (compare Abstr., 1891, 1406, 1408, 1441 ; this vol., p. 2). JN. W. Calorimetry. By P. MAHLEIZ (Compt. re?ul., 113, 174-776 j .-The author has devised a cheap, efficient, and durable modification of Ber- thelot's calorimetric bomb, suitable for use in industrial m d ordinary laboratories. The chief alteration is in the combustion chamber, which, instead of consisting of platinum, is made of mild steel, forged and turned to a suitable shape, asd enamelled inside.The mouthpiece is closed by a screw stopper packed with a lend washer. The substance under examination is supported and ignited by appa- ratus attached to the stopper, and the oxygen for the combustion is supplied a t a pressure of 25 atmospheres froin an ordinary pressure cj-linder through a stopcock screwed into the stopper. The calori- meter and agitator are constructed on the original model, with slight, modifications to reduce the cost. Trial determinations of the heat of combustion of naphthalene gave good results. The npparatiis is adapted f o r the study of fui=nace and other gases. Thermal Constants of Active Malic Acid and Potassium and Sodium Malates.By G. MASSOL ( C m p t . qsend., 113,800-801). -The heat of solution of anhydrous nialic acid is -3.31 C'al., whilst that of the monopotassium and dipotassinm salts is -5.78 Cal. and + 1.55 Cal., and that of the corresponding sodium salts -1.66 Cal. and + 1.78 Cal. respectively. The heat oE neutralisation of the acid and of the hydrogen alkali salts is + W 2 3 Cal. and +12.85 Cnl. with potash, +24.86 Cal. and + 12.46 Cal. with soda. The heat of formation of the solid salts from the solid acid and base, as calculated from the above data, allowing f o r the formation of solid water, is +29.74 Cal. and +49.15 Cal. for the moiiopotassium and dipotassium salts, and +32.02 Cal. and +42-12 Cal. for the cor- responding sodium salts. Dipotassium and disodium malates, prepared by neutralising the anhydrous acid with alcoholic alkali, and heating the dried products at 120" in a current of hydrogen, may be ci-jstallised, contrary to the assertion of Kammerer ( J .p?*akt. Chern., 88, 381), by dissolving i n water, evaporating to a syrup, powdering the surface with a little of the anhydrous salt, and keeping over sulphuric acid for some months. Dipotassium malate crystalliscs in small needles, which are scattered through a firm,.pastg mass. Disodiunz snaEate forms long, prismatic needles containing 4 mol. H20. Mo~aopotassiim and .tnonosodiitiiz. JN. W.GENERAL AND PHYSICAL CHEMISTRY. 261 indates crystclllise readily with 1 mol. H,O, which is slowly lost a t 120". JK. W. Heat of Formation of Hydrazine and Hydrazoic Acid.By BERTHELOT and MATIGNOX ( Compt. rend., 113, 672-679) .-Hydrazine snlphate, N2H4,H2S04, prepared by Curtius, was employed. Heat of dissolution a t 10.8" = -8.7 Cal. The heat of neutralisation was determined (1) by exact precipitation with barium hydroxide, and (2) by direct addition of dilute hydrochloric acid to the solution of the free base left after separation of the barium sulphate. H,S04 diss. + N,H4 diss. = N2H4,H2S04 H,SO4 sol. + N2H4 diss. = N2H4,H2S04 diss.. .............................. develops +11-1 CRI. ............................... cryst 7 7 f36.0 ,, ZHCl dil. + N2H4 diss. = N,HA,2HC1. diss. , Y +10-4 ,, Hj-drazine is a feeble base, like ferric oxide, and its heat of neutrali- sation is less than that of ammonia (+ 12-4 Cal. per equiv.) or even hydroxylarnine (+ 9.3 Cal.).The heat of combustion was determined in the calorimetric bomb, the salt being mixed with a known weight of camphor. K,H,,HZSO, cryst. + 0, + Aq = HZSO, dil. + N, + 2H20 ................. develops +127.7 Cal. and consequentlj-- S (octah.) + 0, + H6 + N, = N,H4,H,S04 ............................. cryst.. 9 9 +220*3 ,, PI', + H4 + Aq = N2H4 diss.. 9 , - 9.5 ,, .......... The formation of hydrazine is endothermic ; its conversion into am- monia by loss of hydrogen and nitrogen is exothermic, and so likewise is its direct conversion into ammonia by combination with hydrogen. NZH4 dil. = NH, dil. + N + H.. .. develops +25.75 Cal. 3NzHA dil. = 4NH3 dil. + N, ...... ,, +32*75x3 ,, N2H4 dil. + H, = 2NH, dil.. ....... 7 , +51.5 7 , It is clear that the direct conversion of ammonia into hydrazine is not possible without the intervention of oxidising actions ; but, on the otber hand, the compound may be obtained by the carefully regulated oxidation of hydrogen compounds of nitrogen and the amides and nitrates derived from them, or by the reductioii of oxygen compounds of nitrogen and nitro- or azo-derivatives. It is noteworthy that the endothermic character of the nitrogen hydrides diminishes as the saturation with hydrogen becomes more complete, and this has already proved to be the case with t h e oxy-acids of nitrogen and the hydrides of carbon, thus: HNO dil.-28.7 Cal., HNO, dil. -42 Cal., HNO, dil. +14*3 Cal., and C2H2 -60.4 Cal., C2H4 -14.8 Cal.. C,H, +25-2 Cal. Hydrazoic Acid.-The experiments were made with the ammonium salt supplied by Cui-tius.Heat of dissolution (N,H,NH,) at 11" =2ii2 ABSTRACTS OF OHEMICAL PAPERS. -7.08 Cal. Heat of neutralisation by baryta +10.0 Cal., by am- monia +8.2 Cal. Hydrazoic acid is therefore comparable to amido- benzoic acid in the energy of its acid function. Heat of combustion (in the calorimetric bomb, both with and without camphor) a t const. vol. = +163-8 Cal. ; a t const. press. +163-3 C d . N4 + IT, = N3H,NH3 ciyst.. . . . . . . . develops -25.3 Cal. N, + €II = N3H,NH3 diss. . . . . . . . . 3 , -32.3 -, N3 + H + Aq = N3H diss. . . . . . . . 7, -61.6 ,, Hydrazoic acid is the most enilotherinic of the nitrogen hydricles. It is most, probably ammonia in which two atoms of hydrogen havc been displaced by a ciolecule of nitrogen, NH:N2, the substitution of the electronegative nitrogen f o r the hydrogen conferring upon the compound its acidic pyoperties. C.H. B. By C. M. VAN I)EvENTEit and L. T. &CICIIER ( Z e d . physikaz. Chewz., 8, 536-542 ; compare Abstr., 1890, 553).-Continuing their investigations on the heats of formation of metallic salts in alcoholic solution, the authors have measnred the heats of neutralisation of sodium and potassiuni ethoxides by a number of acids in the presence of an excess of alcohol. The salts formed, with the heat evolved in each case, are given in tlie following table :- Sodium acetate. . . . 7.3 Cal. I Sodium chloride . . 11.2 Cal. Potassium acetate . 7.2 ,, I Sodium bromide. - . 18.4 .. Potassium biacetate 7.8 ,, i Sodium iodide .. . . . 11.2 :, Sodium benzoate.. (j.44 ,, 1 The authors propose to continue theii. investigations with other Formation of Salts in Alcoholic Solution. acids and bases. H. C. Critical Temperatures of Mixed Liquids. By G. C. SCHNlJrr { AnnaEeiz, 266, 266--2'92).-The author has determined the critical temperatures of a number of mixtures of two liquids in order to test the validity of Pawlewski's foi.mula 9i17 = -- pare Ber., 15, 460 and 2460). In the place of tlie &=bath dcscribed by Galitzine (dim. Phys. C'!r.eru. [2], 41,6231, the author employed :L beaker, 250 mm. in height and about 60 mm. in diameter, which was half filled with paraffin; the liquid was contained in a small scaled tnbe which was attached to a thermo- meter placed in R paraffin-bath ; the temperature a t which the liquid completely disappeared and thc tempemture at the moment of the reappearance of the meniscus were both noted.Very good results are obtained with this apparatus, but it can only be employed for temperatures below 260", as t h o paraffin darkens very rapidly when heated more strongly. The experimental values obtained in this way were in some cases rather greater, in others rather less, than those calculated by Pawlewski's formula, tahe maximum difference being 3.9" ; as, in tllc ?I3 + (100 - 49' (colll- 100GENERAL AND PHYSICAL CHEMISTRY. 263 Case of any particular mixture, tlie differences were, aR a rule, either all positive or all negative, i t would seem that Pawlewski's formula is not quite accurate ; it is possible, however, that the deviations from the calculated values are due to a slight decomposition of one or both liquids.The observed and the calculated critical temperatures of the mix- tures are given in tables. Vapour Pressure of Aqueous Solutions of Cobalt Chloride. By G. CHARPY (Compt. vend., 113, 794-795).-The cnrve showing the variation of the vapour pressure of 32 per cent. aqueous cobalt chloride with the temperature comprises two approximately rectilinear portioils, one ranging from 2W t o 40", and corresponding with the red mlution, the other ranging above 75" nud corresponding with the blue solution. The intermediate portion is curved. These fncts point to the existence of two stable modifications of the salt, perhaps hydrates or other molecular aggregates.The c u i w is similar to that obtained by Jhard from a consideration of the so1ubilit)y of the chloride, but the intermediate limiting temperatures am not, t h e same, those observed by Ward being. :?5" and SO"; this, however, is probably accounted for by the fact that lie dealt throughout with saturated solutions. Jx. W. Pressure and Specific Volume of Saturated Vapours. By C. Dw, LUXGO (Herid. h a d . Linc., 7 , i, 141--145).-The equation log p = k - - - b log T, where p is the pressure, T the absolute temperature, and a, z1, and 7; are constants, is derived by Bertram1 (Thermodpanzique, 1887, 93) from Boylc'~ law and equations given by Clapeyron, Clausius, and Regiiault. From the same sources the a' author derives the equation log B = li' + + b' log T, where s is thc Apecific volume of the saturated vapour.The specific voliime~ of carbon bisnlphide vaponr a t different temperatures calculated by this formula agree well to the third decimal place with the values given by Hirn. The function p = 0 when T = 0, and then increases until the critical temperature i R reached, when T = a/b, after which i t decreases indefinitely, and has no further physical significance. Similarly 8 is infinite when 1' = 0, and decreases to a minimum at the critical tem- perature, when T = a'/b'. For the same vapour, therefore a/b = a'/b'. Zeuner's equation, prr = constant, where n is a constant such that a = nur and b = nb', may bc a t once deduced from the above two equations. W. J. P. The Freezing Points of Aqueous Solutions of Boric Acid and Mlannitol.By G. MAGNAXISI (Gozzetta, 21, ii, 134--141).-A Rtudy of the electrical conductivities of aqueous solutions of boric acid ant1 mannitol has already enabled the mthor to determine the composition OP the compound of the two substances which exists in solutioii (Abstr., 1890, 1357) ; 110 cluc was, however, obtained to the amount of the compound produced. F. S. K. a T 'r264 ABSTRACTS OF OHEMIOAL PAPERS. An investigation of the solutions by the cryoscopic method shows that the number of molecules existing in an aqueous solution contain- ing both boric acid and mannitol is abont 5.4 per cent. less than it would be if no combination occurred, the cryoscopic constant of the solvent for water (16.5) being diminished by 5.4 per cent. in solutions containing bot,h constituentq whilst for solutions only containing one of the substances, the constant is considerably increased in value.The author has also determined the electrical conductivity at differ- ent temperatures (20-50") of solutions containing boric acid and mannitol in varying proportions, and finds that the conductivity decreases b r about 6 per cent., with a rise of temperature of 30" (20-50"); the rate of decrease is almost tlie same for differently constituted solutionP. The author considem that this abnormal change in the condcctivity of such solutions is only apparent, the diminution in conductivity with rise of temperature being clue to increased hydrolytic dissociation. The true temperature coefficient of the electrical conductivity is, therefore, most probably positive.As a rise in temperature causes a decrease in the amount of the com- pound of boric acid and mannitol in the solution, the formation of ihis substance is probably accompanied by development of heat. W. J. P. The New Theories of Solution. By J. WALKER (PhiZ. Mug. [5], 32, 355-365) .-This paper contains a reply to some of the objections advanced by Pickering against the theories of osmotic pressure and of electrolytic dissociation. The author doubts if Pickering's deter- mhations of the freezing point of sulphuric acid solutions (Trans., 1890, 331) have the degree of accuracy claimed for them, and gives an example t o shorn that the " potential dissociation " advocated by Lodge is insufficient to explain tlie known facts of electrolysis.Change of Volume on Dissolution. By J. A. WAKKLTN, W. JOHNSTONE, and W. J. COOPER (P7i,iZ. J h g . [ 5 ] , 32,473-477).--Wheii R solid dissolves in water, one of three things may happen with respect to the volume. The volume of t,he solution may be equal to the sum of the volumes of the dissolved substance and the water, or i t may be greater, or it may be less, as is usual. When there is con- traction, the authors measure it by the weight of water, which, instead of overflowing from a vessel of 100 C.C. capacity filled with water, is retained when 1 gram of salt dissolves so as to give 100 C.C. of solution. In the case of mgar there is no condensate, as there is no change of volume. With some ammonium salts there is expansion, and the condensa,te is cou- sequeiitly negative.The authors state that, " i n the case of very many salts, the condensate bears an atomic relation to the gram of salt which occasions i t " (compare Sbstr., 1891, 1412). Mutual Solubility of Salts in Water. By J. E. TREVOR (Phi,?. lllug. [.5], 32, 75-78).-With reference t o Nicol's paper under the above title (this vol., p. 8 ) , the author draws attention to the fact that the problem therein discussed has received a theoretical solution, with experimental confirmation f o r many cases, from the work of Nernst, J. W. This constant they term the " condensate." J. W. Noyes, and himself. J. w.GENERAL AND PHYSICAL CHEMISTRY. 265 Solubility of Mixed Crystals, especially of two Isomorphous Substances. By H. W. B. ROOZEROOM ( Z e d . yhysikab. Chenz., 8, 504-530) .-According to the rules laid down by Gibbs for equilibrium between three phases, two of which are solid salls and the other their solution, the composition of the saturated solution at constant tem- perature will be dependent on the pressure.Experiment up to the present has confirmed the above for a number of solutions of mixed salts, but there are a number of exceptions where the salts taken are capable of forming a double salt or an isomorphous mixture, The exception has been shown to be only an apparent one in the case of double salts by the author’s investigation of the behaviour of astracanite (Abstr., 1888, 1164). Riidorff’s researches on the solu- bility of mixtures of isomorphous salts have, however, placed it beyond doubt that the composition of their solution is variable, and not constant, for constant pressure, even when excess of both salts is present.The explanation of this behaviour must be sought in the fact that the isomorphous salts combine with one another to form homo- geneous mixed crystals, the equilibrium coiiditions being thus altered. This difference between isomorphous and other mixed salts is of im- portance, as it is evident that the solubility of mixed salts becomes a criterion of their isomorphism, but, before this property can be made any extensive use of, it will be necessary to establish the conditions of equilibrium existing between isomorphous mixtures and their solutions. If, with Van’t Hoff (Abstr., 1890, 1044), we regard isomorphous mixtures as solid solntions, the dissolution of the mixed crystals may be compared with the evaporation of a liquid made up of two com- ponents, both of which are volatile.Osmotic pressure then takes the place of vapour pressure, and, in place of the concentration of the liquid solution, that of the solid solution must be taken. I f there are N molecules cf the one salt, and n molecules of the second with osmotic pressurep, in the solid solution, then we get, as the expres- sion €or the law of Henry, kp = n / ( N + n), or, since saturation is complete when the osmotic pressure of the solid is equal to that of the solution, if the second salt is present in the solid in the molecular pro- portion x per cent., and if in the saturated solution the concentration is represented by c2 molecules, then l i c 2 = z.This, of course, assumes the absence of electrolytic dissociation. It also assumes the identity of the solid and liquid molecule, but if this is not the case, and *n of the latter combine to form one of the former, the formula becomes kcz = 2’1. If x becomes smaller during solution and greater during the separa- tion of the mixed crystals, the solution will be richer in the com- ponent x than the crystals. Hence, if the osmotic pressure of a saturated solution of mixed crystals increases or decreases with increasing proportion of one of the components of the mixed crystals, the ratio of this component to the other in the solution will in the one case be greater, and in the other less, than in the mixed cryfitals. This enables a distinction to be made of the possible cases during eolution or crystallisation of mixed crystds.If the mixed crystals are miscible in all proportions, three casts 1 -266 ABSTRACTS OF BHEMIOAL PAPERS. are possible. The osmotic pressure of the saturated solution is 8 continuous function of the concentration, and may either incl-ease continuously wit.h the concentration, it may increase to a maxi- mum and then fall, or it may fall to a minimum and then rise. In tlie first case, on evaporation of a solution of the two constituents, the crystals separating out would contain increasing quantities of that component the saturated solution of which had the greatest osmotic pressure, until at length nothing but a solution of this component was left. In the second caRe, the crystals would be of varying composition, until a point is reached corresponding with the maximum, when the composition of the crystals would be the same as that of the solution.The third case would be similar in character to the second. If the mixed crystals are not miscible in all proportions, the osmotic pressure is no longer a continuous function of the concentra- tion. The curve for the pressure as a function of the concentration will then be represented for a certain portion of its length by a straight line, parallel to the abscism axis, and terminating at one end with a certain limiting value of the concentration of the one constitu- ent, and at the other end with a certain limiting value of the other constituent in the mixed crystals. Prom these end points to the points representing the pressures of the saturated solutions of the pure component8, the curve may take various forms.Some of these are considered by the author, and he points out that isodimorphous mixtures probably all give a discontinuous curve of the above form. H. C. Solubility of Mixed Crystals of Potassium and Thallium Chlorates. By H. W. 13. ROOZEBOON (Zeit. physiknl, Clzem., 8, 5.71-535).-The author has determined the solubility of mixtures of potassium and thallium chlorates i n varying proportions. He finds that these salts present one of the cases considered in a former paper (preceding abstract) of mixed crystals which are not miscible in all proportions, and obtains results which generally confirm his theoreti- cal conclusions. H. C. Affinity Coefficients of Organic Acids and their Relation to Chemical Constitution.By P. WALDEN (Zed. physiknl. Chem., 8 , 433--503) .-The author has determined the affinity coefficients of a large number of dicarboxylic acids from the conductivities of theii- aqueous solutions (see Ostwald, Abstr., 1889, €418). The values ob- tained f o r K = lOOk are given in the following tables :- I. MALONTC ACID AND ITS DEB~VATITES. Dimethylmalonic acid. . . Methylmatonic acid. . . . . Isobutylmalonic acid. . . . Butylmalonic acid . . . . . . Propylmalonic acid. . . . . Isopropylmalonic acid. . . Ethylmalonic acid . . . . . . Benxylmalonic acid . . . . . Ally lm alonic acid. . . . . . . 0.076 0-086 0.090 0-103 0-112 0.127 0.127 0.151 0.154 Ethylmethylmalonic acid Malonic acid . , . .. . . . . . Diet,hylrnnlonic acid . . . . Diallylmalonic acid . . . . . Benzy let hylmalonic acid. Dibe~zylmalonic acid . . . Chloromalonic acid.. . . . . Benzyltartronic acid . . . . 0.161 0.163 0.74 0.76 1-48 4.1 4.0 0-55GENERAL AND PHYSICAL CHEMISTRY. Sncciiiic acid. . . . . . . . . . 0.0068 Isopropylsuccinic acid. . 0.0075 Ethylsuccinic acid. . . . . 0.008-5 Methylsuccinic acid. . . . 0.0086 26 7 Isobixtylsiiccinic acid. . 0.008822 Propylsnccinic acid . . . 0.00886 Benzylsuccinic acid I . . 0.0091 Allylsuccirlic acid. . . . . 0.109 Trimethylsiiccinic acid . 0.0307 Benz yldimeth ylsuccin ic acid ..... .. ...... .. 0.0455 A ntidime thylsiiccinic acid . . . . . . . . . . . . . . . Paradimethylsuccinic acid . . . . . . . . . . . . . . . u-E t,hylme thyls u ccinic acid.. . . . . . . . . . . . . . . Pare t h ylme thylsnccinic acid . . . . . . . . . . . . . . . Paradiet hylsucciiiic acid Antidiethylsuccinic acid Diethylsuccinic acid ( 3 ) Parallylethylsnccinic acid p-Allylethylsuccinic acid p-Phenylmethylsnccinic acid . . . . . . . . . . . . . . . Pnraphenylmethylsncci- nic acid . . . . . . . . . . . PropyldimetliSlsuccinic Ethyldimethylsuccinic acid .......... .. .. .. acid . .. .. .. ........ 0.0551 0.0556 0.0123 0.0191 0.0201 0,0207 0,0245 0,0343 0-0386 0.0269 0.0359 0.0233 0.0372, Paraben z ylmethylsucci - iiic acid . . . . . . . . . . . . p-Benzyliiiet h ylsuccinic acid . . . . . . . . . . . . . . . Pai.abeiizyletliylsuccinic acid. . . . . . . . . . . . . . . . ~~-Benzylethylsnccinic acid . .... I ....... .. ParadiphcnSlsnccinic acid .. . . . . . . . . . . . . . Ant id iphcny lsuccinic acid . . . . . . . . . . . . . . . Antidilly droxysuccinic (inactive tartaric) acid Parscli hydroxysnccinic (tartaric) acid . . . . . . Dextrotnrtaric acid . . . Laxotartaric acid.. . . . . 0.0210 0.0247 0.02Ci2 0.0414 0-0200 0.026 0.060 0.097 0.097 0.097 111. GLUTAIZIC AXI) PI~IIELIC ACIDS ASD THEIR DERIVATIVES. Glutaric acid.. . . . . . . . cc-Methylglut.ayic acid . Paradimethylglutark acid . . . . . . . . . . . . . . Antidimethylglutaric acid . . . . . . . . . . . . . . Bfetapropylrnethylglut- aric acid . . . . . . . . . . Paradiethylglutaric acid Mete thylmethylglut - wic acid . . . . . . . . . . 13-Methylglutaric acid . Parethylmethylghtaric acid . . . . . . . . . . . . . . 0.00475 0.0052 0.0055 0.0055 0-0054 0.0055 0-0056 0.0059 0.0059 Benzylmethyl glutaric Pimelic acid : From suberone, Schor- lemmei... . . . . . . . . . . From castor-oil, Hell.. OmO0348 From pentanetetracarb- oxylic acid, Perkin.. 0.00345 Of unknown origin, Ost- wald.. . . . . . . . . . . . 0.00357 p-Pimelic acid, Arth.. . 0.00420 Pirnelic acid from smy- acid .. .. .. .. .... .. 0.0059 0.0032 lene bromide : ( a ) Bauer ...... .. 0.0097 ( b . ) Hell . . . . . . . . . 0.0091 I Perapropylmethylglut- aric acid . . . . . . . . . . OmO0592 68 ABSTRACTS OF CHEMICAL PAPERS. IV. UNSATL'RATEII D~BMC ACIDS. Methylitaconic acid.. .. 0.0095 Ethylmethylrnale'ic an- Pyrocinchonic anhydride 0.0108 1 taconic acid .......... 0.0120 Benzylglutaconic acid. . 0.0153 Glutaconic acid ....... 0.0183 Mesaconic acid ........0.0794 hydridc ............ 0.0097 Fumaric acid .......... 0.093 Methylmesaconic acid. .. 0.094 Ethylmesaconic acid .... 0.093 Isopropylmesaconic acid . 0.093 Methylcitraconic acid. ... 0.238 Citraconic acid ......... 0.340 Mnle'ic acid ............ 1-17 It will be seen that, with the exception of dimethylmalonic acid, all the di-substitn tion compounds of inalonic acid have higher affinity coefficients than malonic acid itself. The mono-alkyl deriva- tives, on the other hand, have smaller coefficients than the parent acid. In the cases of succinic acid, the mono-alkyl derivatives are better conductors than the free acid, the di-derivatives better than the mono-derivatives, and the tri-derivatives better than the di- derivatives.When succiiiic anhydride is dissolved in cold water, the electrolyte obtained is identical with ordinary succinic acid, and no evidence of the existence of a second snccinic acid is obtained. The author points out that the antidihydroxy-, antidimethyl-, and u-ethylmethyl-succinic acids have smaller coefficients than the corre- sponding para-acids. It would, therefore, appear possible, although in opposition to the accepted view, that the first contain the malei'noi'd, and the second the fumaro'id, grouping. Chemical Action at a Distance. By W. OSTWALD (PAiZ. llILtg. [ 5 ] , 32, 145--156).-A short glass tube of about 2 cm. diameter, closed below with parchment paper, is introduced into a small beaker. Both these vessels are filled with a solution of potassium sulphate, -are being taken that the level of the liquid i n the tube is higher t h m the level in the beaker.A rod of pure zinc is dipped into the solution in the tube, and connected electrically with a piece of platinum wire, which reaches to the bottom of the beaker. A few drops of it solution of sulphuric acid specifically heavier than the potassium sulphate solution are then carefully brought with a pipette upon the bottom of the outer vessel, so as not to come into contact with the parchment diaphragm. Hydrogen is a t once evolved on the platinurn, and R subsequent investigation of the solution in the inner vessel shows that a quantity of zinc has dissolved in the potassium sulphate solution as zinc sulphate. Such an action as this, where the specific solvetrt for a metal (here zinc) is applied at a place where it can have no direct action and yet exerts its solvent power, is termed by the author a chemical action a t a distance. Many instances of similar phenomena are given.For example, gold may be dissolved in a solution of com- mon salt, by bringing the platinum with which it is connected into contact with a salt solution saturated with chlorine. Again, if two makers-one containing a solution of ferrous chloride, the other a solution of common salt saturated with chlorine or bromine-are connected by means of a siphon filled with salt solution and closed at H. C.GENERAL AND PHYSICAL CHEMISTRY. 269 both ends with parchment paper, then on introducing platinum electrodes into the beakers and coniiecting them through a galvanad meter, a current is at owe indicated, and the ferrous chloride becomes oxidised to ferric chloride in the neighbourhood of the electrode, as may be shown by the previous addition of a little potassium thiocyanate solution.All such reactions receive a ready explanation from the theory of electrolytic dissociation, the author laying emphasis on the fact that the description of many of the experiments made by him waR com- pletely worked out at his writing table, on the basis of this theory, before he had Been any of the phenomena in question ; and that after the experiments had been performed, nothing in the description required to be altered. Chemical Action at a Distance. By S. U. PICKERING (Phil. *Wag. [5], 32, 478).-The author holds that a simple explanation of Ostwald's experiments (see preceding abstract) may be obtained without having recourse to the theory of free ions in solution, and that, therefore, these experiments cannot be accepted as proofs of this theory.By 0. LEHMAYN (Zeit. pkysikal. Chem., 8, 543-553) .-Senarmonti discovered that salt crystals may be coloured by certain organic dyes without any change in the form or homogeneity of the crystal. The author has on former occasions made similar observations with other inorganic and organic com- pounds, and in order to ascertain something more with reference to the conditions under which this phenomenoii takes place, has now made a large number of experiments on the artificial coloration of crystals. The crystals made use of were those of certain organic acids, such as succinic, protocatechuic, and phthalic acids, and theee were coloured by means of different organic dyes.The author summarises his results as follows :- The crystals always become darker in colour than the solution from which they separate. They are usually observed to be surrounded by a lighter coloured, or even quite colourless, layer, the colouring matter being deposited with such rapidity upon the growing crystal that the slow diffusion of the dye from the more distant parts of the solution is not sufficient to make up for the decreasing concentration in the neighbourhood of t,he crystal. The colouring of' the crystals is in nearly all cases dichroic, a proof that the colouring matter actually enters in some way into the struc- txre of the crystal.The remarkable rule is observed that only one of the two rays produced by double refraction is coloured, whilst the other appears to be perfectly white, the colonrless ray being always the one which has undergone the least refraction. If two colouring matters are present in the solution, the presence of the one often hinders the absorption of the other. In some cases, however, the reverse takes place, and a colouring matter which alone would not be absorbed may become so when some second colouring matter is added. Change of the solvent, or the addition of other solid or liquid foreign matter, msy act in a similar manner. J. W. s. u. P. Artificial Colouring of Crystals. VOL. LXII. 2c2 70 ABSTRACTS OF CHEMICAL PAPERS. Different crystals are only capable of taking up certain organic dyes, so that two compounds of perfectly similar appearance may be capable of combining the one only with one, and the second only with some other dye.This fact may obviously be made available in dis- tinguishing crystals one from another. It may also perhaps be applicable for the purification of certain dye stuffs. Rapid Weighing on Precision Balances by means of a Scale read by a Microscope. By A. COLLOT ( B d . SOC. Chim. [3], 6, 98--100).-The needle of B balance carries a scale illuminated from behind the balance, and viewed by a small microscope containing a, scale in the focal plane of the eye-piece. The centre of gravity of the beam may be lowered considerably, and t h u s the rapidity of oscillation of the beam increased materially by the aid of this device.The value of each division of the scale carried by the needle being known in centigrams and milligrams, the position of rest of the indicator is ascertained by the method of oscillations, and from its deviation from the central point the weight t o be added t.0 that in the pan is known. With a little care, weighings only take one-fourth or one-fifth as long by this method as they usually do. A Siphon for Hot Liquids or for those Evolving Gases or Vapours. By 5. C. ESSPI’EIE (Bull. SOC. Chim. [3], 6, 19-21).- Between the two arms of the siphon 5 yeservoir is interposed ; this is filled with some of the liquid to be siphoned, and hermetically closed. When the long arm of the siphon is opened, the fall of the liquid de- termines a diminution in the pressure of the reservoir, and a continuous flow results.T. G. N. H. C. W. T.253General a n d Physical Chemistry.Measurement of Light Intensity by the Expansion ofChlorine. By A. RICHARDSOX (Phil. Mag. [ 5 ] , 32, 277--284).-Theauthor has confirmed Budde's observation (PhiZ. Mag., 1871) thatwhen chlorine is exposed to sunlight an expansion of the gas occurs,which is independent of direct heating effects due to the light ; andthat the volume to which the gas first expands is maintained duringexposure, provided that the intensity of the light remains constant,contraction to the original volume taking place when the gas isshaded.In order to compare the expansion obtained in this way with thelight intensity, as determined by means of a Bunsen and Roscoe'spendulum actinometer, a differential apparatus was constructed, con-sisting of two tubes of 55 C.C. capacity and 10 cm.in length, whichwere connected with a graduated horizontal gauge, provided with asmall bulb at each end. The gauge and bulbs contained strongsulphuric acid, a, short column of air serving as index. The tubes tobe exposed were suspended in a box, which could be placed at anyrequired angle to face the sun, and when filled with dry air werefound to bo equally heated. One tube was then filled with drychlorine, and the acid, up to the index, was saturated with this gas.The bulbs containing the acid were in all cases protected from the light.When the maximum expansion of the chlorine was reached at anyone time, as shown by the index remaining stationary, the lightintensity was measured.A comparison of the numbers thus obtainedshowed that the change in volume of the chlorine is very nearly pro-portional to the actinic intensity of the light, as given by the actino-meter.Experiments were also made with mixture: of chlorine and air.The effect of dilution with air is a t first very marked, diminishingafter a time, but finally increasing when only a small proportion ofchlorine remains. It was found that the expansion of chlorine bylight is unaffected by change of temperatwe within a range of from14" to 138".The author finally constructed an automatic registering apparatusfor measuring light intensity. This was done by suspending a differ-ential apparatus on the beam of a balance in such a manner that theflow of acid from one arm to the other produced a movement of thebeam, which was communicated by means of a lever to a pen, and wasrecorded on a rotating drum.This instrument will record continu-ously the actinic intensity of the light undei. all conditions of weatherthroughout the year. J. W.The Application of Ketteler's Formulae to Optical Chemistry.By R. Nasixr (Rend. Acad. Lint., 6, ii, 324-331).-!I!he author com-pares Ketteler's formula, N = (12' - l ) ( v - /3) (Abstr., 1889, 3%),VOL. LXII. 254 ABSTRACTS OF CHEMICAL PAPERS.with those of Lorenz and Lorentz, Gladstone and Landolt, and pointsout that the constants p and M vary much in valne under differentconditions of temperature and pressure.Thus, for a-bromonaphthal-ene, the value of p between 16.5" and 28.1" is 0.03226, between 28.1"and 77.6" 0.15966, and the mean value betwecn 16.5' and 77.6" is0.13620, the numbers being for infinite wave-lengt'h. A small changein the index of refraction makes an enormous difference in the valuesof p and M, and as the index of a substance varies somewhat withdifferent samples, each as pure as possible, the values calculated for/3 and Ill are very discordant, and hence of little value in optical:chemistry. Ketteler's formulae, although of great theoretical interestfrom a purely physical point of view, cannot be advantageouslyapplied t o optical chemistry, simply because the experimental dataare not sufficiently exact.Rotatory Power of Silk.By 1;. VI(;NOX (Compt. rend., 113,802-804).-Silk may be expected to act on polarised light, as itreadily yields leucine and tyrosine on hydrolysis. Attempts to find asuitable solvent for the material a5 a whole proving unsuccessful, thetwo chief constituents were examined separately.The colouring matter of the silk of Bombyx nzori having beenextracted by repeated treatment with hot alcohol acidified withhydrochloric acid, the skein is plunged into cold 3 per cent. aqueoussoda solution, which dissolves the enveloping material, but leaves thematrix or fibrolin untouched. The rotatory power of a yellowish,limpid solution thus obtained was [alj = -39.2".To preparc the fibro'in for examination, the silk is boiled twicewikh 10 per cent.soap solution, the soap being washed away with waterafter each boiling ; it is then washed with acidified water (0.1 percent. of hydrochloric acid), and finally with alcohol. The white sub-stance thus obtained is dried and dissolved in moderately stronghydrochloric acid. A clear, dilute solution prepared in this wayshowed a rotatory power of [a]j = --OD, which was not materiallyaltered by further dilution, or by the addition of excess of ammonia.The rotatory powers of the two chief constituents of silii are, therc-fore, practically identical, and are of the same sign as those of theprot eids. JN. W.W. J. P.Changes of Voltaic Energy of Alloys during Fusion. ByG. GORE (Phil. Xag. [ 5 ] , 32, 27--31).-Regnauld (Chem.News, 38,53) observed that liquid gallium is electropositive t o solid gallium ina neutral solution of gallium sulphate. The author hao made corrc-sponding observations with various alloys. A glass dish and atobacco pipe with a wide bowl were partially filled with a conductingliquid (solution of hydrogen chloride o r sodium chloride), and con-nected by means of a siphon. A rod of the solid alloy was placed inthe cup, and a second portion was melted in the bowl of the pipe.Connection was made through a galvanometer by means of iron wires,The alloy in the bowl was alternately heated and cooled, the galvano-meter being observed in order to ascertain if there was any deflectionof unusual inagoitude when the temperature passed the melting poinGENERAL AND PHYSICAL CHEMISTRY. 255c ~ f the alloy.As most of the alloys employed did not melt sharply,no very sudden deflection was noted, but in the case of an amalgamof 1 part of cadmium aud 4 parts of mercury in a solution of sodiumchloride, there was a sudden reversal of the current when theamalgam completely liquefied, the liquid being electronegative i o theElectromotive Forces of Metallic Salts. By C. L. SPEYERS(Arnar. Ohem. J., 13, $72--486).-1n continuation of previous work(Abstr., 1890, 843), the dserence of pot entia: between mercury andcopper, iron, and tin has been measured in various electrolytes inten different states of concentration, varying from molecular propor-tion (gram-litre) to molecular proportion, each solution havingone-half the concentration of the preceding.The metals were usedin the state of amalgam wherever practicable. In the case of copper,the electrolytes were hydrochloric, nitric, acetic, and sulphuric acids,alone and in pairs ; the copper salts of these acids, with the exceptionof the chloride, which attacked the mercury; pairs of these salts,iiamely, nitrate with acetate and sulphate, and acetate with sulphate ;mixtures of the salts with acids, namely, the nitrate, acetate, andsulphate with nitric, acetic, and sulphuric acids ; and, finally, the zincselts of the same acids. In the case of iron, the same series ofelectrolytes was used, with the addition of the metallic chlorides,ferrous and ferric salts being substituted for copper salts.In the caseof tin, the electrolytes used were the above acids, alone or in pairs ; thechlorides, alone, or mixed with acids ; the above-mentioned zinc salts,and the corresponding ferric salts.The general conclusions which tho author deduces from thenumerous data thus obtained are : That the electromotive force in-creases, as a rule, with dilution ; that in solutions containing hydro-chloric acid it is lower than in those containing the other acids, andis not materially affected by the admixture of those acids or of metallicsalts ; that in solutions containing different pairs of metallic and acidradicles it is only slightly greater than in the solutions of the pairyielding the lower value; and that it is lessened by substitutingcopper, stannous tin, or, in the case of chlorides, ferrous iron forhydrogen, but is practically unaffected by the substitution of stannictin.The increase of electromotive force with dilution may be explainedby means of the dissociation hypothesis, if the assumption is madethat the mean free path of the ions is increased by dilution, so thatthe ions have less influence on one another, and give up, therefore,more electricity t o their respective electrodes.A theory of chemical affinity, which is proposed, is based on the non-conductivity of the non-metals.The atoms of these are supposed tocontain it constant amount of negative electricity, neglecting artificialsurface charges, whilst the metallic atoms contain positive, o r bothpositive and negative, electricity, the total quantity, however, beingconstant. When an atom of a non-metal comes in contact with ametal, its charge attracts the positive charge of the latter, and, as i tcannot unite with it, a portion of the metal is detached, and a corn-solid a t this point.J. W.t 256 ABSTRACTS OF CBEMICAL PAPERS.pound formed, the stability of which depends on the completeness ofthe internal insulation of the negative ion and the magnitude of thepositive charge of the positive ion. This explains the weakness ofthe combinations of metals with metals, and non-metals with non-metals, and the strength of those of metals with non-metals.The lowering effect produced on the electromotive force by stannoustin, and to a less general extent by ferrous iron, may be explained inaccordance with the above hypothesis, by supposing that the negativeelectricity in the non-cond ucting ion is inextricably entangled withthe matter.The initial action of the ion on the metal is to dislodgeand combine with a portion of the latter containing unit positivecharge, and a molecule of an ous compound is formed ; this, however,meets with more negative ions, and gives up part of its positive charget o one of them, so that 2 moleculels of the ic compound are formed.Siuce the negative electrode is charged with negative electricity bythe negative ions, and partially discharged by the positive ions, itfollows that when the ic compound is present, the charge removed isless, and the potential of the electrode numerically greater than whenthe 02~s compound is present.Influence of Boric Acid on the Electrical Conductivity ofAqueous Solutions of Organic Acids.By G. MAGRABIKI (Gazzetta,21, ii, 215--228).-1t has been previously shown (Guzsetta, 20)that the electrical conductivity of solutions of tartaric acid is sensiblyincreased by the addition of boric acid and is t o some extent de-pendent on the dilution and the quantity of boric acid used; thisbehavionr was explained by assuming the formation of a combina-tion of the two compounds which has electrolytic properties and ispartially dissociated by water. In the present paper, the results of aseries of experiments on the influence of boric acid on the electricalconductivity of aqueous solutions of acetic, benzoic, butyric, succinic,crotonic, salicylic, lactic, glyceric, gallic, amygdalic, and glycollicacids are described.There is a marked difference between the be-hariour of hydroxy- and other acids, the conductivity of solut,ions ofthe former being materially increased by the addition of boric acideven in very dilute solutions ; this increment rises with the quantityof boric acid added, but falls on dilution ; it varies considerably withthe nature of the acid under observation. Solutions of hydroxyiso-butyric, pyrocntechuic, malic, and citric acids similarly show an in-crease of conductivity on the addition of boric acid, whilst pyruvic,dehydracetic, formic, oxah, valeric, monochloracetic, levulinic,camphoric, and aspartic acids, which do not contain the hydroxylgroup in their acid radicles, exhibit no such increase. This beliaviourmay possibly be of use in deciding as to the presence of an hydroxylgroup in organic acids.The electrical conductivity of aqueous solutions of resorcinol,quinol, phenol, ortho- meha- and para-cresol, guaiacol, and phloro-q1ucinol is only very slightly increased by the addition of boricacid; on the other hand, that of solutions of catechol, and moreespecially of pyrogallol, is considerably increased.The author be-lieves this t o be due t o the presence and position of the hydroxylJN. WGENERAL AND PHYSICAL CHEMISTRY. 257group in these compounds, and proposes to investigate the behaviourof polyhydric phenols containing two hjdroxyl groups in ortho-position i n this respect.S. B. A. A.Some Points on Electrolysis. By J. SWIA-BCRNE (Phil. J h g . [ S ] .32, l-g).-The author considers a one-fluid reversible cell, with itsexternal circuit closed through a resistance so high that, in corn-prison, the internal refiistance is negligibIe. A coulomb passingthrough the cell has work done on it numerically equal to the elec-tromotive force E. A t the electrodes p and n there is chemical action,c , and local heating, h, so that as there is assumed to be no work donein overcoming the resistance of the electrolyte, E = Epc + En, + I+,, + E,J~. The seat of E.M.F. is here supposed to be in the cell andnot a t the metallic junction outside.Jf the chemical work is assumed to be independent of the tem-perature of the cell, _ _ it can be shown from the above equation thatCEEE = E,,, -+ E,, + e de, when 0 is the temperature (Helmholtz’sequation).The author further shows how the Peltier effect a t eacheontact in the cell can be obtained sepa~ately. When there is anysecondary or “ non-adjuvant ” action, the cell is not reversible. Theformation of lead sulphate on both plates of a secondary battery isconsidered by the author to be a primary reaction (that is, there is110 intermediate formation of lead monoxide) and the cause of the:Lctirity of the cell.His views of nascent action are as foIlows :-Sodium amalgam indilute acid gives off hydrogen, and will ’reduce a ferric salt to theferrous stage. This reduction he does not attribute to the action of“ nascent ” hydrogen.A better explanation would be that themetal can dissolve if it e i t h e ~ reduces the ferric salt or evolveshydrogen. “ Evolution of hydrogen and reduction of the salt are thusalternate, not consecutive, results. Similarly, in an engine, the steameither works the engine 01’ comes out at the safety-valve; it doesnot begin to lift the safety-valve, and then change its mind and workthe engine in a iiascent state.” J. W.Relation of E.M.F. to Latent Heat, Specific Gravity, &c., ofElectrolytes. By G. GORE (Phil. Mug. [S], 32, 157--168).-1norder to ascertain whether, in cases where t’he mixture or dilution ofelectrolytes is attended by a heat-effect, a change in the power ofexciting electromotive force occurs, the author took various pairs ofsolutions (or one solution and pure water) a t the same temperature,measnred the E.M.F.of a, cadmium-platinum couple in each liquidseparately, then mixed the liquids, observed the 1,emperat ure of themixture, and, a8fter allowing the liquid t o acquire the former tem-pel-atnre, measured the EMF. of the couple in it. This E.M.F. hethen compared with the mean valae of the E.M. Ir’. in the liquid beforemixture. The results are contained in the following table. Thesolutions of the chlorides of sodium and potassium were nieasured w i t ha zinc-platinum couple :258 ABSTRACTS OF CIHEMICAL PAPERS.Mixture. Chniige of temperaturein degi-ees centigrade.Change iiiE.M.F........... ! NkSO, solution + dil.H2S0,CH,-COOH + water. ................Tartaric acid solution + miter ........ INH,NO, 7 - .......... jNaNO, I . . . . . . . . . . . ,S r W " Y . . . . . . . . . .NaCl . . . . . . . . . .I Na2S04(NH4),S0, ., . . . . . . . . . .Na2C0, I . . . . . . . . . . I KNO:S . . . . . . . . . . !NHdCl 1 CH,*COONa ,. .. ........'KCl 1 . . . . . . . . . . 1 M g WNaOH . . . . . . . . . . tHCl 9 , . . . . . . . . . . ~ .. ........IIEt.4I NH,J w3 , . . . . . . . . . .,.>, . . . . . . . . . .9 , . . . . . . . . . .,,3I , . . . . . . . . . .Y l . . . . . . . . . .- 0.66- 0.9- 0.16- 4'44- 1-42 - 1.08?- 0.14 - 0.14- 0.28 - 0.54- 0.19 + 0.14 + 0.22 + 0-04 + 7-14 + 2-38 + 11 -00 + 0'02 + 0.10+ Os0$O1 + 0*0'130+ 0 '1923 + 0 '04.00 + 0 '1228 + 0 '0'141 + 0 '0668 + 0 -0359 + 0 -0402-0 '0445+0.0'715 + 0 *0345 + 0 -0360 + 0 '0787 + 0 '1219 + 0 -0298t.0 '2872 + 0,2375 + 0 -0150 + 0 '0040Special experiments weye also made on the contractiou of saltsolutions and water. The author concludes that " in cases of merephysical mixture, the changes of mean specific gravity and of meanelectromotive force of electrolytes are probably related t o each otheras concomitant effects of the same cause, change of molecular motion."J. W.Specific Inductive Capacity and Latent Heat of Vaporisa-tion. By E. OBACEI (Phil. Nag. [ 5 ] , 32, 113-127).-From a con-sideration of the specific inductive capacities published by Tereschin(Ann. Phys. Chem. [2], 36, 792) and the heats of vaporisation ob-served by Schiff (Anden, 234, 3:38), the author finds a relationbetween these two magnitudes for members of vmious homologousseries.In any one series, the quotient of the latent heat of vaporisa-tion, X, by the specific inductive capacity, I(, is practically constant.Thus, for the ethered salts of acetic acid the following values of AiKare obtained :-Nethyl. 35thjI. l'ropjl. Isobutylyl. Amyl.12.0 12.8 12.3 1'2.1 12.8 KThe mean value of the ratios for the corresponding formates is 9-83,Monatomic alcohols give a meanThe relation thus obtained in hornologous series may be combinedand that of the benzoates, 10.33.ratio of 7-56, and eOhy1 salts of the acetic series, 12.42.with othei- similar relations. Tc3i For example, Trouton gives X QENERAL AND PHYSTCAL CHEMISTRY.2592350240a45S50255where T is the boiling point in the absolute scale, 31 the molecularweight, and C a constant. It' we make X = riK and introduce thisvalue in the equation, then rlK = CA,., or KhI = C'T; that is, inany series the boiling points ilz the absolute scale are proportioiial tothe molecular inductive capacities. Similarly, by making use of DeHeen's results, it follows that the coefficient of expansion at 0" isinversely propoytional to the molecular inductive capacity.The ratio X/K for ethyl oxide is 20.8 ; for carbon tetrachloride, 21.0 ;f o r carbon bisulpliide, 33.0 ; and for oil of turpentine, 31.1.TJ. W.10 248 260"10 -243 26510 239 27010 -233 27510 -229 280Chmge of the Empirical and Theoretical Isotherrnals ofMixtures of two Substances with the Temperature.By A.BL~~MCKE (Zeit. physikal. Chem., 8, 554-565).--Y1he method whichthe author has employed in a former papel- (Abstr., 1891, 375) fortracing the connection between the empirical and theoretical iso-thermals of mixtures is still furthey extended, the effect of changc: oftemperature on the relation between the isothermah of mixtures oftwo substances being here considered. H. C.Thermal Expansion of Liquid Bismuth. By C. CATTANEO(Rend. Acad. Linc., 7, i i , 88--93).--Viiicentini ( A t t i 3. Ac. T o r i n o ,22, 1886) stated that liquid bismuth has a maximum density a t itspoint of solidification. This was contested by Liideking (Abstr., 1888,790), who found the temperature of maxiniuni density to be a, fewdegrees above the melting point.The author confirms Vincentini'sstatement by observing the expansion of an amalgam of bismuthpi-epaiwl by dissolving the metal in an equal weight of mercury. Theexperiments were conducted in dilatometers holding about 220 gramsof the amalgam, those used by previous experimenters being muchsmaller. The saturation temperature of the amalgam was 162.7",and the density was measured between 236" and 279". On examining+,he curve obtained b ~ - plotting densities against temperatures, nobreaks could be detected, the curye being practically a straight line.The author therefore concludes that liquid bismuth has a maximumdensity a t its solidifying point. The density of liquid bismuth atvarious temperatures is given below :-ncnsity ofliquid Ri.--I---I--Dcnsity ofliquid Bi.-I---10 - 22410 -21910 -21410 -80910 - 905W.J. P260 ABSTRACTS OF CHEMICAL PAPERS.Calculation of the Boiling Points of Normal IsomericEthereal Salts of the Fatty Series. By G. HIXKICHS (COW@ rend.,113, 798--800).-The boiling points of the normal fatty etherealsalts having the general formula C,H21,+,*C,H?,-,0, are plotted out incurves, the ordinates of which are proportional to khe logarithms ofthe maximum momeiits of inertia of the molecules (Conapt. Tend., 76,1592; 112, 1128), and the abscism proportional to p , that is, tothe length of the alkyl chains. Four different curves are thusobtained, corresponding to the four values 6, 7, 8, 9 of p + q, and theactual boiling points fall very fairly on them (compare Abstr., 1891,1406, 1408, 1441 ; this vol., p. 2).JN. W.Calorimetry. By P. MAHLEIZ (Compt. re?ul., 113, 174-776 j .-Theauthor has devised a cheap, efficient, and durable modification of Ber-thelot's calorimetric bomb, suitable for use in industrial m d ordinarylaboratories. The chief alteration is in the combustion chamber,which, instead of consisting of platinum, is made of mild steel,forged and turned to a suitable shape, asd enamelled inside. Themouthpiece is closed by a screw stopper packed with a lend washer.The substance under examination is supported and ignited by appa-ratus attached to the stopper, and the oxygen for the combustion issupplied a t a pressure of 25 atmospheres froin an ordinary pressurecj-linder through a stopcock screwed into the stopper.The calori-meter and agitator are constructed on the original model, with slight,modifications to reduce the cost. Trial determinations of the heat ofcombustion of naphthalene gave good results. The npparatiis isadapted f o r the study of fui=nace and other gases.Thermal Constants of Active Malic Acid and Potassiumand Sodium Malates. By G. MASSOL ( C m p t . qsend., 113,800-801).-The heat of solution of anhydrous nialic acid is -3.31 C'al., whilstthat of the monopotassium and dipotassinm salts is -5.78 Cal. and + 1.55 Cal., and that of the corresponding sodium salts -1.66 Cal.and + 1.78 Cal.respectively.The heat oE neutralisation of the acid and of the hydrogen alkalisalts is + W 2 3 Cal. and +12.85 Cnl. with potash, +24.86 Cal. and + 12.46 Cal. with soda.The heat of formation of the solid salts from the solid acid andbase, as calculated from the above data, allowing f o r the formation ofsolid water, is +29.74 Cal. and +49.15 Cal. for the moiiopotassiumand dipotassium salts, and +32.02 Cal. and +42-12 Cal. for the cor-responding sodium salts.Dipotassium and disodium malates, prepared by neutralising theanhydrous acid with alcoholic alkali, and heating the dried productsat 120" in a current of hydrogen, may be ci-jstallised, contrary to theassertion of Kammerer ( J . p?*akt. Chern., 88, 381), by dissolving i nwater, evaporating to a syrup, powdering the surface with a little ofthe anhydrous salt, and keeping over sulphuric acid for some months.Dipotassium malate crystalliscs in small needles, which are scatteredthrough a firm,.pastg mass.Disodiunz snaEate forms long, prismaticneedles containing 4 mol. H20. Mo~aopotassiim and .tnonosodiitiiz.JN. WGENERAL AND PHYSICAL CHEMISTRY. 261indates crystclllise readily with 1 mol. H,O, which is slowly lost a t120". JK. W.Heat of Formation of Hydrazine and Hydrazoic Acid. ByBERTHELOT and MATIGNOX ( Compt. rend., 113, 672-679) .-Hydrazinesnlphate, N2H4,H2S04, prepared by Curtius, was employed. Heat ofdissolution a t 10.8" = -8.7 Cal. The heat of neutralisation wasdetermined (1) by exact precipitation with barium hydroxide, and (2)by direct addition of dilute hydrochloric acid to the solution of thefree base left after separation of the barium sulphate.H,S04 diss.+ N,H4 diss. = N2H4,H2S04H,SO4 sol. + N2H4 diss. = N2H4,H2S04diss.. .............................. develops +11-1 CRI................................ cryst 7 7 f36.0 ,,ZHCl dil. + N2H4 diss. = N,HA,2HC1. diss. , Y +10-4 ,,Hj-drazine is a feeble base, like ferric oxide, and its heat of neutrali-sation is less than that of ammonia (+ 12-4 Cal. per equiv.) or evenhydroxylarnine (+ 9.3 Cal.).The heat of combustion was determined in the calorimetric bomb,the salt being mixed with a known weight of camphor.K,H,,HZSO, cryst. + 0, + Aq = HZSO,dil. + N, + 2H20 ................. develops +127.7 Cal.and consequentlj--S (octah.) + 0, + H6 + N, = N,H4,H,S04 .............................cryst.. 9 9 +220*3 ,,PI', + H4 + Aq = N2H4 diss.. 9 , - 9.5 ,, ..........The formation of hydrazine is endothermic ; its conversion into am-monia by loss of hydrogen and nitrogen is exothermic, and so likewiseis its direct conversion into ammonia by combination with hydrogen.NZH4 dil. = NH, dil. + N + H.. .. develops +25.75 Cal.3NzHA dil. = 4NH3 dil. + N, ...... ,, +32*75x3 ,,N2H4 dil. + H, = 2NH, dil.. ....... 7 , +51.5 7 ,It is clear that the direct conversion of ammonia into hydrazine isnot possible without the intervention of oxidising actions ; but, onthe otber hand, the compound may be obtained by the carefullyregulated oxidation of hydrogen compounds of nitrogen and theamides and nitrates derived from them, or by the reductioii of oxygencompounds of nitrogen and nitro- or azo-derivatives.It is noteworthy that the endothermic character of the nitrogenhydrides diminishes as the saturation with hydrogen becomes morecomplete, and this has already proved to be the case with t h eoxy-acids of nitrogen and the hydrides of carbon, thus: HNO dil.-28.7 Cal., HNO, dil.-42 Cal., HNO, dil. +14*3 Cal., and C2H2-60.4 Cal., C2H4 -14.8 Cal.. C,H, +25-2 Cal.Hydrazoic Acid.-The experiments were made with the ammoniumsalt supplied by Cui-tius. Heat of dissolution (N,H,NH,) at 11" 2ii2 ABSTRACTS OF OHEMICAL PAPERS.-7.08 Cal. Heat of neutralisation by baryta +10.0 Cal., by am-monia +8.2 Cal. Hydrazoic acid is therefore comparable to amido-benzoic acid in the energy of its acid function.Heat of combustion(in the calorimetric bomb, both with and without camphor) a t const.vol. = +163-8 Cal. ; a t const. press. +163-3 C d .N4 + IT, = N3H,NH3 ciyst.. . . . . . . . develops -25.3 Cal.N, + €II = N3H,NH3 diss. . . . . . . . . 3 , -32.3 -,N3 + H + Aq = N3H diss. . . . . . . . 7, -61.6 ,,Hydrazoic acid is the most enilotherinic of the nitrogen hydricles.It is most, probably ammonia in which two atoms of hydrogen havcbeen displaced by a ciolecule of nitrogen, NH:N2, the substitution ofthe electronegative nitrogen f o r the hydrogen conferring upon thecompound its acidic pyoperties. C. H. B.By C. M. VANI)EvENTEit and L. T. &CICIIER ( Z e d .physikaz. Chewz., 8, 536-542 ;compare Abstr., 1890, 553).-Continuing their investigations on theheats of formation of metallic salts in alcoholic solution, the authorshave measnred the heats of neutralisation of sodium and potassiuniethoxides by a number of acids in the presence of an excess of alcohol.The salts formed, with the heat evolved in each case, are given in tliefollowing table :-Sodium acetate. . . . 7.3 Cal. I Sodium chloride . . 11.2 Cal.Potassium acetate . 7.2 ,, I Sodium bromide. - . 18.4 ..Potassium biacetate 7.8 ,, i Sodium iodide . . . . . 11.2 :,Sodium benzoate.. (j.44 ,, 1The authors propose to continue theii. investigations with otherFormation of Salts in Alcoholic Solution.acids and bases. H. C.Critical Temperatures of Mixed Liquids.By G. C. SCHNlJrr{ AnnaEeiz, 266, 266--2'92).-The author has determined the criticaltemperatures of a number of mixtures of two liquids in order to testthe validity of Pawlewski's foi.mula 9i17 = --pare Ber., 15, 460 and 2460).In the place of tlie &=bath dcscribed by Galitzine (dim. Phys. C'!r.eru.[2], 41,6231, the author employed :L beaker, 250 mm. in height and about60 mm. in diameter, which was half filled with paraffin; the liquidwas contained in a small scaled tnbe which was attached to a thermo-meter placed in R paraffin-bath ; the temperature a t which the liquidcompletely disappeared and thc tempemture at the moment of thereappearance of the meniscus were both noted. Very good resultsare obtained with this apparatus, but it can only be employed fortemperatures below 260", as t h o paraffin darkens very rapidly whenheated more strongly.The experimental values obtained in this way were in some casesrather greater, in others rather less, than those calculated byPawlewski's formula, tahe maximum difference being 3.9" ; as, in tllc?I3 + (100 - 49' (colll-10GENERAL AND PHYSICAL CHEMISTRY. 263Case of any particular mixture, tlie differences were, aR a rule, eitherall positive or all negative, i t would seem that Pawlewski's formula isnot quite accurate ; it is possible, however, that the deviations fromthe calculated values are due to a slight decomposition of one or bothliquids.The observed and the calculated critical temperatures of the mix-tures are given in tables.Vapour Pressure of Aqueous Solutions of Cobalt Chloride.By G.CHARPY (Compt. vend., 113, 794-795).-The cnrve showingthe variation of the vapour pressure of 32 per cent. aqueous cobaltchloride with the temperature comprises two approximately rectilinearportioils, one ranging from 2W t o 40", and corresponding with the redmlution, the other ranging above 75" nud corresponding with the bluesolution. The intermediate portion is curved. These fncts point tothe existence of two stable modifications of the salt, perhaps hydratesor other molecular aggregates. The c u i w is similar to that obtainedby Jhard from a consideration of the so1ubilit)y of the chloride, butthe intermediate limiting temperatures am not, t h e same, thoseobserved by Ward being.:?5" and SO"; this, however, is probablyaccounted for by the fact that lie dealt throughout with saturatedsolutions. Jx. W.Pressure and Specific Volume of Saturated Vapours. By C.Dw, LUXGO (Herid. h a d . Linc., 7 , i, 141--145).-The equationlog p = k - - - b log T, where p is the pressure, T the absolutetemperature, and a, z1, and 7; are constants, is derived by Bertram1(Thermodpanzique, 1887, 93) from Boylc'~ law and equations givenby Clapeyron, Clausius, and Regiiault. From the same sources thea' author derives the equation log B = li' + + b' log T, where s is thcApecific volume of the saturated vapour. The specific voliime~ ofcarbon bisnlphide vaponr a t different temperatures calculated by thisformula agree well to the third decimal place with the values given byHirn.The function p = 0 when T = 0, and then increases until thecritical temperature i R reached, when T = a/b, after which i t decreasesindefinitely, and has no further physical significance. Similarly 8 isinfinite when 1' = 0, and decreases to a minimum at the critical tem-perature, when T = a'/b'. For the same vapour, therefore a/b =a'/b'.Zeuner's equation, prr = constant, where n is a constant such thata = nur and b = nb', may bc a t once deduced from the above twoequations. W. J. P.The Freezing Points of Aqueous Solutions of Boric Acid andMlannitol. By G. MAGNAXISI (Gozzetta, 21, ii, 134--141).-A Rtudyof the electrical conductivities of aqueous solutions of boric acid ant1mannitol has already enabled the mthor to determine the compositionOP the compound of the two substances which exists in solutioii(Abstr., 1890, 1357) ; 110 cluc was, however, obtained to the amountof the compound produced.F.S. K.aT'264 ABSTRACTS OF OHEMIOAL PAPERS.An investigation of the solutions by the cryoscopic method showsthat the number of molecules existing in an aqueous solution contain-ing both boric acid and mannitol is abont 5.4 per cent. less than itwould be if no combination occurred, the cryoscopic constant of thesolvent for water (16.5) being diminished by 5.4 per cent. in solutionscontaining bot,h constituentq whilst for solutions only containing oneof the substances, the constant is considerably increased in value.The author has also determined the electrical conductivity at differ-ent temperatures (20-50") of solutions containing boric acid andmannitol in varying proportions, and finds that the conductivitydecreases b r about 6 per cent., with a rise of temperature of 30"(20-50"); the rate of decrease is almost tlie same for differentlyconstituted solutionP. The author considem that this abnormalchange in the condcctivity of such solutions is only apparent, thediminution in conductivity with rise of temperature being clue toincreased hydrolytic dissociation.The true temperature coefficient ofthe electrical conductivity is, therefore, most probably positive. Asa rise in temperature causes a decrease in the amount of the com-pound of boric acid and mannitol in the solution, the formation ofihis substance is probably accompanied by development of heat.W.J. P.The New Theories of Solution. By J. WALKER (PhiZ. Mug. [5],32, 355-365) .-This paper contains a reply to some of the objectionsadvanced by Pickering against the theories of osmotic pressure andof electrolytic dissociation. The author doubts if Pickering's deter-mhations of the freezing point of sulphuric acid solutions (Trans.,1890, 331) have the degree of accuracy claimed for them, and givesan example t o shorn that the " potential dissociation " advocated byLodge is insufficient to explain tlie known facts of electrolysis.Change of Volume on Dissolution. By J. A. WAKKLTN, W.JOHNSTONE, and W. J. COOPER (P7i,iZ. J h g . [ 5 ] , 32,473-477).--WheiiR solid dissolves in water, one of three things may happen withrespect to the volume.The volume of t,he solution may be equal tothe sum of the volumes of the dissolved substance and the water, ori t may be greater, or it may be less, as is usual. When there is con-traction, the authors measure it by the weight of water, which, insteadof overflowing from a vessel of 100 C.C. capacity filled with water, isretained when 1 gram of salt dissolves so as to give 100 C.C. ofsolution. In the case ofmgar there is no condensate, as there is no change of volume. Withsome ammonium salts there is expansion, and the condensa,te is cou-sequeiitly negative. The authors state that, " i n the case of verymany salts, the condensate bears an atomic relation to the gram ofsalt which occasions i t " (compare Sbstr., 1891, 1412).Mutual Solubility of Salts in Water.By J. E. TREVOR (Phi,?.lllug. [.5], 32, 75-78).-With reference t o Nicol's paper under theabove title (this vol., p. 8 ) , the author draws attention to the fact thatthe problem therein discussed has received a theoretical solution, withexperimental confirmation f o r many cases, from the work of Nernst,J. W.This constant they term the " condensate."J. W.Noyes, and himself. J. wGENERAL AND PHYSICAL CHEMISTRY. 265Solubility of Mixed Crystals, especially of two IsomorphousSubstances. By H. W. B. ROOZEROOM ( Z e d . yhysikab. Chenz., 8,504-530) .-According to the rules laid down by Gibbs for equilibriumbetween three phases, two of which are solid salls and the other theirsolution, the composition of the saturated solution at constant tem-perature will be dependent on the pressure.Experiment up to thepresent has confirmed the above for a number of solutions of mixedsalts, but there are a number of exceptions where the salts taken arecapable of forming a double salt or an isomorphous mixture, Theexception has been shown to be only an apparent one in the case ofdouble salts by the author’s investigation of the behaviour ofastracanite (Abstr., 1888, 1164). Riidorff’s researches on the solu-bility of mixtures of isomorphous salts have, however, placed itbeyond doubt that the composition of their solution is variable, andnot constant, for constant pressure, even when excess of both salts ispresent.The explanation of this behaviour must be sought in the factthat the isomorphous salts combine with one another to form homo-geneous mixed crystals, the equilibrium coiiditions being thus altered.This difference between isomorphous and other mixed salts is of im-portance, as it is evident that the solubility of mixed salts becomes acriterion of their isomorphism, but, before this property can be madeany extensive use of, it will be necessary to establish the conditions ofequilibrium existing between isomorphous mixtures and their solutions.If, with Van’t Hoff (Abstr., 1890, 1044), we regard isomorphousmixtures as solid solntions, the dissolution of the mixed crystals maybe compared with the evaporation of a liquid made up of two com-ponents, both of which are volatile.Osmotic pressure then takes theplace of vapour pressure, and, in place of the concentration of theliquid solution, that of the solid solution must be taken. I f there areN molecules cf the one salt, and n molecules of the second withosmotic pressurep, in the solid solution, then we get, as the expres-sion €or the law of Henry, kp = n / ( N + n), or, since saturation iscomplete when the osmotic pressure of the solid is equal to that of thesolution, if the second salt is present in the solid in the molecular pro-portion x per cent., and if in the saturated solution the concentrationis represented by c2 molecules, then l i c 2 = z. This, of course, assumesthe absence of electrolytic dissociation. It also assumes the identity ofthe solid and liquid molecule, but if this is not the case, and *n of thelatter combine to form one of the former, the formula becomeskcz = 2’1.If x becomes smaller during solution and greater during the separa-tion of the mixed crystals, the solution will be richer in the com-ponent x than the crystals.Hence, if the osmotic pressure of asaturated solution of mixed crystals increases or decreases withincreasing proportion of one of the components of the mixed crystals,the ratio of this component to the other in the solution will in theone case be greater, and in the other less, than in the mixed cryfitals.This enables a distinction to be made of the possible cases duringeolution or crystallisation of mixed crystds.If the mixed crystals are miscible in all proportions, three casts1 266 ABSTRACTS OF BHEMIOAL PAPERS.are possible.The osmotic pressure of the saturated solution is 8continuous function of the concentration, and may either incl-easecontinuously wit.h the concentration, it may increase to a maxi-mum and then fall, or it may fall to a minimum and then rise. Intlie first case, on evaporation of a solution of the two constituents, thecrystals separating out would contain increasing quantities of thatcomponent the saturated solution of which had the greatest osmoticpressure, until at length nothing but a solution of this component wasleft. In the second caRe, the crystals would be of varying composition,until a point is reached corresponding with the maximum, when thecomposition of the crystals would be the same as that of the solution.The third case would be similar in character to the second.If the mixed crystals are not miscible in all proportions, theosmotic pressure is no longer a continuous function of the concentra-tion.The curve for the pressure as a function of the concentrationwill then be represented for a certain portion of its length by astraight line, parallel to the abscism axis, and terminating at one endwith a certain limiting value of the concentration of the one constitu-ent, and at the other end with a certain limiting value of the otherconstituent in the mixed crystals. Prom these end points to thepoints representing the pressures of the saturated solutions of thepure component8, the curve may take various forms.Some of theseare considered by the author, and he points out that isodimorphousmixtures probably all give a discontinuous curve of the above form.H. C.Solubility of Mixed Crystals of Potassium and ThalliumChlorates. By H. W. 13. ROOZEBOON (Zeit. physiknl, Clzem., 8,5.71-535).-The author has determined the solubility of mixtures ofpotassium and thallium chlorates i n varying proportions. He findsthat these salts present one of the cases considered in a former paper(preceding abstract) of mixed crystals which are not miscible in allproportions, and obtains results which generally confirm his theoreti-cal conclusions. H. C.Affinity Coefficients of Organic Acids and their Relation toChemical Constitution. By P.WALDEN (Zed. physiknl. Chem., 8 ,433--503) .-The author has determined the affinity coefficients of alarge number of dicarboxylic acids from the conductivities of theii-aqueous solutions (see Ostwald, Abstr., 1889, €418). The values ob-tained f o r K = lOOk are given in the following tables :-I. MALONTC ACID AND ITS DEB~VATITES.Dimethylmalonic acid. . .Methylmatonic acid. . . . .Isobutylmalonic acid. . . .Butylmalonic acid . . . . . .Propylmalonic acid. . . . .Isopropylmalonic acid. . .Ethylmalonic acid . . . . . .Benxylmalonic acid . . . . .Ally lm alonic acid. . . . . . .0.0760-0860.0900-1030-1120.1270.1270.1510.154Ethylmethylmalonic acidMalonic acid ., . . . . . . . .Diet,hylrnnlonic acid . . . .Diallylmalonic acid . . . . .Benzy let hylmalonic acid.Dibe~zylmalonic acid . . .Chloromalonic acid.. . . . .Benzyltartronic acid . . . .0.1610.1630.740.761-484.14.00-5GENERAL AND PHYSICAL CHEMISTRY.Sncciiiic acid. . . . . . . . . . 0.0068Isopropylsuccinic acid. . 0.0075Ethylsuccinic acid. . . . . 0.008-5Methylsuccinic acid. . . . 0.008626 7Isobixtylsiiccinic acid. . 0.008822Propylsnccinic acid . . . 0.00886Benzylsuccinic acid I . . 0.0091Allylsuccirlic acid. . . . . 0.109Trimethylsiiccinic acid . 0.0307Benz yldimeth ylsuccin icacid ..... .. ...... .. 0.0455A ntidime thylsiiccinicacid . . . . . . . . . . . . . . .Paradimethylsuccinicacid . . . . . . .. . . . . . . .u-E t,hylme thyls u ccinicacid. . . . . . . . . . . . . . . .Pare t h ylme thylsnccinicacid . . . . . . . . . . . . . . .Paradiet hylsucciiiic acidAntidiethylsuccinic acidDiethylsuccinic acid ( 3 )Parallylethylsnccinic acidp-Allylethylsuccinic acidp-Phenylmethylsnccinicacid . . . . . . . . . . . . . . .Pnraphenylmethylsncci-nic acid . . . . . . . . . . .PropyldimetliSlsuccinicEthyldimethylsuccinicacid .......... .. .. ..acid . .. .. .. ........0.05510.05560.01230.01910.02010,02070,02450,03430-03860.02690.03590.02330.0372,Paraben z ylmethylsucci -iiic acid . . . . . . . . . . . .p-Benzyliiiet h ylsuccinicacid . . . . . . . . . . . . . . .Pai.abeiizyletliylsuccinicacid. . . . . .. . . . . . . . . .~~-Benzylethylsnccinicacid . .... I ....... ..ParadiphcnSlsnccinicacid . . . . . . . . . . . . . . .Ant id iphcny lsuccinicacid . . . . . . . . . . . . . . .Antidilly droxysuccinic(inactive tartaric) acidParscli hydroxysnccinic(tartaric) acid . . . . . .Dextrotnrtaric acid . . .Laxotartaric acid.. . . . .0.02100.02470.02Ci20.04140-02000.0260.0600.0970.0970.097111. GLUTAIZIC AXI) PI~IIELIC ACIDS ASD THEIR DERIVATIVES.Glutaric acid.. . . . . . . .cc-Methylglut.ayic acid .Paradimethylglutarkacid . . . . . . . . . . . . . .Antidimethylglutaricacid . . . . . . . . . . . . . .Bfetapropylrnethylglut-aric acid . . . . . . . . . .Paradiethylglutaric acidMete thylmethylglut -wic acid .. . . . . . . . .13-Methylglutaric acid .Parethylmethylghtaricacid . . . . . . . . . . . . . .0.004750.00520.00550.00550-00540.00550-00560.00590.0059Benzylmethyl glutaricPimelic acid :From suberone, Schor-lemmei.. . . . . . . . . . . .From castor-oil, Hell.. OmO0348From pentanetetracarb-oxylic acid, Perkin.. 0.00345Of unknown origin, Ost-wald.. . . . . . . . . . . . 0.00357p-Pimelic acid, Arth.. . 0.00420Pirnelic acid from smy-acid .. .. .. .. .... .. 0.00590.0032lene bromide :( a ) Bauer ...... .. 0.0097( b . ) Hell . . . . . . . . . 0.0091 I Perapropylmethylglut-aric acid . . . . . . . . . . OmO052 68 ABSTRACTS OF CHEMICAL PAPERS.IV. UNSATL'RATEII D~BMC ACIDS.Methylitaconic acid.. .. 0.0095Ethylmethylrnale'ic an-Pyrocinchonic anhydride 0.01081 taconic acid ..........0.0120Benzylglutaconic acid. . 0.0153Glutaconic acid ....... 0.0183Mesaconic acid ........ 0.0794hydridc ............ 0.0097Fumaric acid .......... 0.093Methylmesaconic acid. .. 0.094Ethylmesaconic acid .... 0.093Isopropylmesaconic acid . 0.093Methylcitraconic acid. ... 0.238Citraconic acid ......... 0.340Mnle'ic acid ............ 1-17It will be seen that, with the exception of dimethylmalonicacid, all the di-substitn tion compounds of inalonic acid have higheraffinity coefficients than malonic acid itself. The mono-alkyl deriva-tives, on the other hand, have smaller coefficients than the parentacid. In the cases of succinic acid, the mono-alkyl derivatives arebetter conductors than the free acid, the di-derivatives better thanthe mono-derivatives, and the tri-derivatives better than the di-derivatives.When succiiiic anhydride is dissolved in cold water, theelectrolyte obtained is identical with ordinary succinic acid, andno evidence of the existence of a second snccinic acid is obtained.The author points out that the antidihydroxy-, antidimethyl-, andu-ethylmethyl-succinic acids have smaller coefficients than the corre-sponding para-acids. It would, therefore, appear possible, althoughin opposition to the accepted view, that the first contain the malei'noi'd,and the second the fumaro'id, grouping.Chemical Action at a Distance. By W. OSTWALD (PAiZ. llILtg.[ 5 ] , 32, 145--156).-A short glass tube of about 2 cm.diameter,closed below with parchment paper, is introduced into a small beaker.Both these vessels are filled with a solution of potassium sulphate,-are being taken that the level of the liquid i n the tube is higher t h mthe level in the beaker. A rod of pure zinc is dipped into the solutionin the tube, and connected electrically with a piece of platinum wire,which reaches to the bottom of the beaker. A few drops of it solutionof sulphuric acid specifically heavier than the potassium sulphatesolution are then carefully brought with a pipette upon the bottomof the outer vessel, so as not to come into contact with the parchmentdiaphragm. Hydrogen is a t once evolved on the platinurn, and Rsubsequent investigation of the solution in the inner vessel shows thata quantity of zinc has dissolved in the potassium sulphate solution aszinc sulphate.Such an action as this, where the specific solvetrt fora metal (here zinc) is applied at a place where it can have no directaction and yet exerts its solvent power, is termed by the author achemical action a t a distance. Many instances of similar phenomenaare given. For example, gold may be dissolved in a solution of com-mon salt, by bringing the platinum with which it is connected intocontact with a salt solution saturated with chlorine. Again, if twomakers-one containing a solution of ferrous chloride, the other asolution of common salt saturated with chlorine or bromine-areconnected by means of a siphon filled with salt solution and closed atH. CGENERAL AND PHYSICAL CHEMISTRY.269both ends with parchment paper, then on introducing platinumelectrodes into the beakers and coniiecting them through a galvanadmeter, a current is at owe indicated, and the ferrous chloride becomesoxidised to ferric chloride in the neighbourhood of the electrode, asmay be shown by the previous addition of a little potassium thiocyanatesolution.All such reactions receive a ready explanation from the theory ofelectrolytic dissociation, the author laying emphasis on the fact thatthe description of many of the experiments made by him waR com-pletely worked out at his writing table, on the basis of this theory,before he had Been any of the phenomena in question ; and that afterthe experiments had been performed, nothing in the descriptionrequired to be altered.Chemical Action at a Distance. By S. U. PICKERING (Phil.*Wag. [5], 32, 478).-The author holds that a simple explanation ofOstwald's experiments (see preceding abstract) may be obtainedwithout having recourse to the theory of free ions in solution, and that,therefore, these experiments cannot be accepted as proofs of this theory.By 0. LEHMAYN (Zeit. pkysikal.Chem., 8, 543-553) .-Senarmonti discovered that salt crystals maybe coloured by certain organic dyes without any change in the formor homogeneity of the crystal. The author has on former occasionsmade similar observations with other inorganic and organic com-pounds, and in order to ascertain something more with reference tothe conditions under which this phenomenoii takes place, has nowmade a large number of experiments on the artificial colorationof crystals. The crystals made use of were those of certain organicacids, such as succinic, protocatechuic, and phthalic acids, andtheee were coloured by means of different organic dyes. The authorsummarises his results as follows :-The crystals always become darker in colour than the solution fromwhich they separate. They are usually observed to be surrounded bya lighter coloured, or even quite colourless, layer, the colouringmatter being deposited with such rapidity upon the growing crystalthat the slow diffusion of the dye from the more distant parts of thesolution is not sufficient to make up for the decreasing concentrationin the neighbourhood of t,he crystal.The colouring of' the crystals is in nearly all cases dichroic, a proofthat the colouring matter actually enters in some way into the struc-txre of the crystal. The remarkable rule is observed that only oneof the two rays produced by double refraction is coloured, whilst theother appears to be perfectly white, the colonrless ray being alwaysthe one which has undergone the least refraction.If two colouring matters are present in the solution, the presenceof the one often hinders the absorption of the other. In some cases,however, the reverse takes place, and a colouring matter which alonewould not be absorbed may become so when some second colouringmatter is added. Change of the solvent, or the addition of other solidor liquid foreign matter, msy act in a similar manner.J. W.s. u. P.Artificial Colouring of Crystals.VOL. LXII. 22 70 ABSTRACTS OF CHEMICAL PAPERS.Different crystals are only capable of taking up certain organicdyes, so that two compounds of perfectly similar appearance may becapable of combining the one only with one, and the second only withsome other dye. This fact may obviously be made available in dis-tinguishing crystals one from another. It may also perhaps beapplicable for the purification of certain dye stuffs.Rapid Weighing on Precision Balances by means of a Scaleread by a Microscope. By A. COLLOT ( B d . SOC. Chim. [3], 6,98--100).-The needle of B balance carries a scale illuminated frombehind the balance, and viewed by a small microscope containing a, scalein the focal plane of the eye-piece. The centre of gravity of the beammay be lowered considerably, and t h u s the rapidity of oscillation ofthe beam increased materially by the aid of this device. The valueof each division of the scale carried by the needle being knownin centigrams and milligrams, the position of rest of the indicator isascertained by the method of oscillations, and from its deviation fromthe central point the weight t o be added t.0 that in the pan is known.With a little care, weighings only take one-fourth or one-fifth aslong by this method as they usually do.A Siphon for Hot Liquids or for those Evolving Gases orVapours. By 5. C. ESSPI’EIE (Bull. SOC. Chim. [3], 6, 19-21).-Between the two arms of the siphon 5 yeservoir is interposed ; this isfilled with some of the liquid to be siphoned, and hermetically closed.When the long arm of the siphon is opened, the fall of the liquid de-termines a diminution in the pressure of the reservoir, and a continuousflow results. T. G. N.H. C.W. T

ISSN:0368-1769    

DOI:10.1039/CA8926200253

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

2 70 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h e m i s t r y. Preparation of Pure Hydrogen Peroxide Solution. By L. CR~SMER (BUZZ. Soc. Chim. [3], 6, 24--25).-The solution of hydrogen peroxide which results from the action of hydrochloric acid (sp. gr. 1.1) on barium dioxide is extracted by shaking with ether, and the ethereal solution is agitated with distilled water, to which it yields the dissolved hydrogen peroxide. By repetitions of this process, a pure, neutral solution corresponding with 0.8-0.9 per cent of hydro- gen peroxide is obtainable, from which the dissolved ether may be eliminated by distillation under reduced pressure. Preparation of Hydrobromic Acid. By G. S. NEWTH (Chena. News, 64, 215).-By means of the following arrangement a large quantity of bromine can be rapidly converted into hydrobromic acid :- A glass tube, 7 inches long and 8 inch in diameter, is fitted at each end with a cork carrying a piece of small tubing and a piece of fitout wire.The ends of these pieces of stout wire, within the longer tube, T. G. N.INORQANlO OHEMISTRY. 271 are joined hy a spiral of platinum wire 1 inch long, and after expelling the air the spiral is heated to bright redness by Rn e1ecOric current; a stream of hydrogen, impregnated with bromine by bubbling through that liquid, which may be heated at GO", is passed through the longer tube, and, as long as a Blight excess of hydrogen is maintained, hydro- bromic acid quite free from bromine issues from the other end, and is collected in water. There is very little danger of explosion, but t o render it impossible, the small supply tube may be plugged with a little glass -vr7001.Solubility of Gases in Water. By I;. W. WINKLER (Ber., 24, 3602-3610; compare Abstr., 1891, 384).-In this paper the author gives in tabular form the results of experiments on the solubility of nitrogen and of oxygen in water, a t temperatures ranging from 0" to 80"; the calculated values for the solubility of the two gases at temperatures ranging from 80--100" are also given. As regards the solubility of nitrogen, the author's values are considerably larger than those given by Bunsen. The Densities of Sulphuric Acid Solutions. By S. U. PICKER- ING (Chem. News, 64,31l).-Lunge's doubts as t o the accuracy of the author's density determinations are, in the opinion of the latter, due to a misapprehension as to the method employed to determine the strength of the acid, and as to the experimental error involved.D. A. L. E'. S. K. s. u. P. The Contraction on Mixing Sulphuric Acid and Water. By S. U. PICKERING (Chem. Netus, 64, 14--15).-From his own results the author has calculated the strength a t which the maximum contraction occurs, and finds that this maximum, when calculated for unit weight of solution, shifts from 67 per cent. at 8" to 70.1 per cent. at 38", whereas the maximum contraction calculated per unit volume remains practically constant at 76 per cent. throughout this range of tempera- ture. Neither of these maxima occurs at the composition of the di- hydrate (73.1 per cent.) or of that of any other hydrate of which indications have been obtained.The rate atr which the amount of contraction is influenced by the temperature varies irregularly with the actual value of the temperatnre ; tlhus with solutions from 64 to 80 per cent. st,rength, the contraction diminishes at nearly the same rate for the intervals 8" to 18", and 28" to 38", whereas for the inter- mediate interval, 18" t o 28", the rate of diminution is about 25 per cent. smaller. s. u. P. Density and Composition of Dilute Sulphuric Acid. By A. W. R ~ C K E R (Phil. Mug. [ 5],32,304-313) .-Pickering (Trans., 1890, 64) deduced the existence of various hydrates in sulphuric acid solu- tions from sudden changes of curvature in the curves representing the variation of the density, &c., of such solutions with the composition. The author considers the " first diflerential " curve for 18" between 46 per cent.and 80 per cent., in which there are supposed to be f o u r breaks, and shows that it is possible to find an equation, and, therefore, a continuous curve, which will represent the results within the limits of the experimental error. The equation is of the form u 2272 ABSTRACTS OF OHEMIOAL PAPERS. and contains fieven ai-bitrary constants. The author thus doubts the value of '' differentiation " or of the bent ruler, as used by Pickering, in discovering changes of curvature in curves drawn to represent experimental numbers. J. W. The Densities of Sulphuric Acid Solutions. By S . U. PICKERING (Phil. Xag. [ 5 ] , 33, 132).-The curve used by RiicBer (see preceding abstract) to bridge over four of what the writer con- sidered to be breaks in the figure foymed by the first differentials of the densities of the acid can, he maintains, prove nothing about one of these breaks, and very little about another, for it extends too short a, distance beyond them.The formula for the curve suggested by Rucker consists of a combination of an exponential curve and a straight line, on to part of which (as this curve did not agree with the results) a hump was engrafted by means of a complex fourth term, tlhe whole forming a curve for which, as an expression of physical facts, there would seem to be no precedent. The points, moreover, at which the term expressing the hump begins to be appreciable and again becomes inappreciable correspond exactly with the positions assigned by the author to two of t,he breaks, thus confirming, rather than disproving, the existence of these as points where some new conditions in the solutions become sensible.The only break which Bucker's curve does successfully bridge over is that particular one which the author pointed out to be especially doubtful: and even in favour of this break the evidence is not thereby entirely negatived. The author maintains that even the most successful attempt to offer an alternative explanation of a small portion of some of his results could not upset his conclusions which were based entirely on the cumulative evidence derived from many sources, and of which he here gives a summary. s. u. P. Boron Phosphides. By H. MOISSAN (Compt.rend., 113, 726- ~29).--Bo~on phosphide, PB, is obt,ained by reducing the phospha- iodide in hydrogen at 450-500". The product is powdered, and again heated in hydrogen at the same temperature in order to remove excess of iodine, and the process is repeated two or three times if necessary, care being taken that the temperature does not exceed 500". I t is a very light, amorphous, maroon-coloured powdel., insoluble in the chlorides of arsenic, phosphorus, carbon, and anti- mony, and in all solvents, organic and ino~ganic, that were tried. It is n o t volatile in a, vacuum at 500". At 200", in presence of oxygen, it burns and yields boric and phosphoric anhydrides ; when thrown into fused alkaline nitrates, there is incandescence and deflagration ; fused sulphur has no action, hut sulphur vapour converts it into boi-on and phosphorus sulphides.Chlorine converts boron phosphide into boron trichloride and phosphorus pentachloride, with incand- escence ; bromine has no action in the cold, but combination takes place if the temperature is raised. Vapour of iodine, arsenic, orINORQANIC CHEMISTRY. 273 phosphorus has no action at a dull-red heat. When heated at 5OO"in a current of nitrogen, boron phosphide yields no nitride, and, although a,t higher temperatures it loses phosphorus (as it does in a vacuum), no nitride is formed. When a mixture of boron phosphide and sodium is gently heated in a current of hydrogen, it rapidly becomes incandescent, with formation of sodium phosphide and boride. Potas- sium yields the same products at a lower temperature.A mixture of the boron phosphide with powdered magnesium becomes incand- escent at about 500", but aluminium has no action, except at a much higher temperature. Finely-divided silver, copper, and platinum react with the phosphide when gently heated, biit mercury has no action at its boiling point. When boron phosphide is thrown into the strongest nitric acid, it takes fire, even in the vapour, and burns brilliantly on the surface of the liquid; on slightly heating, it dis- solves immediately and completely. Concentrated solutions of hydro- chloric and hydriodic acids have no action on the phosphide, and sulphuric acid has no action in the cold, but is reduced on heating. Concentrated hot solutions of potash and soda dissolve i t slowly, whilst fused potash dissolves it completely with formation of hydrogen phosphide and potassium borate.Gaseous hydrogen fluoride attacks it below dull redness, with formation of boron fluoride, hydrogen, and phosphorus. Gaseous hydrogen chloride behaves similarly at R higher temperature. Boiling water has no action on the phosphide, but water vapour decomposes it at 400" with production o€ boric acid and hydrogen phosphide. Hydrogen sulphide at A dull-red heat yields boron sulphide and hydrogen phospliicle. I n ammonia at about 300" the phosphide burns, with formation of boron nitride and libera- tion of phosphorus. Boron phosphide, B5P3, is obtained by heating the preceding com- pound at 1000" in a current of hydrogen. It has a paler colour than the phosphide PB, does not inflame in chlorine or nitric acid, and is not attacked by the latter, even when boiling.It is insoluble in all inorganic and organic solvents, burns with some difficulty in oxygen, and is attacked by fused nitrates with incandescence, but only with difficulty by metals and non-metals. It does not burn in chlorine below a dull-red heat. I f the hydrogen used for reduction contains water or oxygen, a white phosphoboric acid, also known as boron phosphate, is formed, and the same compound is obtained by the action of nitrogen oxides on a mixture of the phosphides. Boron Phosphide. By A. BESSON (Compt. Tend., 113, 772-7731, -The author draws attention to his previous note on the subject (Abstr., 1891, 1418), and describes 'an additional property of the phosphide.It is oxidised by dilute nitric acid to a substance, prob- ably phosphoboric acid, which is left in nacreous plates on evaporating the solution to dryness, is soluble in water, and gives a white, gelatin- ous precipitate with excess of ammonia. Moissan (ibid., 787-788), commenting on this and the previous note, draws attention to the absence of numerical data justifying the formula, BP attributed to the phosphide, and claims priority in the C. H. B.274 ABSTRACTS OF CEEMTOAL PAPERS. Rystematic study of boron phosphides (Compt. rend.! 112, 71 7, and 113, 19). JN. w. The Influence of Steam and other Gases on the Combustion of Carbonic Oxide and Oxygen. By N. BBK~TOFF (Ckenz. Centr., 1831, ii,449-450 ; from Bull. Acad. St. PrStersbourg [2], 2, 175-179). -Having repeated Dixon's experiments (Trans., 1885,94), the author has obtained the same results, namely, that, a mixture of carbonic oxide and oxygen, when dried by nieans of phosphoric anhydride, is not exploded by the passage of an electric spark, and further, that if the gases be dried by sulphuric acid, which appears to leave a trace of moisture in the gas, the combustion proceeds so slowly that it may be followed with the eye.The presence of other gases, sulphurous anhydride, o r nitrous oxide, had not a similar effect. Cyanogen, on the other hand, when present to the extent of 10 per cent., exerted an influence similar to that of steam, and caused an immediate explosion on the passage of the spark. BBkbtoff suggests that the action of cyanogen may be explained on the assumption that the beak liberated in the decomposition of the cyaiiogen is added to the heat of conibustion of the carbon, and he further assumes that the dissociation tempern- ture of the water niolecule being lower than that of the oxygen molecule is the proper explanation of the fact that the presence of water in a mixture of carbonic oxide and oxygen assists the com- bustion of the latter gases.J. W. L. Reactions of Carbonic Anhydride at High Pressures. By A. D'ARSONVAL (Conzpt. rend. SOC. Biol., 1891, 320--321).--Liquefied carb- onic anhydride is a powerful antiseptic. It does not coagulate albu- min. At high pressures it can displace both organic and mineral acids. When urine is subjected to a pressure of 40 atmospheres of carbonic, anhydride, crystals of uric acid are deposited.A dilute solu- tion of potassium silicate similarly treated becomes solidified from the deposition of silicic acid. Carbonic anhydride at the same pressure is also able t o liberate hydriodic and hydrobromic acids from solu- tions of potassium iodide and bromide respectively. By N. BEKBTOFF (Chenz. Centr., 1891, ii, 450-451 ; from Bull. Acad. St. Pe'tersbourg [2], 2, 169--17G).-The author has prepared considerable quantities of cssium by redncing the hydroxide with aluminium. The reaction proceeds well, and is as readily carried out as the reduction of rubidium. The author refers t o the results, which Winkler has recently published, on the heat of combination of the alkali metals, and points out that the deductions which Winkler has made are diametrically opposed to his own.The author finds that the combining heat of the alkali metals varies inversely with their atomic weights. He further urges that Winkler has not employed the oxides, but the hydroxides and carbonate5, for his determinations, which are not suitable for the purpose. Properties of Czesium and its Hydroxide. By N. BEKETOFF (Chem. Centr., 1891, ii, 451 ; from Bull. Acad. St. Pe'teysbourg [SJ, 2, W. D. H. Reduction of CEsium. J. W. L.INORGANIC CHEMISTRY. 275 171--173).--The author has used a very pure specimen of caesium sulphate as material on which t o work. A determination of the sulphnric acid gave almost the theoretical amount, and by means of the spectroscope only a trace of rubidium could be detected.The hydroxide was obtained from the sulphate by precipitation with barium hydroxide, and concentration of the filtrate in a silver dish, which was placed in a metal retort. In this manner carbonic an- hydride was excluded. After concentration in the retort, the solution was transferred to a small silver dish, the remainder of the water evaporated, and the hydroxide finally fused. The silver dish was slightly attacked, and the silver oxide dissolved in the fused caesium hydroxide ; it was again precipitated, however, as the latter cooled. The quantity of silver oxide was inconsiderable. Cmium hydroxide has a sp. gr. 4.0178, compared with water at 4" ; the molecular volume = 57.3 (sodium hydroxide = 18 ; potassium hydroxide = 27 ; rubidium hydroxide = 32 ?).The molecular volume of the hydroxide corresponds with a very considerable diminution of volume during its formation from the elements. The heat of solution of the hydroxide in water is 15,876, which is higher than f o r all other alkali hydroxides. The heat of neutralisation of the hydroxide with hydrogen chloride (dilute) is 13,790, or nearly the same as that found by Thomsen for potassium hydroxide, or, indeed, for the other alkali hydroxides. Metallic cEsium was obtained by heating 114 grams of the hydroxide in a nickel retort wit,h 27 grams of aluminium, and collecting the distilled metal in glass receivers; 20-25 grams of the metal were thus obtained. The heat of combination of cmium with water was found to be from 50 to 53 Cal. J. W. L. Action of Sodammonium and Potassammonium on Metals.By JOAXNIS (Cornpi!. rend., 113, 795-798).- Sodammonium and potassammonium are decomposed by mercury, lead, and antimony, but are not affected by aluminium, silver, zinc, or copper. When a solution of sodammonium in liquefied ammonia is allowed to fall drop by drop on mercury, it is decomposed with the formation of a crystalline amalgam, Hg,Na, which can be washed free from excess of the reagent with liquefied ammonia. Potassammonium under similar conditions yields an amalgam of the composition Hgl8K. When pure lead is brought into contact with sodammonium, the reddish-brown liquid turns blue, and then green, and a little hydrogen is disengaged, owing to the spontaneous decomposition of the sod- ammonium. Finally, however, the metal is partially converted into an indigo-blue mass, which dissolves in liquefied ammonia to a bottle- green solution, and has the composition Pb4Na,2NH,.This substance decomposes at ordinary pressures, leaving a grey mass resembling spongy platinum, and oxidises rapidly on exposure to air, with evolu- tion of heat. When thrown into water, the first portion dissolves completely, owing to the combination of the lead with the dissolved oxygen, and the subsequent solution of the oxide in the sodium hydroxide simultaneously formed, but as soon as the oxygen is used up, metallic lead is thrown down as a black, curdy precipitate. JN. W.276 ABSTRACTS OF OHEMICAL PAPERS. Influence of Ammonia on the Solubility of Ammonium Chloride. By R. EXGEL (BUZZ. Xoc:Chim.[3], 6, 17).-The pre- sence of ammonia diminishes the solubility of ammonium chloride in water at 0' at first, but as the quantity of ammonia is increased, a corresponding increase in the chloride dissolved obtains. This result is probably due to the formation of compounds of ammonium chloride and hydroxide. Tables of values are given. T. G. N. Precipitation of Copper by Iron and the Action of Iron on Ferric Solutions. By J. C. Essmit (BdZ. SOC. Chin%. [ 3 ] , 6, 147- 148) .-In the wet method of copper extraction, very mixed qualities of acrap iron are employed. The reduced copper occurs in powder, grains, and filaments which cannot be readily washed free from the mud of ferric hydroxide formed. The author finds that the structure of the iron used exerts a marked influence on that of the copper obtained.By selecting the iron to be used, it is possible to obtaiii the reduced copper in a fibrous or granular condition, when i t admits of being readily washed free from ferric hydroxide. The occurrence of the mud of ferric hydroxide is due to the form- ation of a basic ferric sulphate, Fez(OH)aS04. This salt is decom- posed by iron as follows :-6Fe2(0H)4SOa + Fez = 6FeS04 + 4E'e,(OK),. On reduction with iron, dilute Rolutions of ferric sulphate give ferrous sulphate only. The addition of R little sulphuric acid to the copper solution prevents the formation of the mud, and enables a clean deposit of copper to be obtained. W. T. Mercurammonium Compounds. By E. BALESTRA (Gatxettn, 21, ii, 294-305) .-The author has examined some of the ammonia- cal mercury compounds prepared by Millon (Ann.Chim. Phys. [3], IS), and also described by Gmelin. A. NHzHgC1,HgC1,.-T his compound was obtained by Millon by adding small quantities of ammonia to a large excess of corrosive sublimate. The author succeeded in preparing a compound having the same physical and chemical characteristics by gradually adding to a solution of corrosive sublimate half the quantity of dilute ammonia required for the complete precipitation of the mercury. It does not evolve ammonia when boiled with potash, but a large quan- tity is given of€ on treating it with a cold concentrated solution of ammonium bromide, according to Pesci's reaction (Abstr., 1890, 1211), showing that. the nitrogen is wholly contained in the mercur- ammonium radicle.Its composition was found to be NHg$1,2HCI. When it is suspended in water and exactly neutralised with potash, it is converted into dimercurammonium chloride, NHgzCl. B. 4NH,HgCl,NH,(Hg,O) Cl.-Millon obtained a yellow powder of the above composition by pouring a boiling solution of corrosive sublimate into a large excess of ammonia and thoroughly washing the product. Under hhese conditions, however, the author finds that a white precipitate is formed which loses ammonium chloride, on re- peatedly washing with water, gradually acquiring a yellowish tinge ; i t then approximates in composition to dimercurammonium chloride.INORQANIC CHEMISTRY. 27'7 The unaltered product has the composition of infusible white pre- cipitate, NHg2C1,NH4C1. C. NH2HgCI,2NH2(Hg,0) C12.-This compound was obtained by Millon in two ways : (1) by washing A completely with water, and (2) .by adding small quantities of ammonia to a large excess of R boiling solution of corrosive sublimate.By washing A with water, the author, however, obtained a bright yellow powder of the compo- sition 2NHg$1,HgC1,,H20, which loses + mol. H,O at 105-110". By Millon's second method (the author added to a boiling 7 per cent. solution of corrosive sublimate half tho quantity of ammonia required for neutralisation) ; a, pale-yellow, amorphous powder was obtained having the composition NHg,Cl,HCl. On neutralising this compound with potash, dimercurammoniuin chloride is formed. When it is washed with water, it is converted into the compound 2NHg2CI ,HgC1,,H20.S. B. A. A. Solubility of Glass in Cold Water. By 17. KOHLRAUSCII. ( B e y . , 24, 3560--5575).-The author has made experiments on the solu- bility of various kinds of glass by measuring the electrical con- ductivity of the solutions obtained on treating the glass with distilled water at 18". He finds that the quantity of glass dissolved increases with the time, but not proportionately, the solvent action being more rapid at first ; in the case of some of the best samples of glass, no appreciable action takes place even on prolonged contact. It was also found ttliat of two solutions, prepared in like manner from two kinds of glass having approximately the same composition, the one may have almost twice the conductivity of the other ; this result may be due t o the two samples having undergone different treatment in their manufacture.The composition of the various kinds of glass cinployed and the numerical results of the experiments are given in tables. The author also points out. that the best and most rapid test for inorganic salts in distilled water is a measurement of its electrical Conductivity ; the presence of carbonic anhydride can be ascertained in the same way. IF. S. K. Reaction between Potassium Permanganate and Hydrogen Peroxide Solution. By R. EXGEL (BUZZ. XOC. chi^. [3], 6, 17-19) -It often happens that when potassium permanganate solution i s xdded to hydrogen peroxide solution, decolorisation does not at once ensue, but thst when once the reaction has begun, decolorisatioii proceeds rapidly.Brodie attributed this result to the degree of dilution of the hydrogen peroxide, and Schone to the action of light on this compound. The author regards neither of these hypo- theses as tenable, and shows that the onset of the reaction is deter- mined by the presence of r?, trace of a manganous salt in the mixed solutions; this results from the action of traces of sulphurous o r nitrous compounds in the hydrogen peroxide solution on the per- manganate ; the maiiganous salt is then oxidised t o manganic sulphate, which is unstable in presence of hydrogen peroxide. The addition278 ABSTRACTS OF CHEMICAL PAPERS. of 8 trace of mnnganons sulphate t o the hydrogeu peroxide solution before running in the permanganste solution determines decolorisa- tion at the onset.T. G. N. Action of Ferric Chloride on Metallic Sulphides. By CAMMERER (Chem.. Centr., 1891, ii, 525; from Berg. Hiitten Zeit., 50, 295--298).-(For the first part of this work, see this vol., p.' 18.) l!'ei*ric chloride reacts wTith stannic sulphide forming stannic chloride, sulphur, and ferrous chloride. Mercuric sulphide is converted into mercuric chloride, sulphur and ferrous chloride being formed at the same time. The mercuric chloride at first formed reacts again with two more molecules of mercuric sulphide, with production of Heumann's double salt, 2HgS,HgCl2. This is a white substance, which is blackened by alkalis, but appears to be regenerated by the subsequent action of nitric acid. With silver sulphide, ferric chloride reacts, forming silver chloride, sulphur, and ferrous chloride.With the snlphides of lead, bismuth, cobalt, and manganese, ferric chloride reacts, the corresponding chloride of the metal is formed togethey mit'h ferrous chloride, and the sulphur is set free. Most of the reactions take place readily and completely . J. W. L. Coloration of Solutions of: Cobalt and the State of the Salts By A. ETARD (Compt. rend., 113, 699-701).- Its solubility a t in the Solutions. Cobalt iodide yields red, green, and blue solutions. various temperatures is as follows :- t .. .. -22" -8" -2" +go 14" 25" 34" 46" Sol.. . 52.4 56.7 58.7 61.4 61.6 66.4 73.0 79.0 t .... 60" 82" 111" 156" Sol.. . 79.2 80.7 80.9 83.1 Cobalt chloride yields rose-coloured or blue solutions, and its solu- bilities are as follows :- t ....-22" -4" +7" 11" 12" 25" 34" 41" Sol. . . 24.7 28.0 31.2 31.3 32.5 34.4 37.5 398 t . . . . 45" 49" 56" 78" 94" 96" 112" Sol.. . 41.7 4!6.7 48.4 48.8 50.5 51.2 52.3 The garnet-red, hexahydrated cobalt iodide yields a dull red solu- tion between -222" and about +20", the solubility between these limits being represented by a right line. Above 20", the liquid becomes brown, then olive, and finally at 35" deep chrome-green, this crolour persisting even up to 320". The deep green liquid yields green, lamellar crystals of the composition Co12,4H20. The formation of this salt begins at 20", and since it is more soluble than the red salt, and the two solubilities are superposed, there is a gradual increase in the total solubility between 20" and 35", the curve being convex towards the axis of temperature.Above 35", the green salt alone exists in solution, and its solubility is represented by a rightINORGANIC OHEMISTRY. 279 line. If it were possible to make experiments above 320", it is prob- able that the green liquid would become blue, and would contain a lower hydrate analogous to CoCl2,2H20. Such a blue solution is obtained when a solution of the cobalt iodide is poured into a satu- rated solution of magnesium chloride. In the case of cobalt chloride, the hydrate, CoCI, + 6H20, dissolves without change between -22" and +25", the solution has a pure rose colour, and the solubility is represented by a right line. At 25", dissociation begins, and the more soluble blue hydrate, CoCl, + 2H20, is formed, the colour of the solution changing to purple, and finally, at 50", to blue, this colour persisting up t o 300".Between 25" and 50", the curve of solubility is convex towards the axis of temperature, but beyond 50", it again becomes a right line. The changes of colour are not due to the presence of free acid or an acid salt, for they can be observed in presence of calcium carbonate or precipitated cobalt carbonate. Oxidation of Nickel Carbonyl. By BERTHELOT (Compt. rend., 113, 679--680).-Nickel carboiiyl can be kept under water in a flask wit,hont undergoing any alteration, provided that air is excluded, but i n presence of air, green nicbelous hydroxide, free from carbon, separates, and, at the same time, some of the nickel carbonyl escapes into the air and is oxidised t o a whit'e powder which, in mass, has a pale greenish tinge.It has the composition C, 5.3; NiO, 53.3; H20, 40.1 = 98.7, whilst the formula C203Ni3,10H20 requires C, 5.6 ; NiO, 52-5 ; H20, 41.9 = 100. The compound would, therefore, seem t o be the oxide of a complex radicle, analogous to croconic and rhodi- eonic acids. It is possible that one part of the nickel may be present in the form of nickel monoxide, mixed or combined with a complex oxide of the simpler formula C20Ni, belonging to the ethylene type or to a more condensed type of the same order, this oxide being formed thus, CaOtNi + 0 = C20Ni + 2C0,. C. H. B. C. H. B. Action of Hydrogen Phosphide on an Ethereal Solution of Bismuth Tribromide. By A. CAVAZZI and D. TIVOLI (Gazetta, 21, ii, 306--308).-When a solution of bismuth tribromide in dry ether is allowed t o fall gradually into a vessel containing dry hydrogen phosphide, a lustrous, black substance is formed which strongly adheres to the sides of the vessel.It becomes dull and hard on dry- ing in a vacuum, and probably has the composition PBrH(BiBr,),, being formed according to the equation SBiBr, + PI-& = 2HBr + PBrH( BiBr2)3. It is very hygroscopic, and is gradually decomposed by cold water and rapidly by boiling water, hydrogen phosphide, hydrobromic and phosphoric acids being formed and bismuth liberated. On heating it with a solution of potash, potassium bromide and phosphate are formed with evolution of hydrogen and hydrogen phosphide. Concentrated sulphnric acid has no action 011 it at the ordinary tem- perature, but, on boiling, bismuth sulphate, phosphoric acid, hydro- bromic acid, bromine, and sulphurous anhydride are formed.Concen- trated nitric acid also acts very violently on it. When triturated280 ABSTRAOTS OF CHEMICAL PAPERS. with fragments of sodium amalgam, it ignites and decomposes with more or less violence, according to the richness of the amalgam in sodium. When heated at 220" in an airnosphere of dry carbonic anhydride, it has the same composition as when dried in a vacuum. When heated in the air, it becomes viscid and decomposes with some violence and with evolution of fumes of bromine, bismuth bromide, and phosphoric anhydride. S. B. A. A. Auric Sulphide. By U. ANTOSY and A. LUCCHESI (Gazzetta, 21, ii, 209-212) .-Auric sulphide, prepared by the authors' method (Abstr., 1891, 526), is a graphitic, amorphous powder having a sp.gr. of 8-754 compared with water at 0" ; it decomposes into its elements at 197-200". Hydrochloric acid has no action on nuric sulphide, concentrated nitric acid oxidises it in the cold with separation of gold, whilst a,qua regia readily dissolves it. Caustic alkalis (15 per cent,) decompose the sulphide on heating, metallic gold and alkali sulphide and ttiio- sulpbate being obtained. Ammonia solution, on prolonged contact, decomposes it., yielding snlphuric acid, free sulphur, and a. little hydrogen sulphide. The action of potassium cyanide solution on auric sulphide differs from its action on aurous sulphide and auroso- auric snlphide, both of which dissolve and are reprecipitated by acids, Auric sulphide dissolves in aqueous potassium cyanide (25 per cent.) to a yellow solution, which, on boiling, becomes colourless and deposits xurous potassium cyanide on cooling, AuzS3 + 6KCN = 2AuKCzN, + K,S + SKCNS.This reaction shows the substance to be homo- geneous, the auric sulphide prepared by Berzelius having been shown by Kruss and Hoffmann (Abstr., 1887,1019 ; 1888,28) to be a mixture of aurosoauric sulphide with sulphur. Hydrosulphide and polysulphides of ammonia dissolve auric sulph- ide readily on warming, gold being deposited. The sulphides and polysulphides of the alkali metals dissolve the substance slowly ; whilst the alkali hydrosnlphides dissolve it i n the cold, yielding a deep reddish-brown solution, which, on boiling, becomes pale yellow and deposits gold. These solutions, on treatment with hydrochloric acid, give a flocculent, yellow precipitate, probably consisting of auric hydrosulphide, which soon turns brown with formation of hydrogen sulphide and auric sulphide.On precipitation with alcohol at -lo", a concentrated solution of nuric sulphide in sodium hydrosulphide gives a yellowish precipitate ; this, when filtered through asbestos at the same temperature in an atmo- sphere of nitrogen and washed wihh alcohol, yields a white, crystalline product which soon darkeiis in colour. The freshly prepared sub- stance is very soluble in water and is probably fiodium sulphaurate, but it decomposes so rapidly that tiaustmorthy analyses could not be made. W. J. P. Iodonitro- and Bromonitro-platinum Compounds.By M. VEZES (Compt. rend., 113, 696--698).-The relative stability of the nitro- and hdoid groups in the iodonitro-platinum compounds is the inverse of that observed in the case of the chloronitro- and bromo-INORQANIC OEEMISTRY. 281 nitro-compounds (Abstr., 1891, 807). The iodine is displaced by nitrogen oxides, and the stable term of the series is the platonitrite and not the platoiodide. Nitrogen oxides readily decompose potassium platniodide wit>h liberation of iodine ; whilst, on the other hand, iodine in the forin of vapour or in solution in hydriodic acid or a solution of potassium iodide does not decompose potassium platonitrite. The action of an alcoliolic solution of iodine on a warm solution of potassium platonitrite, however, yields large, brilliant prisms of t'he compound Pt,2N02,K,T, + 2Hz0, described by Nilson, but this, ttlthough stable in warm solutions, is decomposed by nitrogen oxides o r potassium nitrite, with liberation of iodine and formation of the platonitrite.The author has so far failed to obtain a compound Pt,4N0,,KzI,, analogous to the platichloronitrite and the platibromo- nitrite previously described. If, however, an excess of an alcoholic solution of iodine is added to a warm concentrated solution of the platonitrite, and the mixture is concentrated as rapidly as possible at a gentle heat, potassium nityoso- plati-iodide, PtT3,N0,K212, separates on cooling in small, brilliant, black crystals, which remain unaltered a t 100". When heated in a current of hydrogen, this compound yields water, ammonium iodide, iodine, hydrogen iodide, and a, residue of potassium iodide and platinum.If the liquid is slcwly concentrated (without ebullition) a different compound is obtained on cooling. T t is potassium platitetraiodonitrite, Pt14,2NOz,Kz, and separates in small, well-defined, black crystals with a greenish lustre. Like the preceding compound, it is only slightly soluble in water, yielding a deep brown solution, and it undergoes no change at 100". When heated in a current, of hydrogen, it yields water, ammonium iodide, iodine, and hydrogen iodide, with a residue of potassium iodide and pIatinum. When the mixture yielding these two salts is submitted t o pro- longed ebullition, the excess of iodine is expelled and potassium platoiodonitrite is formed.When bromine-water is added t o a solution of potassium platoiodo- nitrite until a11 the iodine is expelled, the brown liquid, when con- centrated in a dry vacuum, yields yellow, tabular crystals. The same crystals are obtained by heating n solution of potassium platibromo- nitrite, Pt,4N0,,K(,Rr2, with alcohol at 80", aldehyde and other gases being evolved. This new cornpound is potassium platobronionitrite, Pt,2NO2,K,Br, + H,O, and ib very soluble in water. At loo", it becomes anhydrous and biaiglit yellow ; at a higher temperature, it blackens with evolution of nitrogen oxides, a residue containing potassium bromide and platinum in the proportions Pt + 2KBr being left. When heated in hydrogen, it yields the same residue without any formation of ammoni urn bromide, bromine, o r hydrogen bromide, By R.SCIINEIDER (J. pr. Ckem. [ 21, 44, 507--512).-Potassium plati?ao~eleilostannate, K,Pt,SnSe,, is prepared by melting together 10 parts of platinum sponge, 6-8 parts of tin selen- ide, 30-40 parts of potassium carbonate, and 30-40 parts of selenium in a covered porcelain crucible SO that the mass shall remain liquid for 8-10 minutes after the frothing has ceased. The melt is extracted C. H. B. Two New Seleno-salts.282 ABSTRACTS OF CHEMICAL PAPERS. with water, and the undissolved residue digested with concentrated potassium hydroxide solution, whereby the selenostannate is left un- attacked. It forms small, well-defined, hexagonal tables which are leaden-grey by reflected light and have a strong metallic lustre ; in thin layers they are reddish-brown by transmitted light.In its general habitus it is very similar to the author's potassium platino- sulphostmnate (Ann. Phys. Chem., 138, 612). At the ordinary tem- perature, it is stable in air ; when heated in air, it loses all its selenium, the residue consisting of a mixture of platinum with potassium stan- nate. It is not attacked by water, ammonia, potash, 01- hydrochloric acid, either hot or cold. Sodium pZat inoseZenostnnnate, Na,Pt,SnSe,, cannot be obtained by merely substituting sodium carbonate for potassium carbonate in the above prescription. It is readily formed, however, when 10 parts of platinum sponge, 5-6 parts of tin selenide, 40 parts of potassium carbonate, 5-6 parts of sodium carbonate, and 40 parts of selenium are fused together, and the melt treated as described above.It forms leaden-grey, microscopical, hexagonal lamin* with a brilliant, metallic lustre ; the remarks concerning the potassium salt apply also to this. A. G. B. Saline Compounds of the Lower Ruthenium Oxides with the Higher Oxides. By A. JOLY (C'ontpt. rend., 113,694-695.)-When the products of the sudden decomposition of potassium perruthenate at 440" are kept for a long time at this temperature, interaction takes place with formation of a black, crystalline compound of the composi- tion K20,6Ru205. Sodium permthenate at 440" loses oxygen and water, and after treatment of the residue with water, which removes sodium oxide and the orange sodium ruthenate, a black crystalline powder is left with a, composition approximating very closely to that for Na20, 3Ru205. Barium ruthenate, IBaRuO4, at 440" loses oxygen, and yields a ruthenite, BaRuO,, different in properties from a mixture of barium monoxide and ruthenium dioxide.The author directs atten- tion t o the analogy between these compounds and the products obtained by Rousseau from the permanganates, and the product K,O,Oe,O,, obtained by himself from potassium osmiamate. Action of Light on Ruthenium Peroxide. By A. JOLY (t%~~pt. rend., 113, 693--694).-When sealed tubes containing perfectly dry ruthenium peroxide are kept in the dark, no alteration takes place, but on exposure to sunlight, the walls of the tube become coated with a pale brown layer, which gradually increases in thickness and eventually transmits only red light.Beyond this point, the peroxide behind undergoes no further change. The brown deposit dissolves at once in potassium hydroxide solution, forming a yellow liquid without any trace of green, and in hydrochloric acid with evolution of chlorine and formation of a solution of ruthenium sesquichloride. It seems, therefore, t,hat when exposed to sunlight, ruthenium per- oxide is reduced to the trioxide, Ru03. C. H. B. C. H. B.2 70 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e m i s t r y.Preparation of Pure Hydrogen Peroxide Solution. By L.CR~SMER (BUZZ. Soc. Chim. [3], 6, 24--25).-The solution of hydrogenperoxide which results from the action of hydrochloric acid (sp. gr.1.1) on barium dioxide is extracted by shaking with ether, and theethereal solution is agitated with distilled water, to which it yieldsthe dissolved hydrogen peroxide.By repetitions of this process, apure, neutral solution corresponding with 0.8-0.9 per cent of hydro-gen peroxide is obtainable, from which the dissolved ether may beeliminated by distillation under reduced pressure.Preparation of Hydrobromic Acid. By G. S. NEWTH (Chena.News, 64, 215).-By means of the following arrangement a largequantity of bromine can be rapidly converted into hydrobromic acid :-A glass tube, 7 inches long and 8 inch in diameter, is fitted at eachend with a cork carrying a piece of small tubing and a piece of fitoutwire. The ends of these pieces of stout wire, within the longer tube,T.G. NINORQANlO OHEMISTRY. 271are joined hy a spiral of platinum wire 1 inch long, and after expellingthe air the spiral is heated to bright redness by Rn e1ecOric current; astream of hydrogen, impregnated with bromine by bubbling throughthat liquid, which may be heated at GO", is passed through the longertube, and, as long as a Blight excess of hydrogen is maintained, hydro-bromic acid quite free from bromine issues from the other end, and iscollected in water. There is very little danger of explosion, but t orender it impossible, the small supply tube may be plugged with alittle glass -vr7001.Solubility of Gases in Water. By I;. W. WINKLER (Ber., 24,3602-3610; compare Abstr., 1891, 384).-In this paper the authorgives in tabular form the results of experiments on the solubility ofnitrogen and of oxygen in water, a t temperatures ranging from 0" to80"; the calculated values for the solubility of the two gases attemperatures ranging from 80--100" are also given.As regards thesolubility of nitrogen, the author's values are considerably larger thanthose given by Bunsen.The Densities of Sulphuric Acid Solutions. By S. U. PICKER-ING (Chem. News, 64,31l).-Lunge's doubts as t o the accuracy of theauthor's density determinations are, in the opinion of the latter, dueto a misapprehension as to the method employed to determine thestrength of the acid, and as to the experimental error involved.D. A. L.E'. S. K.s. u. P.The Contraction on Mixing Sulphuric Acid and Water. ByS.U. PICKERING (Chem. Netus, 64, 14--15).-From his own results theauthor has calculated the strength a t which the maximum contractionoccurs, and finds that this maximum, when calculated for unit weightof solution, shifts from 67 per cent. at 8" to 70.1 per cent. at 38",whereas the maximum contraction calculated per unit volume remainspractically constant at 76 per cent. throughout this range of tempera-ture. Neither of these maxima occurs at the composition of the di-hydrate (73.1 per cent.) or of that of any other hydrate of whichindications have been obtained. The rate atr which the amount ofcontraction is influenced by the temperature varies irregularly withthe actual value of the temperatnre ; tlhus with solutions from 64 to80 per cent. st,rength, the contraction diminishes at nearly the samerate for the intervals 8" to 18", and 28" to 38", whereas for the inter-mediate interval, 18" t o 28", the rate of diminution is about 25 percent. smaller.s. u. P.Density and Composition of Dilute Sulphuric Acid. By A.W. R ~ C K E R (Phil. Mug. [ 5],32,304-313) .-Pickering (Trans., 1890,64) deduced the existence of various hydrates in sulphuric acid solu-tions from sudden changes of curvature in the curves representing thevariation of the density, &c., of such solutions with the composition.The author considers the " first diflerential " curve for 18" between 46per cent. and 80 per cent., in which there are supposed to be f o u r breaks,and shows that it is possible to find an equation, and, therefore, acontinuous curve, which will represent the results within the limits ofthe experimental error.The equation is of the formu 272 ABSTRACTS OF OHEMIOAL PAPERS.and contains fieven ai-bitrary constants. The author thus doubts thevalue of '' differentiation " or of the bent ruler, as used by Pickering,in discovering changes of curvature in curves drawn to representexperimental numbers. J. W.The Densities of Sulphuric Acid Solutions. By S . U.PICKERING (Phil. Xag. [ 5 ] , 33, 132).-The curve used by RiicBer(see preceding abstract) to bridge over four of what the writer con-sidered to be breaks in the figure foymed by the first differentials of thedensities of the acid can, he maintains, prove nothing about one ofthese breaks, and very little about another, for it extends too short a,distance beyond them.The formula for the curve suggested byRucker consists of a combination of an exponential curve and astraight line, on to part of which (as this curve did not agree withthe results) a hump was engrafted by means of a complex fourth term,tlhe whole forming a curve for which, as an expression of physicalfacts, there would seem to be no precedent. The points, moreover, atwhich the term expressing the hump begins to be appreciable andagain becomes inappreciable correspond exactly with the positionsassigned by the author to two of t,he breaks, thus confirming, ratherthan disproving, the existence of these as points where some newconditions in the solutions become sensible.The only break whichBucker's curve does successfully bridge over is that particular onewhich the author pointed out to be especially doubtful: and evenin favour of this break the evidence is not thereby entirely negatived.The author maintains that even the most successful attempt to offeran alternative explanation of a small portion of some of his resultscould not upset his conclusions which were based entirely on thecumulative evidence derived from many sources, and of which hehere gives a summary. s. u. P.Boron Phosphides. By H. MOISSAN (Compt. rend., 113, 726-~29).--Bo~on phosphide, PB, is obt,ained by reducing the phospha-iodide in hydrogen at 450-500". The product is powdered, andagain heated in hydrogen at the same temperature in order toremove excess of iodine, and the process is repeated two or threetimes if necessary, care being taken that the temperature does notexceed 500".I t is a very light, amorphous, maroon-coloured powdel.,insoluble in the chlorides of arsenic, phosphorus, carbon, and anti-mony, and in all solvents, organic and ino~ganic, that were tried.It is n o t volatile in a, vacuum at 500". At 200", in presence of oxygen,it burns and yields boric and phosphoric anhydrides ; when throwninto fused alkaline nitrates, there is incandescence and deflagration ;fused sulphur has no action, hut sulphur vapour converts it intoboi-on and phosphorus sulphides. Chlorine converts boron phosphideinto boron trichloride and phosphorus pentachloride, with incand-escence ; bromine has no action in the cold, but combination takesplace if the temperature is raised.Vapour of iodine, arsenic, oINORQANIC CHEMISTRY. 273phosphorus has no action at a dull-red heat. When heated at 5OO"ina current of nitrogen, boron phosphide yields no nitride, and, althougha,t higher temperatures it loses phosphorus (as it does in a vacuum),no nitride is formed. When a mixture of boron phosphide andsodium is gently heated in a current of hydrogen, it rapidly becomesincandescent, with formation of sodium phosphide and boride. Potas-sium yields the same products at a lower temperature. A mixtureof the boron phosphide with powdered magnesium becomes incand-escent at about 500", but aluminium has no action, except at a muchhigher temperature. Finely-divided silver, copper, and platinumreact with the phosphide when gently heated, biit mercury has noaction at its boiling point.When boron phosphide is thrown into thestrongest nitric acid, it takes fire, even in the vapour, and burnsbrilliantly on the surface of the liquid; on slightly heating, it dis-solves immediately and completely. Concentrated solutions of hydro-chloric and hydriodic acids have no action on the phosphide, andsulphuric acid has no action in the cold, but is reduced on heating.Concentrated hot solutions of potash and soda dissolve i t slowly,whilst fused potash dissolves it completely with formation of hydrogenphosphide and potassium borate. Gaseous hydrogen fluoride attacksit below dull redness, with formation of boron fluoride, hydrogen,and phosphorus.Gaseous hydrogen chloride behaves similarly at Rhigher temperature. Boiling water has no action on the phosphide,but water vapour decomposes it at 400" with production o€ boric acidand hydrogen phosphide. Hydrogen sulphide at A dull-red heatyields boron sulphide and hydrogen phospliicle. I n ammonia at about300" the phosphide burns, with formation of boron nitride and libera-tion of phosphorus.Boron phosphide, B5P3, is obtained by heating the preceding com-pound at 1000" in a current of hydrogen. It has a paler colour thanthe phosphide PB, does not inflame in chlorine or nitric acid, and isnot attacked by the latter, even when boiling. It is insoluble in allinorganic and organic solvents, burns with some difficulty in oxygen,and is attacked by fused nitrates with incandescence, but only withdifficulty by metals and non-metals.It does not burn in chlorinebelow a dull-red heat.I f the hydrogen used for reduction contains water or oxygen, awhite phosphoboric acid, also known as boron phosphate, is formed,and the same compound is obtained by the action of nitrogen oxideson a mixture of the phosphides.Boron Phosphide. By A. BESSON (Compt. Tend., 113, 772-7731,-The author draws attention to his previous note on the subject(Abstr., 1891, 1418), and describes 'an additional property of thephosphide. It is oxidised by dilute nitric acid to a substance, prob-ably phosphoboric acid, which is left in nacreous plates on evaporatingthe solution to dryness, is soluble in water, and gives a white, gelatin-ous precipitate with excess of ammonia.Moissan (ibid., 787-788), commenting on this and the previousnote, draws attention to the absence of numerical data justifying theformula, BP attributed to the phosphide, and claims priority in theC.H. B274 ABSTRACTS OF CEEMTOAL PAPERS.Rystematic study of boron phosphides (Compt. rend.! 112, 71 7, and113, 19). JN. w.The Influence of Steam and other Gases on the Combustionof Carbonic Oxide and Oxygen. By N. BBK~TOFF (Ckenz. Centr.,1831, ii,449-450 ; from Bull. Acad. St. PrStersbourg [2], 2, 175-179).-Having repeated Dixon's experiments (Trans., 1885,94), the authorhas obtained the same results, namely, that, a mixture of carbonicoxide and oxygen, when dried by nieans of phosphoric anhydride, isnot exploded by the passage of an electric spark, and further, that ifthe gases be dried by sulphuric acid, which appears to leave a trace ofmoisture in the gas, the combustion proceeds so slowly that it maybe followed with the eye.The presence of other gases, sulphurousanhydride, o r nitrous oxide, had not a similar effect. Cyanogen, onthe other hand, when present to the extent of 10 per cent., exerted aninfluence similar to that of steam, and caused an immediate explosionon the passage of the spark. BBkbtoff suggests that the action ofcyanogen may be explained on the assumption that the beak liberated inthe decomposition of the cyaiiogen is added to the heat of conibustionof the carbon, and he further assumes that the dissociation tempern-ture of the water niolecule being lower than that of the oxygenmolecule is the proper explanation of the fact that the presence ofwater in a mixture of carbonic oxide and oxygen assists the com-bustion of the latter gases.J. W. L.Reactions of Carbonic Anhydride at High Pressures. By A.D'ARSONVAL (Conzpt. rend. SOC. Biol., 1891, 320--321).--Liquefied carb-onic anhydride is a powerful antiseptic. It does not coagulate albu-min. At high pressures it can displace both organic and mineralacids. When urine is subjected to a pressure of 40 atmospheres ofcarbonic, anhydride, crystals of uric acid are deposited. A dilute solu-tion of potassium silicate similarly treated becomes solidified from thedeposition of silicic acid.Carbonic anhydride at the same pressureis also able t o liberate hydriodic and hydrobromic acids from solu-tions of potassium iodide and bromide respectively.By N. BEKBTOFF (Chenz. Centr., 1891, ii,450-451 ; from Bull. Acad. St. Pe'tersbourg [2], 2, 169--17G).-Theauthor has prepared considerable quantities of cssium by redncingthe hydroxide with aluminium. The reaction proceeds well, and isas readily carried out as the reduction of rubidium. The author referst o the results, which Winkler has recently published, on the heat ofcombination of the alkali metals, and points out that the deductionswhich Winkler has made are diametrically opposed to his own. Theauthor finds that the combining heat of the alkali metals variesinversely with their atomic weights.He further urges that Winklerhas not employed the oxides, but the hydroxides and carbonate5,for his determinations, which are not suitable for the purpose.Properties of Czesium and its Hydroxide. By N. BEKETOFF(Chem. Centr., 1891, ii, 451 ; from Bull. Acad. St. Pe'teysbourg [SJ, 2,W. D. H.Reduction of CEsium.J. W. LINORGANIC CHEMISTRY. 275171--173).--The author has used a very pure specimen of caesiumsulphate as material on which t o work. A determination of thesulphnric acid gave almost the theoretical amount, and by means ofthe spectroscope only a trace of rubidium could be detected.The hydroxide was obtained from the sulphate by precipitation withbarium hydroxide, and concentration of the filtrate in a silver dish,which was placed in a metal retort.In this manner carbonic an-hydride was excluded. After concentration in the retort, the solutionwas transferred to a small silver dish, the remainder of the waterevaporated, and the hydroxide finally fused. The silver dish wasslightly attacked, and the silver oxide dissolved in the fused caesiumhydroxide ; it was again precipitated, however, as the latter cooled.The quantity of silver oxide was inconsiderable. Cmium hydroxidehas a sp. gr. 4.0178, compared with water at 4" ; the molecularvolume = 57.3 (sodium hydroxide = 18 ; potassium hydroxide = 27 ;rubidium hydroxide = 32 ?). The molecular volume of the hydroxidecorresponds with a very considerable diminution of volume during itsformation from the elements.The heat of solution of the hydroxidein water is 15,876, which is higher than f o r all other alkali hydroxides.The heat of neutralisation of the hydroxide with hydrogen chloride(dilute) is 13,790, or nearly the same as that found by Thomsen forpotassium hydroxide, or, indeed, for the other alkali hydroxides.Metallic cEsium was obtained by heating 114 grams of the hydroxidein a nickel retort wit,h 27 grams of aluminium, and collecting thedistilled metal in glass receivers; 20-25 grams of the metal werethus obtained.The heat of combination of cmium with water was found to befrom 50 to 53 Cal. J. W. L.Action of Sodammonium and Potassammonium on Metals.By JOAXNIS (Cornpi!. rend., 113, 795-798).- Sodammonium andpotassammonium are decomposed by mercury, lead, and antimony, butare not affected by aluminium, silver, zinc, or copper.When a solutionof sodammonium in liquefied ammonia is allowed to fall drop by dropon mercury, it is decomposed with the formation of a crystallineamalgam, Hg,Na, which can be washed free from excess of the reagentwith liquefied ammonia. Potassammonium under similar conditionsyields an amalgam of the composition Hgl8K.When pure lead is brought into contact with sodammonium, thereddish-brown liquid turns blue, and then green, and a little hydrogenis disengaged, owing to the spontaneous decomposition of the sod-ammonium. Finally, however, the metal is partially converted into anindigo-blue mass, which dissolves in liquefied ammonia to a bottle-green solution, and has the composition Pb4Na,2NH,.This substancedecomposes at ordinary pressures, leaving a grey mass resemblingspongy platinum, and oxidises rapidly on exposure to air, with evolu-tion of heat. When thrown into water, the first portion dissolvescompletely, owing to the combination of the lead with the dissolvedoxygen, and the subsequent solution of the oxide in the sodiumhydroxide simultaneously formed, but as soon as the oxygen is usedup, metallic lead is thrown down as a black, curdy precipitate.JN. W276 ABSTRACTS OF OHEMICAL PAPERS.Influence of Ammonia on the Solubility of AmmoniumChloride. By R. EXGEL (BUZZ. Xoc:Chim. [3], 6, 17).-The pre-sence of ammonia diminishes the solubility of ammonium chloride inwater at 0' at first, but as the quantity of ammonia is increased, acorresponding increase in the chloride dissolved obtains.This resultis probably due to the formation of compounds of ammonium chlorideand hydroxide. Tables of values are given. T. G. N.Precipitation of Copper by Iron and the Action of Iron onFerric Solutions. By J. C. Essmit (BdZ. SOC. Chin%. [ 3 ] , 6, 147-148) .-In the wet method of copper extraction, very mixed qualitiesof acrap iron are employed. The reduced copper occurs in powder,grains, and filaments which cannot be readily washed free from themud of ferric hydroxide formed. The author finds that the structureof the iron used exerts a marked influence on that of the copperobtained.By selecting the iron to be used, it is possible to obtaiiithe reduced copper in a fibrous or granular condition, when i t admitsof being readily washed free from ferric hydroxide.The occurrence of the mud of ferric hydroxide is due to the form-ation of a basic ferric sulphate, Fez(OH)aS04. This salt is decom-posed by iron as follows :-6Fe2(0H)4SOa + Fez = 6FeS04 +4E'e,(OK),. On reduction with iron, dilute Rolutions of ferric sulphategive ferrous sulphate only.The addition of R little sulphuric acid to the copper solutionprevents the formation of the mud, and enables a clean deposit ofcopper to be obtained. W. T.Mercurammonium Compounds. By E. BALESTRA (Gatxettn,21, ii, 294-305) .-The author has examined some of the ammonia-cal mercury compounds prepared by Millon (Ann.Chim. Phys. [3],IS), and also described by Gmelin.A. NHzHgC1,HgC1,.-T his compound was obtained by Millon byadding small quantities of ammonia to a large excess of corrosivesublimate. The author succeeded in preparing a compound havingthe same physical and chemical characteristics by gradually addingto a solution of corrosive sublimate half the quantity of diluteammonia required for the complete precipitation of the mercury. Itdoes not evolve ammonia when boiled with potash, but a large quan-tity is given of€ on treating it with a cold concentrated solution ofammonium bromide, according to Pesci's reaction (Abstr., 1890,1211), showing that. the nitrogen is wholly contained in the mercur-ammonium radicle.Its composition was found to be NHg$1,2HCI.When it is suspended in water and exactly neutralised with potash,it is converted into dimercurammonium chloride, NHgzCl.B. 4NH,HgCl,NH,(Hg,O) Cl.-Millon obtained a yellow powder ofthe above composition by pouring a boiling solution of corrosivesublimate into a large excess of ammonia and thoroughly washingthe product. Under hhese conditions, however, the author finds thata white precipitate is formed which loses ammonium chloride, on re-peatedly washing with water, gradually acquiring a yellowish tinge ;i t then approximates in composition to dimercurammonium chlorideINORQANIC CHEMISTRY. 27'7The unaltered product has the composition of infusible white pre-cipitate, NHg2C1,NH4C1.C. NH2HgCI,2NH2(Hg,0) C12.-This compound was obtained byMillon in two ways : (1) by washing A completely with water, and(2) .by adding small quantities of ammonia to a large excess of Rboiling solution of corrosive sublimate.By washing A with water,the author, however, obtained a bright yellow powder of the compo-sition 2NHg$1,HgC1,,H20, which loses + mol. H,O at 105-110".By Millon's second method (the author added to a boiling 7 percent. solution of corrosive sublimate half tho quantity of ammoniarequired for neutralisation) ; a, pale-yellow, amorphous powder wasobtained having the composition NHg,Cl,HCl. On neutralising thiscompound with potash, dimercurammoniuin chloride is formed. Whenit is washed with water, it is converted into the compound2NHg2CI ,HgC1,,H20.S. B. A. A.Solubility of Glass in Cold Water. By 17. KOHLRAUSCII. ( B e y . ,24, 3560--5575).-The author has made experiments on the solu-bility of various kinds of glass by measuring the electrical con-ductivity of the solutions obtained on treating the glass with distilledwater at 18". He finds that the quantity of glass dissolved increaseswith the time, but not proportionately, the solvent action being morerapid at first ; in the case of some of the best samples of glass, noappreciable action takes place even on prolonged contact. It was alsofound ttliat of two solutions, prepared in like manner from two kindsof glass having approximately the same composition, the one mayhave almost twice the conductivity of the other ; this result may bedue t o the two samples having undergone different treatment intheir manufacture.The composition of the various kinds of glasscinployed and the numerical results of the experiments are given intables.The author also points out. that the best and most rapid test forinorganic salts in distilled water is a measurement of its electricalConductivity ; the presence of carbonic anhydride can be ascertainedin the same way. IF. S. K.Reaction between Potassium Permanganate and HydrogenPeroxide Solution. By R. EXGEL (BUZZ. XOC. chi^. [3], 6, 17-19)-It often happens that when potassium permanganate solution i sxdded to hydrogen peroxide solution, decolorisation does not at onceensue, but thst when once the reaction has begun, decolorisatioiiproceeds rapidly.Brodie attributed this result to the degree ofdilution of the hydrogen peroxide, and Schone to the action oflight on this compound. The author regards neither of these hypo-theses as tenable, and shows that the onset of the reaction is deter-mined by the presence of r?, trace of a manganous salt in the mixedsolutions; this results from the action of traces of sulphurous o rnitrous compounds in the hydrogen peroxide solution on the per-manganate ; the maiiganous salt is then oxidised t o manganic sulphate,which is unstable in presence of hydrogen peroxide. The additio278 ABSTRACTS OF CHEMICAL PAPERS.of 8 trace of mnnganons sulphate t o the hydrogeu peroxide solutionbefore running in the permanganste solution determines decolorisa-tion at the onset.T. G. N.Action of Ferric Chloride on Metallic Sulphides. ByCAMMERER (Chem.. Centr., 1891, ii, 525; from Berg. Hiitten Zeit., 50,295--298).-(For the first part of this work, see this vol., p.' 18.)l!'ei*ric chloride reacts wTith stannic sulphide forming stannic chloride,sulphur, and ferrous chloride. Mercuric sulphide is converted intomercuric chloride, sulphur and ferrous chloride being formed at thesame time. The mercuric chloride at first formed reacts again withtwo more molecules of mercuric sulphide, with production ofHeumann's double salt, 2HgS,HgCl2. This is a white substance,which is blackened by alkalis, but appears to be regenerated by thesubsequent action of nitric acid.With silver sulphide, ferric chloride reacts, forming silver chloride,sulphur, and ferrous chloride. With the snlphides of lead, bismuth,cobalt, and manganese, ferric chloride reacts, the correspondingchloride of the metal is formed togethey mit'h ferrous chloride, andthe sulphur is set free.Most of the reactions take place readily andcompletely . J. W. L.Coloration of Solutions of: Cobalt and the State of the SaltsBy A. ETARD (Compt. rend., 113, 699-701).-Its solubility a tin the Solutions.Cobalt iodide yields red, green, and blue solutions.various temperatures is as follows :-t .. .. -22" -8" -2" +go 14" 25" 34" 46"Sol.. . 52.4 56.7 58.7 61.4 61.6 66.4 73.0 79.0t .... 60" 82" 111" 156"Sol.. . 79.2 80.7 80.9 83.1Cobalt chloride yields rose-coloured or blue solutions, and its solu-bilities are as follows :-t ....-22" -4" +7" 11" 12" 25" 34" 41"Sol. . . 24.7 28.0 31.2 31.3 32.5 34.4 37.5 398t . . . . 45" 49" 56" 78" 94" 96" 112"Sol.. . 41.7 4!6.7 48.4 48.8 50.5 51.2 52.3The garnet-red, hexahydrated cobalt iodide yields a dull red solu-tion between -222" and about +20", the solubility between theselimits being represented by a right line. Above 20", the liquidbecomes brown, then olive, and finally at 35" deep chrome-green, thiscrolour persisting even up to 320". The deep green liquid yieldsgreen, lamellar crystals of the composition Co12,4H20. The formationof this salt begins at 20", and since it is more soluble than the redsalt, and the two solubilities are superposed, there is a gradualincrease in the total solubility between 20" and 35", the curve beingconvex towards the axis of temperature.Above 35", the green saltalone exists in solution, and its solubility is represented by a righINORGANIC OHEMISTRY. 279line. If it were possible to make experiments above 320", it is prob-able that the green liquid would become blue, and would contain alower hydrate analogous to CoCl2,2H20. Such a blue solution isobtained when a solution of the cobalt iodide is poured into a satu-rated solution of magnesium chloride.In the case of cobalt chloride, the hydrate, CoCI, + 6H20, dissolveswithout change between -22" and +25", the solution has a purerose colour, and the solubility is represented by a right line. At 25",dissociation begins, and the more soluble blue hydrate, CoCl, +2H20, is formed, the colour of the solution changing to purple, andfinally, at 50", to blue, this colour persisting up t o 300". Between25" and 50", the curve of solubility is convex towards the axis oftemperature, but beyond 50", it again becomes a right line.The changes of colour are not due to the presence of free acid or anacid salt, for they can be observed in presence of calcium carbonateor precipitated cobalt carbonate.Oxidation of Nickel Carbonyl.By BERTHELOT (Compt. rend.,113, 679--680).-Nickel carboiiyl can be kept under water in a flaskwit,hont undergoing any alteration, provided that air is excluded, buti n presence of air, green nicbelous hydroxide, free from carbon,separates, and, at the same time, some of the nickel carbonyl escapesinto the air and is oxidised t o a whit'e powder which, in mass, has apale greenish tinge.It has the composition C, 5.3; NiO, 53.3;H20, 40.1 = 98.7, whilst the formula C203Ni3,10H20 requires C, 5.6 ;NiO, 52-5 ; H20, 41.9 = 100. The compound would, therefore, seemt o be the oxide of a complex radicle, analogous to croconic and rhodi-eonic acids. It is possible that one part of the nickel may be presentin the form of nickel monoxide, mixed or combined with a complexoxide of the simpler formula C20Ni, belonging to the ethylene typeor to a more condensed type of the same order, this oxide being formedthus, CaOtNi + 0 = C20Ni + 2C0,.C. H. B.C. H. B.Action of Hydrogen Phosphide on an Ethereal Solution ofBismuth Tribromide. By A.CAVAZZI and D. TIVOLI (Gazetta,21, ii, 306--308).-When a solution of bismuth tribromide in dryether is allowed t o fall gradually into a vessel containing dry hydrogenphosphide, a lustrous, black substance is formed which stronglyadheres to the sides of the vessel. It becomes dull and hard on dry-ing in a vacuum, and probably has the composition PBrH(BiBr,),,being formed according to the equation SBiBr, + PI-& = 2HBr +PBrH( BiBr2)3. It is very hygroscopic, and is gradually decomposedby cold water and rapidly by boiling water, hydrogen phosphide,hydrobromic and phosphoric acids being formed and bismuth liberated.On heating it with a solution of potash, potassium bromide andphosphate are formed with evolution of hydrogen and hydrogenphosphide.Concentrated sulphnric acid has no action 011 it at the ordinary tem-perature, but, on boiling, bismuth sulphate, phosphoric acid, hydro-bromic acid, bromine, and sulphurous anhydride are formed.Concen-trated nitric acid also acts very violently on it. When triturate280 ABSTRAOTS OF CHEMICAL PAPERS.with fragments of sodium amalgam, it ignites and decomposes withmore or less violence, according to the richness of the amalgam insodium. When heated at 220" in an airnosphere of dry carbonicanhydride, it has the same composition as when dried in a vacuum.When heated in the air, it becomes viscid and decomposes with someviolence and with evolution of fumes of bromine, bismuth bromide,and phosphoric anhydride.S. B. A. A.Auric Sulphide. By U. ANTOSY and A. LUCCHESI (Gazzetta, 21,ii, 209-212) .-Auric sulphide, prepared by the authors' method(Abstr., 1891, 526), is a graphitic, amorphous powder having a sp. gr.of 8-754 compared with water at 0" ; it decomposes into its elementsat 197-200".Hydrochloric acid has no action on nuric sulphide, concentratednitric acid oxidises it in the cold with separation of gold, whilst a,quaregia readily dissolves it. Caustic alkalis (15 per cent,) decomposethe sulphide on heating, metallic gold and alkali sulphide and ttiio-sulpbate being obtained. Ammonia solution, on prolonged contact,decomposes it., yielding snlphuric acid, free sulphur, and a. littlehydrogen sulphide. The action of potassium cyanide solution onauric sulphide differs from its action on aurous sulphide and auroso-auric snlphide, both of which dissolve and are reprecipitated by acids,Auric sulphide dissolves in aqueous potassium cyanide (25 per cent.)to a yellow solution, which, on boiling, becomes colourless and depositsxurous potassium cyanide on cooling, AuzS3 + 6KCN = 2AuKCzN, + K,S + SKCNS.This reaction shows the substance to be homo-geneous, the auric sulphide prepared by Berzelius having been shownby Kruss and Hoffmann (Abstr., 1887,1019 ; 1888,28) to be a mixtureof aurosoauric sulphide with sulphur.Hydrosulphide and polysulphides of ammonia dissolve auric sulph-ide readily on warming, gold being deposited. The sulphides andpolysulphides of the alkali metals dissolve the substance slowly ;whilst the alkali hydrosnlphides dissolve it i n the cold, yielding adeep reddish-brown solution, which, on boiling, becomes pale yellowand deposits gold.These solutions, on treatment with hydrochloricacid, give a flocculent, yellow precipitate, probably consisting of aurichydrosulphide, which soon turns brown with formation of hydrogensulphide and auric sulphide.On precipitation with alcohol at -lo", a concentrated solution ofnuric sulphide in sodium hydrosulphide gives a yellowish precipitate ;this, when filtered through asbestos at the same temperature in an atmo-sphere of nitrogen and washed wihh alcohol, yields a white, crystallineproduct which soon darkeiis in colour. The freshly prepared sub-stance is very soluble in water and is probably fiodium sulphaurate,but it decomposes so rapidly that tiaustmorthy analyses could not bemade.W. J. P.Iodonitro- and Bromonitro-platinum Compounds. By M.VEZES (Compt. rend., 113, 696--698).-The relative stability of thenitro- and hdoid groups in the iodonitro-platinum compounds is theinverse of that observed in the case of the chloronitro- and bromoINORQANIC OEEMISTRY. 281nitro-compounds (Abstr., 1891, 807). The iodine is displaced bynitrogen oxides, and the stable term of the series is the platonitriteand not the platoiodide. Nitrogen oxides readily decompose potassiumplatniodide wit>h liberation of iodine ; whilst, on the other hand, iodinein the forin of vapour or in solution in hydriodic acid or a solution ofpotassium iodide does not decompose potassium platonitrite.The action of an alcoliolic solution of iodine on a warm solution ofpotassium platonitrite, however, yields large, brilliant prisms of t'hecompound Pt,2N02,K,T, + 2Hz0, described by Nilson, but this,ttlthough stable in warm solutions, is decomposed by nitrogen oxideso r potassium nitrite, with liberation of iodine and formation of theplatonitrite.The author has so far failed to obtain a compoundPt,4N0,,KzI,, analogous to the platichloronitrite and the platibromo-nitrite previously described.If, however, an excess of an alcoholic solution of iodine is added toa warm concentrated solution of the platonitrite, and the mixture isconcentrated as rapidly as possible at a gentle heat, potassium nityoso-plati-iodide, PtT3,N0,K212, separates on cooling in small, brilliant, blackcrystals, which remain unaltered a t 100".When heated in a currentof hydrogen, this compound yields water, ammonium iodide, iodine,hydrogen iodide, and a, residue of potassium iodide and platinum.If the liquid is slcwly concentrated (without ebullition) a differentcompound is obtained on cooling. T t is potassium platitetraiodonitrite,Pt14,2NOz,Kz, and separates in small, well-defined, black crystals witha greenish lustre. Like the preceding compound, it is only slightlysoluble in water, yielding a deep brown solution, and it undergoes nochange at 100". When heated in a current, of hydrogen, it yieldswater, ammonium iodide, iodine, and hydrogen iodide, with a residueof potassium iodide and pIatinum.When the mixture yielding these two salts is submitted t o pro-longed ebullition, the excess of iodine is expelled and potassiumplatoiodonitrite is formed.When bromine-water is added t o a solution of potassium platoiodo-nitrite until a11 the iodine is expelled, the brown liquid, when con-centrated in a dry vacuum, yields yellow, tabular crystals.The samecrystals are obtained by heating n solution of potassium platibromo-nitrite, Pt,4N0,,K(,Rr2, with alcohol at 80", aldehyde and other gasesbeing evolved. This new cornpound is potassium platobronionitrite,Pt,2NO2,K,Br, + H,O, and ib very soluble in water. At loo", it becomesanhydrous and biaiglit yellow ; at a higher temperature, it blackenswith evolution of nitrogen oxides, a residue containing potassiumbromide and platinum in the proportions Pt + 2KBr being left.When heated in hydrogen, it yields the same residue without anyformation of ammoni urn bromide, bromine, o r hydrogen bromide,By R.SCIINEIDER (J. pr. Ckem. [ 21, 44,507--512).-Potassium plati?ao~eleilostannate, K,Pt,SnSe,, is preparedby melting together 10 parts of platinum sponge, 6-8 parts of tin selen-ide, 30-40 parts of potassium carbonate, and 30-40 parts of seleniumin a covered porcelain crucible SO that the mass shall remain liquidfor 8-10 minutes after the frothing has ceased. The melt is extractedC. H. B.Two New Seleno-salts282 ABSTRACTS OF CHEMICAL PAPERS.with water, and the undissolved residue digested with concentratedpotassium hydroxide solution, whereby the selenostannate is left un-attacked. It forms small, well-defined, hexagonal tables which areleaden-grey by reflected light and have a strong metallic lustre ; inthin layers they are reddish-brown by transmitted light. In itsgeneral habitus it is very similar to the author's potassium platino-sulphostmnate (Ann. Phys. Chem., 138, 612). At the ordinary tem-perature, it is stable in air ; when heated in air, it loses all its selenium,the residue consisting of a mixture of platinum with potassium stan-nate. It is not attacked by water, ammonia, potash, 01- hydrochloricacid, either hot or cold.Sodium pZat inoseZenostnnnate, Na,Pt,SnSe,, cannot be obtained bymerely substituting sodium carbonate for potassium carbonate in theabove prescription. It is readily formed, however, when 10 parts ofplatinum sponge, 5-6 parts of tin selenide, 40 parts of potassiumcarbonate, 5-6 parts of sodium carbonate, and 40 parts of seleniumare fused together, and the melt treated as described above. It formsleaden-grey, microscopical, hexagonal lamin* with a brilliant, metalliclustre ; the remarks concerning the potassium salt apply also to this.A. G. B.Saline Compounds of the Lower Ruthenium Oxides with theHigher Oxides. By A. JOLY (C'ontpt. rend., 113,694-695.)-Whenthe products of the sudden decomposition of potassium perruthenateat 440" are kept for a long time at this temperature, interaction takesplace with formation of a black, crystalline compound of the composi-tion K20,6Ru205. Sodium permthenate at 440" loses oxygen andwater, and after treatment of the residue with water, which removessodium oxide and the orange sodium ruthenate, a black crystallinepowder is left with a, composition approximating very closely to thatfor Na20, 3Ru205. Barium ruthenate, IBaRuO4, at 440" loses oxygen, andyields a ruthenite, BaRuO,, different in properties from a mixture ofbarium monoxide and ruthenium dioxide. The author directs atten-tion t o the analogy between these compounds and the productsobtained by Rousseau from the permanganates, and the productK,O,Oe,O,, obtained by himself from potassium osmiamate.Action of Light on Ruthenium Peroxide. By A. JOLY (t%~~pt.rend., 113, 693--694).-When sealed tubes containing perfectly dryruthenium peroxide are kept in the dark, no alteration takes place,but on exposure to sunlight, the walls of the tube become coatedwith a pale brown layer, which gradually increases in thickness andeventually transmits only red light. Beyond this point, the peroxidebehind undergoes no further change. The brown deposit dissolvesat once in potassium hydroxide solution, forming a yellow liquidwithout any trace of green, and in hydrochloric acid with evolutionof chlorine and formation of a solution of ruthenium sesquichloride.It seems, therefore, t,hat when exposed to sunlight, ruthenium per-oxide is reduced to the trioxide, Ru03.C. H. B.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8926200270

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

MINERALOGICAL OHEMISTRY. 283 Mi n e r a 1 o g i c a 1 C h e m i s t r y. Sulphur, Orpiment, and Realgar in the Yellowstone National Park. By W. H. WEED and L. V. Pmssorj (Amer. J. Sci., 42, 401-405) .-In the Yellowstone National, Park there are, besides the geyser basins, many small hot-spring areas where fumeroles and solfataras are still active. At most of these places, deposits of sulphur occur in and around the vents from which the vapours issue. At Highland Hot Springs and a t Crater Hill the vents are very abundant, and large deposits of sulphur are found, frequently forming clusters of delicat'e crystals. Details of the measurement of the crystals are given by the authors. Although no analysis was made, the material is apparently of great purity. The presence of arsenic in the hot-spring waters of the Yellowstone Park was noticed by A .Hague (Abstr., 1888, 122), and a, careful search for deposits of arsenical sulphides was rewarded by the dis- covery of realgar and orpiment at the Norris Geyser basin. Siliceous sinter is the only other mineral occurring with these arsenical sulphides. B. H. B. Occurrence of a Natural Gold Sulphide. By T. W. T. ATHERTON (Chenz. News, 64, 278).-The author observed the occurrence of gold i n an exceptionally fine state of sub-division in an arsenical pyrites ; further investigation showed that this gold could be extracted by heating the finelypulverised pyrites for some hours with a solution of sodium sulphide. It hence appears that the gold, or a t least some of it, is present as sulphide.The following is the percentage composi- tion of the ore in general ; it also runs 5 02s. 3 dwts. 8 grs. of gold, and 16 dwts. of silver, to the ton. SiOz. A1,0,. CaO. S. As. Fe. Co. Xi. 13.94 6.59 0.9 16.58 33.27 27.72 0.96 trace It is found in a large irregular lode of arsenical pyrites in a felsite Both in the lode and in its vicinity dyke in a mica-schist country. there are large quantities of pgrophyllite, D. A. 1;. New Analyses of Uraninite. By W. F. RILLEBRAND (Amer. J. Sci., 42, 390--393).-The author gives the following analyses of uraainite. (See next page.) la is a re-analysis of' nivenite from Llano Co. Texas. It agrees in the main with the original analysis by Hidden and Mackintosh, I b (Abstr., 1890, 457). I1 is from a new locality, Marietta, Grenville Co., South Carolina.I11 is from the Villeneuve mica mine, Ottawa Co., Quebec. IV represents the composition of a specimen from Johanngeorgenst,adt, in Sa,xony. None of these specimens was fresh, and consequently no light could be thrown on the ultimate composi- tion of the mineral. Valuable data, however, are afforded as to the284 ABSTRACTS OF OHEM'ICAL PAPERS. presence or absence of nitrogen (compare Abstr., 1890, 456; 1891, 527), and of the rare earths. The species, it will be seen, may be broadly divided into two groups, one of which is charact.erised by the presence of rare earths, and the other by their absence. With the former group, nitrogen appears t o be invariably associated. Probably all the varieties of the first group occur in crystals, whilst the members of the second gronp are generally free from crystalline form.U03. UO,. Tho,. Zi*02. CeO,. La group. Y group. CaO. Ia. 44.17 20.89 6.69 0.34 0.34 2.36 9.46 0.32 I b . 46.75 19.89 7.57 - - - 11-22 - 11. 83.95 1-65 0-20 0.19 2-05 6.16 0.41 111. 4146 34.67 6.41 ? 0.40 1-11 2.57 0.39 IV. 59.30 22.33 none 1.00 Ia. 10.08 1.48 0.54 0.46 1.47 0.14 Ib. 10.16 2.54 - - 1.22 0.58 IT. 3-58 - 111. 11.27 1.47 0.86 0.19 0.13 0-10 IV. 6.39 3.17 0.02 0.50 - 0-21 L----J L-- 7-- PbO. H,O. N. SiOp. Insol. Fez03. 020 trace - - €3. H. B. Discovery of Diamonds in Meteoric Iron. By A. E. FOOTK (Amer. J. Sci., 42, 413-417).-1n 1891, a meteorite was found near Cafion Diablo in Arizona, and was thought to form part of a vein of metallic iron. The largest mass discovered weighs 201 Ibs., and has a somewhat flattened rectangular shape showing deep pits, three of which pass entirely through the iron.One other large mass was found weighing 154 lbs. A mass weighing 40 lbs. was broken in pieces with a trip hammer, and it was in cutting one of the fragments of this mass that diamonds were discovered. The diamoiids are black and white, their nature being established by their hardness and indifference to chemical agents. Carbon in the form of a pulveru- lent iron carbide occurs in the same cavity with the diamonds. The proportion of nickel in the general mass is 3 per cent. The Tonganoxie Meteorite. By E. H. S. BAILEY (Anzer. J . Xei., 42, 385-387).-This meteorite was found in 1886 near Tonganoxie, Leavenworth Co., Kansas. The specimen originally weighed 26 lbs.Its shape is that of an irregular triangular pyramid, 98 inches long, 66 inches wide, and 44 inches deep. As shown by a photograph accompanyirg the author's paper, the surface of the meteorite is covered with numerous depressions. The entire exterior is covered with a reddish-black coating of iron oxide, with occasional drops of chloride of iron exuding after having been exposed t o the air. The analysis of the meteorite gave the following results:- Fe. Ni. c o . P. cu. Total. 91.18 7.93 0.39 0.10 trace 99.60 On treatment with nitric acid, the surface exhibited the Widman B. H. B. The sp. gr. is 7.45. stattian figures very clearly. B. H. B.ORGANIC OHEMISTRY. 285 Composition of some Subterranean Waters fiom near Port- Vendres. By J.C. ESSNER (H,dZ. Soc. Cl~irn. [8], 6, 148-151).-- Eleven samples of water collected from the valley of Cosperons, on the Mediterranean slope of the Albhes, in the commune of Port-Vendres, were found to contain calcium, magnesium, alumininni, chlorine, and sulphuric acid. One sample only was neutral, seven contained from 0064 to 0.065 gram of free sulphuric acid per litre, and three contained respectively 0.175, 0.285, and 0.506 gram of free acid per litre. The neighbowing rocks contain iron pyrites disseminated through- out ; the fissures are filled with a yellow powder consisting of ferric oxide, together with some basic ferric sulphates The natural acidity of these waters is attributed to the formation of this deposit. The waters retain only a trace of iron, as the dissolved salts decom- pose with formation of free sulphuric acid.This view is confirmed by the behaviour of rain-water collected in a cistern at a height of 250 metres above the level of the sea after several months of dry weather. The cistern and works were constructed of stones a,nd debris of the surronnding rocks. Water taken from the cistern, dirty as collected, gave 9.073 grams of dissolved crystallised substances, and 0.105 gram of suspended matter; it was slightly acid. After six days rest, the filtered water already yielded only 6.179 grams of crystallised residue per litre, arid 2.997 grams of basic ferric sulphate had been deposited. After an exposure to free air of one month, the water, after filtration, contained only traces of iron, together with 0.765 gram of sulphuric acid (H&04), and gave 1.010 gramn of residue calcined at EL red heat, cotitaining calcium, magnesium, and aluminium, with traces of chlorine, sulphuric acid, iron, potassium, and sodium.The analysis of the primitive water gave :- Iron calculated as Fc203.. ........ 1.500 grams per litre. CaO ........................... 0.6~37 9 , MgO ........................... 0,354 9, A1,O 3 . . . . . . . . . . . . . . . . . . . . . . . . . . 0.012 9 , Chlorine. ....................... 0.024 .. Total H,S04 .................... 3.672 YP W. T.MINERALOGICAL OHEMISTRY. 283Mi n e r a 1 o g i c a 1 C h e m i s t r y.Sulphur, Orpiment, and Realgar in the Yellowstone NationalPark. By W. H. WEED and L. V. Pmssorj (Amer. J. Sci., 42,401-405) .-In the Yellowstone National, Park there are, besides thegeyser basins, many small hot-spring areas where fumeroles andsolfataras are still active.At most of these places, deposits ofsulphur occur in and around the vents from which the vapoursissue. At Highland Hot Springs and a t Crater Hill the vents arevery abundant, and large deposits of sulphur are found, frequentlyforming clusters of delicat'e crystals. Details of the measurement ofthe crystals are given by the authors. Although no analysis was made,the material is apparently of great purity.The presence of arsenic in the hot-spring waters of the YellowstonePark was noticed by A . Hague (Abstr., 1888, 122), and a, carefulsearch for deposits of arsenical sulphides was rewarded by the dis-covery of realgar and orpiment at the Norris Geyser basin.Siliceoussinter is the only other mineral occurring with these arsenicalsulphides. B. H. B.Occurrence of a Natural Gold Sulphide. By T. W. T. ATHERTON(Chenz. News, 64, 278).-The author observed the occurrence of goldi n an exceptionally fine state of sub-division in an arsenical pyrites ;further investigation showed that this gold could be extracted byheating the finelypulverised pyrites for some hours with a solution ofsodium sulphide. It hence appears that the gold, or a t least some ofit, is present as sulphide. The following is the percentage composi-tion of the ore in general ; it also runs 5 02s. 3 dwts. 8 grs. of gold,and 16 dwts. of silver, to the ton.SiOz. A1,0,. CaO.S. As. Fe. Co. Xi.13.94 6.59 0.9 16.58 33.27 27.72 0.96 traceIt is found in a large irregular lode of arsenical pyrites in a felsiteBoth in the lode and in its vicinity dyke in a mica-schist country.there are large quantities of pgrophyllite, D. A. 1;.New Analyses of Uraninite. By W. F. RILLEBRAND (Amer. J.Sci., 42, 390--393).-The author gives the following analyses ofuraainite. (See next page.)la is a re-analysis of' nivenite from Llano Co. Texas. It agrees inthe main with the original analysis by Hidden and Mackintosh, I b(Abstr., 1890, 457). I1 is from a new locality, Marietta, GrenvilleCo., South Carolina. I11 is from the Villeneuve mica mine, OttawaCo., Quebec. IV represents the composition of a specimen fromJohanngeorgenst,adt, in Sa,xony. None of these specimens was fresh,and consequently no light could be thrown on the ultimate composi-tion of the mineral.Valuable data, however, are afforded as to th284 ABSTRACTS OF OHEM'ICAL PAPERS.presence or absence of nitrogen (compare Abstr., 1890, 456; 1891,527), and of the rare earths. The species, it will be seen, may bebroadly divided into two groups, one of which is charact.erised by thepresence of rare earths, and the other by their absence. With theformer group, nitrogen appears t o be invariably associated. Probablyall the varieties of the first group occur in crystals, whilst themembers of the second gronp are generally free from crystalline form.U03. UO,. Tho,. Zi*02. CeO,. La group. Y group. CaO.Ia. 44.17 20.89 6.69 0.34 0.34 2.36 9.46 0.32I b .46.75 19.89 7.57 - - - 11-22 -11. 83.95 1-65 0-20 0.19 2-05 6.16 0.41111. 4146 34.67 6.41 ? 0.40 1-11 2.57 0.39IV. 59.30 22.33 none 1.00Ia. 10.08 1.48 0.54 0.46 1.47 0.14Ib. 10.16 2.54 - - 1.22 0.58IT. 3-58 -111. 11.27 1.47 0.86 0.19 0.13 0-10IV. 6.39 3.17 0.02 0.50 - 0-21L----JL-- 7--PbO. H,O. N. SiOp. Insol. Fez03.020 trace - -€3. H. B.Discovery of Diamonds in Meteoric Iron. By A. E. FOOTK(Amer. J. Sci., 42, 413-417).-1n 1891, a meteorite was found nearCafion Diablo in Arizona, and was thought to form part of a vein ofmetallic iron. The largest mass discovered weighs 201 Ibs., and hasa somewhat flattened rectangular shape showing deep pits, three ofwhich pass entirely through the iron. One other large mass wasfound weighing 154 lbs.A mass weighing 40 lbs. was broken inpieces with a trip hammer, and it was in cutting one of the fragmentsof this mass that diamonds were discovered. The diamoiids areblack and white, their nature being established by their hardnessand indifference to chemical agents. Carbon in the form of a pulveru-lent iron carbide occurs in the same cavity with the diamonds. Theproportion of nickel in the general mass is 3 per cent.The Tonganoxie Meteorite. By E. H. S. BAILEY (Anzer. J . Xei.,42, 385-387).-This meteorite was found in 1886 near Tonganoxie,Leavenworth Co., Kansas. The specimen originally weighed 26 lbs.Its shape is that of an irregular triangular pyramid, 98 inches long,66 inches wide, and 44 inches deep.As shownby a photograph accompanyirg the author's paper, the surface of themeteorite is covered with numerous depressions. The entire exterioris covered with a reddish-black coating of iron oxide, with occasionaldrops of chloride of iron exuding after having been exposed t o theair. The analysis of the meteorite gave the following results:-Fe. Ni. c o . P. cu. Total.91.18 7.93 0.39 0.10 trace 99.60On treatment with nitric acid, the surface exhibited the WidmanB. H. B.The sp. gr. is 7.45.stattian figures very clearly. B. H. BORGANIC OHEMISTRY. 285Composition of some Subterranean Waters fiom near Port-Vendres. By J. C. ESSNER (H,dZ. Soc. Cl~irn. [8], 6, 148-151).--Eleven samples of water collected from the valley of Cosperons, on theMediterranean slope of the Albhes, in the commune of Port-Vendres,were found to contain calcium, magnesium, alumininni, chlorine,and sulphuric acid.One sample only was neutral, seven containedfrom 0064 to 0.065 gram of free sulphuric acid per litre, and threecontained respectively 0.175, 0.285, and 0.506 gram of free acid perlitre.The neighbowing rocks contain iron pyrites disseminated through-out ; the fissures are filled with a yellow powder consisting of ferricoxide, together with some basic ferric sulphates The naturalacidity of these waters is attributed to the formation of this deposit.The waters retain only a trace of iron, as the dissolved salts decom-pose with formation of free sulphuric acid. This view is confirmedby the behaviour of rain-water collected in a cistern at a height of250 metres above the level of the sea after several months of dryweather. The cistern and works were constructed of stones a,nddebris of the surronnding rocks. Water taken from the cistern, dirtyas collected, gave 9.073 grams of dissolved crystallised substances,and 0.105 gram of suspended matter; it was slightly acid. Aftersix days rest, the filtered water already yielded only 6.179 grams ofcrystallised residue per litre, arid 2.997 grams of basic ferric sulphatehad been deposited. After an exposure to free air of one month, thewater, after filtration, contained only traces of iron, together with0.765 gram of sulphuric acid (H&04), and gave 1.010 gramn ofresidue calcined at EL red heat, cotitaining calcium, magnesium, andaluminium, with traces of chlorine, sulphuric acid, iron, potassium,and sodium.The analysis of the primitive water gave :-Iron calculated as Fc203.. ........ 1.500 grams per litre.CaO ........................... 0.6~37 9 ,MgO ........................... 0,354 9,A1,O 3 . . . . . . . . . . . . . . . . . . . . . . . . . . 0.012 9 ,Chlorine. ....................... 0.024 ..Total H,S04 .................... 3.672 YP W. T

ISSN:0368-1769    

DOI:10.1039/CA8926200283

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

Organic Chemistry.285A Method for Determining the Constitution of Saturatedand Unsaturated Halogen Derivatives and Hydrocarbons.By M. W~LDERXANN (J. pr. Chern. [2], 44, 470-496).-11his is amethod for the determination of the coristitution of the higherVOL. LXII. 286 ABSTRAOTB OF OHEMICAL PAPERS.members (above n = 4) OF the aliphatic series, founded on Pllternntchxlogenisation and removal of the elements of halogen hydro-acids,with determination of the heats of combustion of the various hydrn-c;wbons produced. The paper is not suitable for abstraction, as themethod could not be made intelligible without a full reproductionof the details both of the argument employed and of the variousexamples given. A. G. B.Platinum Thiocyanate and Platinothiocyanates. By T.GUARESCHI (Chem.Centr., 1831, ii, 620-622; from Giorn. R. Amd.Med., 1891) .-The author has prepared potassium phtinothiocyanatcaccording to the methods of nuckton. Wyrouboff and Norton. Hefinds that the salt crystallised from alcohol is anhydrous, whilstthat crystallised from water contains 2 mols H20. This i t loses ifdried over calcium chloride, but he does not find that it is so readilylost on exposure to the air at ordinary temperatures as Wyrouboflstated.Potassium pZatinothbcyanate, &Pt( cNS)6, gives characteristicprecipitates with many organic: bases, and may be used as a test forcertain alkalo'ids. The platinothiocyanates of tJhe tertiary amines areless soluble than the corresponding salts of. the secondary andprimary amines.In many cases, the double salts of the secondarybiises melt a t a lower temperature than those of the primary.Monomethy Zarnine platinofhiocyancrte, (NH,Me),,H,Pt (CNS),, isprepared by allowing the mixed solutions of potassium platinothio-cyaiiate and of methylamine hydrochloride to remain for severiildays, when the double thiocyanate crystallises out in long, red,rliombic prisms. The dimethylamine salt, (NHMe,),,H2Pt(CNS),. i nprecipitated as red prisms o r needles on mixing the not very concen-trated solutions of the respective salts. It, melts a t 160-170" withdecomposition, arid is soluble in cold water, more readily in hot watei.,readily soluble i n alcohol, insoluhle in ether. The trimethyZamine salt,(NMe,),,HzPt(CNS),, forms red prisms, sparingly soluble in coldwater, soluble in alcohol, but insoluble in ether; it melts at 175" withdecomposition.The ethylamine salt is similar to the methylamine salt.Thediethylamine: salt, (EHEt,)2H2Pt(CNS)6 + 2Hz0, is prepared bymixing 1 part of the hydrochloride in 6 parts of water wittipotassium platinothiocyanate. A liquid precipitate at, first sepa-riltes which rapidly solidifies to a mass of sliort prisms, or rect-angular, lemon-yellow plates, which, after drying in the air, meltat 58-58.5", and in the anhydrous condition, melt a t 79-80'.It is sparingly soluble in cold water, more readily in hot water,w r y soluble in adcohol, insoluble in ether. The triethylamine salt,(NEt,),,H,Pt(CNS),, is precipitated, when the solution of the hydro-chloride, acidified with hydrochloric acid, is added to potassiumplatinothiocyanate, a s a thick, red liquid, which solidifies graduallywhen agitated. When recrystallised from water, it separates intl!e same way.It consists of golden-Fellow plates, melts at165-167", and decomposes at 180". It is sparingly soluble in coldwater, more readily in hot water and in alcohol, insoluble in etherORGANIC CHEMISTRY, 28 7Propylamine, butylamine, and amylamine react in the same manner asmet hylamine and ethy lamine.The ethyienediamine sal t, C2H4N,H4,H,Pt(CNS),, is a yellow pre-cipitate, sparingly soluble in water, and blackens a t 140-150".The pentnmethyl~nediarnine salt, C5H14N1,H,Pt;( CNS),, is obtained I yprecipitatinv the solution of the hydrochloride with platinum thio-cyanate.The precipitate soon becomes crystalline, and forms red-dish needles which commence to turn brown a t 160", and becomequite black a t 176", but do not melt. It is soluble in alcohol andwater, hut insoliible in ether.The dincetonenmine salt, ( CO~e.CHz*CMe2*NH,)~,H2Pt (CNS),, isobtained by precipitating the solution of dincetoneamine oxalate withthe platinothiocyanate. It is thus obtained as a crystalline pre-cipitate, which, when recrystallised from hot water, forms red prisms,soluble in alcohol, insoluble in ether It melts at 165" with decom-position. The g.z~nnidine salt, (C,H,N,),,H,Pt(CNS),, is obtainedin beautiful red crystals on mixing solutions of guanidine hydro-chloride with the platinothiocganate.It is also obtained when theso1 ution of guariidine thiocyannte is mixed with platinum chloride.It blackens a t 1'70-175" without melting.The aniline salt, (NH,PIi),,H,Pt(CNS),, forms dark-red crystalswhich melt a t 100-105", soluble in alcohol and water, insnluble inether. The a-?iaphthyZarnine salt forms a dark-yellow precipitate, thep-salt a light-yellow precipitate, from solutions of the hydrochlorides ;they are both somewhat difficult to obtain crystalline ; they decomposereadily on exposure to moist, air, especially the a-salt,. They bobhmelt to brown liquids, the a-salt a t 140", the P-salt a t 180"Paratoluidine, allylamine, and furfurine are precipitated i n likemanner.PhenyZhydmeine reduces the solution of the platinothioopanate.Tetrahydro-a-napb t h y lamine forms a yellow, crystalline precipitate.The py&line salt, (C5H,N),,H,Pt(CNS),, crystnllises in red prisms,and is precipitated from the solution of the hydrochloride.It is notchanged by exposure to the air, but commences to decompose a t100-105" and melts at 170-172' to a black liquid ; it is sduble in hotwater, but only sparingly in cold water. Protracted boiling wit,h watercauses decomposition. The piperidine salt, ( C5H,,N)2,H2Pt(CNS),,is precipitated a t first as a liquid, which later solidifies in lemon-yellow prisms, sparinglg soluble in cold water, readily so in hotwater and in alcohol. Coniiciie as hydrochloride o r as hydrobromideis precipitated, if the solution be not too dilute, as a i-ed oil, whichcould not be obtained crystalline.A solution of coniine hydro-bromide 1 : 1000 is not precipitated, hut nicotine is precipitated asyellow crystals at a dilution of 1: 3000. This salt is almost in-soluble in cold water, and may serve to distinguish coniine fromnicotine. The spartrzne salt forms a sulphur-yellow, powdery pre-cipitate. The a- and /3-guinoline salts are precipitated as yellow,microscopical crystals; the a-salt is the darker; even a solution of1 : 6000 is precipitated.Fphedrine, apomorphine, apocodeine, cocIxi'ne, tind ecgonine are like-wise precipitated. Glycosamine is not precipitated.x 288 ABSTRACTS OF CHEMICAL PAPERS.The reaction was examined in the case of the following alkdoi'dswith the view of determining the delicacy in each case.Strychminebolution, 1 : 40,000, gave a cryst,alline precipitate after some time ;brurine, 1 : 18,000 ; atropine, 1 : 20,000 ; nzorphine, 1 : 1000 ; reratrine,1 : 10,000 ; nicotine, 1 : 3000 ; codeane, 1 : 2000, all precipitate im-mediately. Quinine, cinchonine, quinidine, cinchmidine, I : 100,000,also give precipitates immediately ; aspidospermine, 1 : 40,000 is alsoprecipitated immediately. J. W. L.Decomposition of Hydrocarbons with Steam. By COQUILL~ONand HEKRIVAUX ( C h ~ m . Centr., 1891, ii, S77 ; from J. UsineR ti, Guz,1890, 355).--The authors haye determined the composition of thegaseous mixture obtained by heatirg methane and steam together.When the gases were Rubjected t o the action of an incandescentplatinum wire fixed at the lower end of the eudiometer, the RRSproduced had the composition : 2.45-2-50 per cent.COz. 13.68-16.50per cent. CO, 17.84-14.60 per cent. CH,; 66.03-66.40 percent. H. When the methane and steam were passed through threeiron tubes heated to redness, the resulting gas had the cornposition:l - U U per cent. CO,, 19-86 per cent. CO, 8-24 per cent. CHI, 70-90 percent H. After passing through tubes heatcd to L white heat, theresulting gas has the composit,ion: 12.01 per cent, GO,, 7.35 percent. CO, 50.64 per cent. H, no methane remaining. J. W. L.Hydrocarbons from a- and p-Amyrin. By A. VESTERBERG(Ber., 24, 3834-3836).-As already stated (Abstr., 1887, 733 ; 1891,165), a- and p-amgrin are converted by phosphorus pentachlorideinto dextro-a- and P-amyrilene, Ca0Hd8, and a-amyrin by phosphoruspentoxide into laevo- a-amyrilene, C,,H4,.Dextro-a-amyrilene issparirigly soluble in acetic acid, readily in light petroleurn and ben-zene, and commences to decompose at its boiling point. Laevo-a-amyrilene is prepared by adding a benzene solution of a-amyrin tophosphoxus pentoxide, allowing the cherry-red jelly to remain forsome drlys, and adding water t o remove phosphoric acid. The ben-zene solution, on spontaneous evaporation, deposits prismatic crystalsmrrounded by a glutinous mass ; the latter is removed by ether, andthe residue reci-ystallised from hot bepzene. It fornis rhombic c r p -tala (a : b : c = 0.789 : 1 : 0.505;, melts at 193-194", is Rparinglysoluble in ether, more readily in light petroleum and benzene, and hasthe sp.rotatory power [ol]D = -1lu4.9.p-Amyrilent: is almost insoluble in alcohol and acetic acid, and lessreadily soluble in ether, light petroleum, and benzene t h a n dextro-a-am yrilene. H. G. C.Derivatives of Glycerol. By E. SEELIG (Ber., 24, 3466-3471).-Diacet ylgljcerol (diacetin) is obtained in quantitative yield byboiling 95 per cent. glycerol (4CO grams) with glacial acetic ncid(1000 grams) in a reflux apparatus for t3+ hours, dist.illing up to 116",replacing the distillate (about 270 grams) by an equal weight ofiresh glacial acetic acid, boiling for a further 1 7 honrR, and, after dis-tilling off the acetic acid, rectifying the product under a, pressure oOBGXNIC CHEMISTRY.28940 mm. It boils a t 172-174" (40 mm.), stndnt 259-261" (760 mm.)has a sp. gr. 1.178, is miscible with water, ether, chloroform, andbenzene, but almost insoluble in light petroleum and carbon hisulphideOn one occasion the author treated a sample of ordinary glycerol inthe above manner, and obtained a product which was only misciblewith water to a limited extent, and did not become acid on boilingwith it. Diacetylglycerol can only be converted into the triacetylderivative (triacetin) aw follows :-Coarsely pulverised, anhydmilseodium acetate (60 grams) is well mixed with acetic anhydride (150grams), diacetylglycerol (200 grams) added, and the m'xture boiledin a, reflux apparatus for 16 hours; the product is shaken withl$ times its volume of ether and an equal quantity of water.when thetriecetrl derivative is dissolved by the ether, and is isolated by distil-lation. It boih a t 171" (40 mm.), and a t 258-259" (760 mm.), hasa sp. gr. 1.155, is sparingly soluble in water, and, unlike the diacutylcompound, in not decomposed when boiled with i t ; it is miscible with~lcohol, ether, chloroform, and benzene, but almost insoluble in lightpetroleum and carbon bisulphide. It would thuR appear that thetriacetylglycerol described by Schmidt (Xbstr., 1880. 312) was i nreality the diacetyl derivative, and Rince a mixture of the two cannotbe separated from one another, Rottinger's method (Abstr., 1891,1183) is invalid.When diacetylglycerol is dissolved in glacial acetic acid, saturatedwith hydrogen chloride.and, after heating at 100" for two hourR, dis-tilled under a pressure of 40 mm., two fractions, consisting of im-pure dichloracetpl derivatives, pass over at 101-107" and a t10 7- 115" respectively, whilst chlorodiace tylgly cerol, contami nrttedapparently with chloracetylglycerol, passes over at 137-144" (seebelow), and, lastly, unaltered diacetylglycerol distils ; lower boilingcompounds are also formed. The same result is obtained by leading astream of hydrogen chloride through Soiling diacetylglycerol. Whencooled acetic anhydride (130 grams) is saturated with dry hydrogenchloride, mixed with diacetjlglycurol (190 grams), again Raturatedwith hydrogen chloride, 70 grams of the gas being absorbed iu all,and the mixture heated a t 110" for 30-40 hours, a chlorodiacetyl-glycerol boiling a t 142-149" (40 mm.), or a t 250-240" (760 mm.),a dichloracetylglycerol boiling at 108-112" (40 mm.), or at189-199" (760 mm.), together with much triacetylglycerol andlower boiling compounds, are obtained ; whilst if hydrogen chlorideis passed through boiling triacetylglycerol for 70 hours, a chloro-diacetylglycero t boiling a t the same temperature as the last-men-tioned one, and haviiig a sp.gr. 1.204, is produced. When thefraction boiling a t 137-144" (40 mm.) from diacetylglycerol andhvdrogen chloride is heated with an excess of acetic. anhydride at18U-190°, a chlorodiacetylglgcerol boiling at 141-148" (40 mm.) isobtained, whilst a similar compound is prodnced by heating a-chlor-hydrin with an excess of acetic anhydride.When dirhlorhydrin (pre-pared from a-chlorhydrin) is heated with acetic anhydride, it yields twodichlorticetylglycerols boiling at 108-112" and at 11%116" (4-0 mm.)respectively. The dichlorecetylglycerol boiling at the lower tempera-ture is probably the symmetrical derivative, and, since only ou230 ABSTRACTS OF CHEMICAL PAPERF.monochloro-derivative is formed from the diacetplglycerol, the twoacetoxy-groups in this compound probably occupy consecutive posi-tions, and support is afforded to this view by the fact that thediacetylglycerol yields an aldehyde on oxidation with nitric acid ; thehydrazone from the latter melts a t 161". A. R. L.Reactions of Xyloae and Arabinose.By TOLLENS (BUZZ. SOC.Chim. [3], 6, 161--16~).-This is a note containing extracts frommemoirs by Wheeler and Tollens (Annulen, 254, 314), and by Allenand Tollens (Annulen, 260, 304), which show that the coloured reac-tions of xylose with orcinol and phloroglucinol, given by Bertrand inthe BUZZ. Cs'oc. Chinz. [3], 5, 932, were already known.W. T.Oxidation Products of a- and p-Amyrin. By A. VESTERHERG(Rer., 24, 3836-3843).-Both a- and P-amyrin, when oxidised withchromic acid in acetic acid solution, yield as chief products the corre-sponding ketones (or, possibly, aldehydes), a- aud ,8-amyrone.a-Amyrone, C30H480 + H,O, crystallises from a mixture of alcoholand acetic acid in large tablets, melts a t 125-130", dissolves readilyin ether, hot benzene, and acetic acid, sparingly in light petroleum:mi alcohol.The substance thus obtained is, however, not quite pure,but, on treatment with hydroxylamine, it readily yieldR pure a-umyi*on-oxinae, C30H48:NOH, which crystallises from benzene in needlr s, andmelts with evolution of gas at 233-234". ,%Arnyrone, C30H480, formsnodular aggregates of small prisms, melts a t 178-180", is readilysoluble in chloroform, ether, and benzene, sparingly in light petroleumand alcohol ; its oxime, CBUH4&NOH, crystdlises from benzene in long,pointed plates which melt wit,h evolution of gas a t 862-263".When a-amyrin acetate is subjected to the action of chromic acidi n acetic acid solution, two atoms of hydrogen are replaced by one ofoxygen with formation of oxy-a-uniyrin acelate, CwH4,0.0Ac, whichc.rystallises from benzene in PIX-sided, rhombic plates (a : b : c =Oti845 : 1 : 1.2538), melts a t 278", and is insoluble in alcohol andether, sparingly soluble in acetic acid, readily in benzene.By theaction of alcoholic potash, it is converted into ozy-a-aniyrin,C,H4,0mOH + 2Hz0, which melts a t 207-2808", and forms acicularcrystals readily soluble in alcohol, ether, and benzene, insoluble inlight petroleum; the 2 mols. H?O are slowly evolved a t 100". ItsHolutions in alcohol and benzene, like those of bromo-@-amyrin,solidify to jellies on cooling.P-Amyrin acetate, on oxidation, appears to behave i n a mannersimilar to the a-compound, but the. 0x3 -p-amyrin acetate could not beobtained free from unaltered p-amjrin acetate.The oxygen atom in these compounds is not present in the form ofa hydroxyl or carbonyl group, for oxy-a-nmyrin acetate is not actedon by acetic anhydride or hj-droxylamine ; i t is therefore probablypresent in the same form a s in the alkylene oxides.A similar corn-pound was obtained by Schrot.ter (dbstr., lW2, 6ti) by the oxidationof borneol acetate.The alcohol8 related to amyrin appear to be widely distributed inthe vegetable kingdom Liebermann's cholesterin reagent (acetiORQANIO CHEblISTRY. 291anhydride and concentmted sulphuric acid) gives strongly colouredsolutions witlh almost all amyrin derivatives, the bromine compoundsgiving a blue, and the others a violet or purple-red, coloration.Laevo-a-amyrileae gives only a yellowish, or, at most, pink, coloration.Pectin Substances.By A. HERZFELD (Ckem. Centr., 1891, ii,618-619 ; from Z e i t . Verein Riibenziick. Ind., 1891, 667-678).-Para-pectic a-cid was obtained by the author by heating 500 grams of slicedbeetroot with 1000 grams of water and 50 C.C. of concentrated hydro-chloric acid at 70” for one hour. The liquid was separated fimom thesolid portion, neutralised with sodium carbonate, and precipitatedwith alcohol. The substance thus obtained was not quite free frommineral matter, and contained 29.6 per cent. of mucic acid and 4 percent. of furfuraldehyde. Parapectic acid appears to consist of amixture of substances which yield arabinose and galactose.hetapectic acid was obtained both from the sliced roots and fromparapectin by treatment with calcium carbonate.The specimens thusobtained diil’ered in their optical properties, the one being dextro-rotatory, whilst the other was 1Eevo-rotatory, and the amounts of mucicacid and furfuraldehyde obtained from each were not the same.H. G. C.J. W. L.First Product of the Reduction of Nitro-compounds withTin and Hydrochloric Acid, or with Stannous Chloride. By E.HOFFMANN and V. MEYER (Ber., 24, 3528-3535).--Tt was obfiervedlong ago that, in preparing normal butylamine by the reduction ofnitrobutane with tin and hydrochloric acid, there is formed a con-siderable quantity of a substance which reduces Fehling’s solution.The authors’ recent experiments have shown that other fatty nitro-compounds, such as nitromethane, nitroethane, and secondary nitro-propane, show a like behaviour, but that nitrobenzene and nitrophenoldo not yield any substances which have a reducing action on Fehling’Asolution.It was also found that when nitromethane (I mol.) istreated with piire stannous chloride (1 mol.) in concentrated hydro-chloric acid solution, methylamine hydrochloride, ammonium chloride,and /3-methylhydroxylamine hydrochloride, NHMe-OH, HC1, areiormed ; the three compounds are best separated by fractionally pre-cipitating the alcoholic solution of the mixed products with dryother.These experiments show that the conversion of nitromethane intomethylamine takes place in the follow in^ two phases :--CHyNO, +2H, = H20 + NHMe*OH and NHMeBOH + H2 = H,O + NHrJMe,and that the reduction of the Fehling’s solution is due to the forrna-tion of a, hydroxylaniine derivative.By G.Mrwmr (Gazzetta, 21, ii, 192-205).--The author replies to Hantzsch’s criticisms (Abstr., 1891,823) on his explanation I€ the isomerism of oximes (Abstr., 1891,1354). The conversion of the p-oximes into nitriles is readily ex-plained by snpposing the formation of a nitrouo-derivative as an iiiter-mediate product. The intramolecular change uoted by Beckmann canF. S. K.Isomerism of Oxirnes292 ARSTRAOTS OF OHEMICAL PAPERS.also he explained in a somewhat Rimilar manner. To the argument thatthree, and not two, isomeric oximes are accounted for by the author'shypothesis, i t is replied that the stereochemical hypothesis is, in manyoases, open to the same objection.Finally, the author's hypothesisis in no way dependent on the presence of the benzene nucleus, butonly requires the compound to contain the group X=C-C=X; at3this group is contained in the oximes of succinic acid, the isomerismexisting among them is satisfactorily explained. W. J. P.Action of Oxidising Agents on Aliphatic Thiocarbamides.Ry D. E. HECTOR (J. pr. Chem. [2], 44, 492-506 ; compare Abstr.,1889, 872 ; l890,526).-When thiocarbamide is heated with hydrogenperoxide in hydrochloric acid solution, it is decomposed with theformation of ammonium chloride, sulphur, sulphuric acid, and carb-onic anhydride.Pseudothiocyanogen, HC3N3S3, was the ultimate product of theaction of hydrngen peroxide on ammonium tbiocyanate in hydro-chloric acid solution; it did not dissolve in alcohol, but dissolvedreadily in potassium hydroxide solution, from which it waH precipitatedby hydrochloric acid ; the alkaline solution p v e a yellowish-brownprecipi t8a te with silver nitrate.Allylthiocarbamide is decomposed when heated with hydrogenperoxide in neutral solution, and subsequently with barium hydroxide,*with formation of sulphnric acid, formic acid, allylamine, and am-monia.Allylforma~midine bisulphide, S,[ C (NH*C,H,) INHI,, is prepared byheating ally1 thiocarbamide with hydrogen peroxide (Q mol.proportion)in an acid solution. After filtering off the sulphur, separating sulph-uric acid by barium hydroxide, and the excess of the latter by carb-onic anhydride, the liquid is evaporated, until a viscid oil separatesou cooling.The oil is dried on the water-bath, and cooled in a deRic-cator, when it sets to a vitreous mass, the analysis of which points tothe above formula. The new base is bivalent ; i t dissolves readily in hotwater. but sparingly in cold, and these solutions turn red litmus blue ;it also dissolves i n alcohol, but not in ether, benzene, or chloyoform.It decomposes when heated. Its salts do not crysiallise, but are verysoluble in water. An aqueous solution of the bisulphide gives a whiteprecipitate with silver nitrate, which rapidly becomes black ; it isalso precipitated by platinic chloride, mercuric chloride, picric acid,potassium ferrocyanide, and potassium ferricyanide. When i t isheated with barium hydroxide, ammonia and allylamine are evolved.The suzpphate, C8HI4N4S2,H2SO4 + HzO, forms a viscous, white mass,but does not cr.ystallise ; the picrate, C8Hl4N4SZ,2CeH3N3O7, formsyellow granules, which melt at 178-180" ; the plntinochZorides,C,H14N4S2,H,PtC16 + 2H20 and (CJI,,Nd3,,2HCl),(PtC14)2, wereboth obtained ; the mercurodloride, C8H1i"S2,4HgC12, is a white,crystalline powder, and melts a t 171-172".-This compound isobtained by dropping a solution of potassium nitrite (4 grams) intoC S-y.C,H,C S.N-CqH5' DiaZly ldifhiotetrahydrotriazole, NEORQANIC CHEMISTRY. 293R d u t i o n of allylthiocarhamide ( 5 grams) acidified with sulphuricItcid ; the fiolution is afterwards shaken with ether, and the etherealsolution washed with dilute sodium hydroxide solution, dried, andevaporated. It is a yellow oil, insoluble in water and dilute acids, butsoluble i n alcohol and ether; it is a feeble base, giving precipitateswith platinic chloride, si h e r nitrate, mercuric chloride, and coppersulphate.pimet h.y Zdit hiote trah y dro triazol e, NH<CS.NMe is prepared in likemanner, and is a yellow oil, giving similar reactions.Constitution of Caprylaldehyde. By A. BEHAL (BuEI. SOC. Chim.131, 6, 131-137).-Substances having the formula C,HIsO havebeen prepared by the author in four different ways : (1) by the dis-tillation of castor-oil soap ; (2) by oxidation of capryl alcohol obtainedby the distillation of castor-oil soap in presence of an alkali ; (3) bythe action of zinc methyl on oenanthylic chloride ; (4) by the addi-tion of the elements of water to true acetylenic caprylidene.All these substances have the same odour, and boil at 171-172" ;their densities at 0" me respectively: (1) 0.8331 ; (2) 0.8337; (3)0.8399, 0.8387 ; (4) 0.8399.The smaller values.obtained i n the first two cases are probably dueto the presence of a little capryl alcohol.None of these compoundsreduce ammoniacal silver nitrate in alcoholic solution. The productAare identical, and by the third met,hod of preparation the substance mustbe a methyl ketone. This is substantiated by the preparation of theoxime, which boils at 218", and, on treatment with acetic chloride,yields an acetyl-derivative, which gives barium acetate and theoriginal ketone when distilled with baryta.The products of oxida.+ion of the compound prepared in each ofthe four ways are caproic and acetic acids.The caproic acid obtainedhas been prepared in large quantity and purified. The fractionpassing over at 204-206" readily crystallises from methyl chloride :it fuses at -10.5", a point much lower than that indicated by Fittigfor the normal acid (Annnlen., 200, 49), but this difference is,perhaps, due to a trace of impurity." Its density at 0" is 0-9456.The calcium salt crystallises in plates containing 1 mol. H,O. Thesolubility of this salt is such that at +lo the solution contains2.084 grams of the anhydrous sa.lt per 1OOc.c., and at 23.5" the corre-sponding amount is 2.852 grams.These numbers correspond withthe determinations of the solubility of the calcium salt of normalcaproic acid made by Lieben and Rossi.The so-called caprylaldehyde is therefore normal methyl hexylketone. W. T.Dry Distillation of Orgsnic Silver Salts. By W. KOENIGS(Ber., 24, 3589-3590).-The author points out that the decom-position of organic silver salts when heated frequently takea a course* The difference between the temperature of fusion found, -10 5", and thatgiven for the normal acid, -2', would require as much 8 s 2 per cent. of an im-imrity of low molecular weight, such as water, for its production, according toItaoult's law.-Note by Abstractor.The pZatinochZoride, (C,H,,N,S,),,H,PtC'l,, was obtained.CS-Y MeA.G. B294 ABSTRAOTS OF OHEMXCAL PAFERS.quite different from that rJtdndied by Knchlor (this vol., p. 37). Hequotes a number of well-known cases in which the Rilver salt is de-composed, with evolution of carbonic anhydride, yielding considerablequantities of a substance of which the acid in question is n carboxyl-derivative. 1'. S. R.Glycocine and its Derivatives. By B. GOLDBERG, P. KUXZ,and K. KRAUT (Annalen, 266, 292-310; compare Mauthner andSuida, Abstr., 1891, 38 j.-Amidoacetic acid (glycocine) is best pre-pared by gradually adding a concentrated aqueous snlutim oEchloracetic acid to a large excess of Concentrated ammonia withconstant stirring, and, after keeping for 24 hours, expelling theexcess of ammonia, first with a stream of air, and then bywarming on the water-bath; the acid is isolated by means of itacopper salt.The mother liquors from the copper salt contain di-atid tri-glycolamidic acid (compare Heintz, Annalen, 122, 257 ; 124,297), but 20-30 per cent. of the chloracetic acid is converted intoproducts other than those already named, the nature of which couldnot be determined. The barium salt, (NH,~CH,C'OO),Bn + 4Hz0,is obtained in small, lustrous crystals when the acid (1 part) andcrystalline barium hydroxide (2 parts) are dissolved in a little water,the filtered solution poured info alcohol, and the precipitated oil leftf o r some days in contact with the supernatant liquid; it melts R tFtbont 42", arid cannot be obtained in an anhydrous condition. Thestrontium salt, w i t h l$H,O, calcium d t , with H,O, and the magne&masalt, with 2HI,0, were prepared in like manner, and are all crystalline ;the calcium salt loses the whole of its water a t 105-llO", and itsaqueous solution has a strongly alkaline reaction.These experimentsprove the inaccuracy of Curtius' statements regarding the nou-existence of such salts. A double salt of the compositionNH,GHz-COO Ho'CHzCoo>Zn + 2H20is formed by the union of molecular proportions of, zinc amidoacetateand zinc glycollate ; i t is a crystalline compound, sparingly soluble incold, and decomposed by hot water with separation of zinc oxide.When methyl amidoacetate hydrochloride is boiled with excess ofcopper oxide, it is completely dricomposed, yielding methyl alcohol,copper amidoacetate, a.nd cupric chloride ; ethyl amidoacetate hydro-chloride, under the same conditionp, is decomposed in a similai.manner. There is, therefore, 110 reason for supposing that in thesecompounds copper can be suhst'ituted for the hydrogen of the amido-group (compare Curtius and Goebel, Abstr., 1888, 576), and it, ismobable that all the metallic derivatives of amidoncetic acid are formed I .by the substitution of the hydrogen of the carboxyl group.F. S. R.Diethylamidocaproic Acid. By E. DUVILLIER (BUZZ. SOC. Clrim.[3], 6, 90--92).-Normal a-bromocaproic acid (1 mol.) is heated insealed tubes at 100" with excess of diethylamine (3 mols ) in concen-trated aqueous solution, The base is recovered by boiling withbaryta, the baryta precipitated exactly with sulphuric acid, aud thQRQANIC CHEMISTRY. 295product treated with silver oxide.A little dissolred silver is removedby hydrogen sulphide, and the solution evaporated to a Hyrup, fromwhich the pure amido-acid is obtained by conversion into the coppersalt, which is deposited on evaporation a t a low temperature a s a violetsalt, accompanied by a small quantity of a p e e n salt, and is purified bycrystallisation from aqueous solution over sulphuric acid ; the copperdiethylamidocaproate is then decompofled by hydrogen sulphide.The acicular crystals of the copper salt are of a dark-violet colour,resembling that of chrome alum ; they give fine, violet solutions inwater and alcohol, their solubility in the latter being much the greater.The free acid, CH3.CH&HzCH,-CH(NEtz).COOH, is very solublein water and alcohol, but insoluble in ether.I t s solutions, whenstrongly concentrated, give a crystalline mass which decomposes ondistillation. The hydrochloride is a syrupy substance, soluble in allproportions in water and alcohol.The pZatinochZoride is deposited from very concentrated aqueoussolutions in oTange-red, monoclinic prisms ; it is very soluble in water,and soluble in alcohol, but insoluble in pure, dry ether. Ether precipi-tates it from its alcoholic solution aR an orange-coloured oil. T t con-t sins 1 mol. H20, which it loses at 110". The corresponding aurochlorideis almost insoluble in water; i t is deposited as a yellow oil fromhot solutions, forming small, crystalline plates on cooling, Thecrystals are anhydrous, very soluble in alcohol, also soluble in pure,dry ether.The green copper compound accompanying the copper diethyl-amidocaproate is copper hydroxycaproate ; it yields barium hydroxy-caproate on treatment with barium sulphide.The barium salt crjs-tsllises with 4 mol. H,O in brilliant needles, forming radiating groups,W. T.Derivatives of Tsocrotonic Acid. By P. MELLKOFF and P.PETRENKO-KRITSCHENKO (dnnazen, 266, 358-378).-W hen a slightexcess of hypochlorous acid is gradually added to an aqueous solu-tion of isocrotonic acid, and the solution then extracted with ether, athick, acid syrup is obtained, which consists of /3-chlor-a-hydroxy-hutyric acid (m.p. 8S-8SD), small quautities of a-chloro-p-hydroxy -butgric acid (m. p. 62-63"),. the formatioil of which is probablyduo to the presence of crotonic acid, and a-chloro-p-hydroxp butyricacid (m. p. 80.5").The /3-chlor-a-hydroxybutyric acid (m. p. 85-86") is easily iso-lated by means of its sparingly fioluble zinc salt (compare Abstr.,1884, 1301); the other two acids form readily soluble zinc saltsand are separated from one another by means of their potassium salts,t,hat of the a-chloro-/3-hydroxy-acid (m. p. 62-63") being much themore readily soluble in alcoholic ethcr.a-ChZoro-8-hydl.oxybutyr~c acid (m. p. 80m5"), prepared from ihpotassium salt, crystlallises from ether in .well-defined, rhombic prisms,and is readily soluble i n water, alcahol, and ether.The potassiumd t , CAH,C103K + 14K-0, crystallises from hot 96 per cent. alcohoiin long, silky, efflorescent prisnis, and is readily soluble in water, butonly sparingly in cold 96 per. cent. alcohol. The sodium salt296 ABSTRAOTS Olr OHEMIOAL PAPERS.CdH6CIO,Na, separates from hot alcohol in small, ~ r a n u l a r crystals,and seems to decompose at 70". The cnlciiim salt, zznc Aalt, and silversalt are amorphous. When the acid is distilled witah concentratedsulphuric acid, it is converted into a-chlorocrotonic acid (m. p. 99").l9-Methyhoglycidic acid, isomeric with the P-methylglycidic acidobtained from a-chloro-/?-hydroxybutyric acid (ru. p. 62-63'), isformed when a-chloro-/?-hydroxybutyric acid (m. p. 80.5") is treatedwith hot alcoholic potash, and the crystalline potassium salt decom-posed with dilute sulphuric acid ; it is a thick liquid, having a strongodour of butyric acid.Thepotassium salt, C,H,O,K + H20, separatesfrom alcoholic ether in prismatic crystals, melts a t 82", and is readilysoluble in water and cold alcohol. The silver salt, C4H,03Ag, crys-tallises from hot water in small, colourle.qfi needles.A B-chlor-a-hydi.oxllbutyric acid, melting at 125", and isomeric withthe lJ-chlor-a-hydroxy-acid (m. p. 85-86") referred to above, is ob-tained when the potassium salt of /I-rnethylisoglycidic acid is treatedwith very concentrated hydrochloric acid ; it crystallises in prismsand is readily Holuble in water, ether, and alcohol. The C ~ Z C ~ U ~ I L salt, (c4&clo3)2ca + 4H20, is crystalline ; the zinc salt, (C4H6C1O3)&,crystxlhes in well-dt!fined, transparent plates, and is readily solublein water.When the acid is treated with alcoholic potash, it is recon-verted into /3-methylisoglycidic acid; on boiling a solution of itssodium salt, carbonic anhydride, propaldehyde, and sodium chlorideare formed.When a-chloro-p-hydroxgbutyric acid (m. p. 80.5') is heated withconcentrated hydrochloric acid at 1W0, it yields a dichlorobutyric acid(m. p. 72-73"), identical with the compound obtained from a-chloro-p-hydroxybutyric acid (m. p. 62-63") in like manner.p- Het hy lisqqly ceric acid, C,H,O,, is formed when P-methylisogly cidicacid i R heated with water a t 100" for 5-6 hours in sealed tubes ; i tcrystallises in short, seemingly rhombic prisms, melts at 45', and iureadily soluble in alcohol and water, but only sparinglyin ether.Thepotassium salt, C4B,04K + H,O. crystallises from alcohol in pris-matic plates, and is readily soluble in water. The barium salt,(C,H,04)2Ba + 2H20, is a granular, crystalline compound. Thesilver salt, C4H704Ag, crystallises from water, in which it is onlyRparingly soluble, in large prisms. When the acid is repeatedly melted,its mclting point rises, poksibly because it is partially converted intop-methylglyceric acid (m. p. 80").The authors are of the cpinion that the chlorhydroxy-acids obtainedfrom isocrotonic acid are the geometrical isomerides of the correspond-ing crotonic acid derivatives, and that their experiments afford addi-tional proof of the stru-tural identity of crotonic and isocrotonic acids.Preparation of Dehydracetic Acid.By H. v. PECHMANN (Ber.,24, 3600) .-Dehydracstic acid can be very conreniently prepared bytreating acetonedicarboxylic acid with acetic anhydride, dissolvingthe crystalline substance (m. p. 254") obtained in this way in diluteRoda (1 mol.), evaporating to drgnesn, and then precipitating theaqueous solution of the residue with acetic acid ; the yield i R about3UO grams from 1 kilo. of citric acid.F. S. I(.F. S. KORGANIC OHEMISTRT. 297Resolution of Inactive Lactic Acid by Penicillium Glaucum.By G. LINOSSIER (Bull. SOC. Chim. [S], 6, l0--12).-After threemonths, solutions of ammonium lactate (corresponding with 5 percent.lactic acid) in which pure cultivations oE Penicillium glaucumhave been growing become alkaline and lsvogyrate. From bhe pro-ducts the author has isolated a dextrogjratle lactic acid, which yieldsa lsevogyrate zinc salt. Mixtures of hot solutions of this salt and ofdextrogyrate zinc paralactate deposit, on cooling, ciystals of inactivezinc lactate.During the first two months, when the mould is vigorouRly growing,no active acid appears ; it is only in its later stnges of development,,when fat appears in its hyphse, that the nutrient solution manifestsoptical activity. Hence it appears that the healthy f u g u s attacks bothvarieties of lactic acid equally, but, when weakened, the lsevorotatoryvariety is more easily assimilated.Decomposition of Glutaric Acid at a High Temperature.By W.LOSSEN (AnnaEen, 266, 264-266).--8 reply to Clam (thisvol., p. 40).-The author does not deny that carbonic anhydride isevolved when glutaric acid is heated under certain conditions ; his andWisbar's experiments (Absir., 1891, 101 1) were undertaken simplpin order to ascertain whether, and if so which, butyric acid is formedOIL heating glutaric acid ; they found that butyric acid is not produced,and, consequently, CIaus' original statement is untrue.T. G. N.F. S. K.Conversion of Unsaturated Acids into their StereocherhicalIsomerides by Soda. By A. DELISLE (Her., 24, 3620-3622).-Maleic acid undergoes no change when it is heated with aqueous oralcoholic potash for a short time at loo", as has lately been shown bySkraup (Abstr., 1891, 1338).The author finds that 30 per cent.soda is also without action at loo", but that when the temperatureis raised to 106", the male'ic acid is slowly transformed into fumaricacid ; malic acid is converted into fumaric acid under the same con-ditions.When a solution of citraconic acid (6.5 grams) in 28 per cent. soda(100 c.c.) is heated for six hours on the water-bath, it yields mesa-conic acid (3.7 grams) and itaconic acid (1.2 grams), but a consider-able .quantity of citraconic acid remains unchanged ; when mesaconicacid (6.5 grams) is treated in like manner, it gives citraconic acid(1% grams) and itaconic acid (1 gram), a large quantity (3.7 grams)remaining unchanged.Pyrocinchonic acid is not acted on by concentrated soda at loo",but diphenylmale'ic acid is converted into a substance which meltsconsiderably above 25U", and which seems to have the same percentagecomposition as diphenylmaleic anhydride.ap-Dimethylglyceric Acid from Angelic Acid.By P. MEL~KOFFand P. PETRENKO-KR~TSCEENKO (Annulen., 226, 378--38U).-When theliquid dimethplglyceric acid obtained from angelic acid (Abstr., 1891 j,862) is kept for a long time, it gradually solidifies to a mass ofF. S. K298 ABSTRACTS OF CHEMICAL PAPENS.crystals ; this crystalline acid is identical with the alp-dimethyl-glyceric acid obtained from tiglic acid.Derivatives of Glutamic Acid. By A. MENOZZI and G. APPIAxr(Rend. Acrid. Linc., 7, i, 33-40).-Glutamic acid, prepared by themethod of Hlasiwetz and Habermann, melts at 200", and in aqueonss Blution (2-4 per cent.) has a specific rotatory power [ a ] n = +1;1.5"a t 22". For the hydrochloride in aqueous eolutions (4 per cent.)[ a ] D = +27*5"at 15", and for the calcium salt [a],, = -3.6" a t 16".'J'hese results agree fairly with those.of Scheibler (Abstr., 1884, 1308).The authors were unable to prepwe the diammonium salt describedby Habermann (Annalen, 179, 248).Glutimide is best prepared by passing dry hydrogen chloride into asolution of glutamic acid (20 grams) in absolute alcohol (100 grams) ;the ethyl glutamate hydrochloride t h u s obtained is decomposed hymoist silver oxide, and the dissolved silver precipitated by hydro-gen sulphide ; on concentration, ethyl glutamate separates, and,nft,er heirig recrystallised from dilute alcohol, is conveyted intoglutimide by heating in a closed tube with alcoholic ammonia for7-8 hours a t 140".Or an alcoholic solubion of glutamic acid may besaturated with hydrogen chloride, alcoholic ammonia added, t8hesolution filtered from aitimoninm chloride, saturated with ammonia,and then heated in a closed tube for conversion into glutimide. Theglutimide thus obtained is optically inactive, and crystallises with-out water of crystallisation i n the oblique system, a : b : c =Active glutinaide, CSH8N,0,, is prepared by saturating the solutionof ethyl glutamate obtained as above with ammonia in the cold ; aftersome time glutimide separates, and, on recrystnllisation from water,is obtained in large, orthorhombic pyisms or tables (a : b : c =0.661 : 1 : 1.016) containing 1 mol.HzO, which is lost on drying oversulphuric acid or on heating at 1UO". It melts at about 165", and itsspecific rotatory power [a]D =: -140" in aqneous solutiou (8.5 percent.) at 15". The aqueous solution is not changed by boiling withmagnesia, but readily yields ammonia when boiled with hydroxides ofthe alkalis or alkaline earths. The anhydrous compound dissolves in13 parts of water a t 9", and in 125 parts of absolute alcohol at 13".When heated with alcoholic ammonia in a closed tube for 8-9 hoursat 140-1.50", i t is completely converted into inactive glutimide.On treating inactive glutimide with conceutrated hydrochloric acid,ammonium chloride and inactive glutamic acid hydrochloride areobtained.The latter substance forms orthorhombic crystals ( a : b : c= 0.8852 : 1 : 0*3866), part of which show right-handed and part left-handed hemihedrism ; it is therefore a mixture of the hydrochloridesof dextro- and lsvo-glutamic acid.On boiling the aqueous solution of inactive glutimide with bariumhydroxide, precipitating with sulphiiric acid, and concentrating thefiltrate, inactive glutamic acid is obtained in orthorhombic crystals.These crystals are completely holohedral, but, on repeated crystullisa-tion from water, crystals showing right- and left-handed hemihedrismare obtained. W. J. P,F. S. K.1.403 : 1 : 1.421 ; /3 = 86" 58'.ORGANIC OHEMZSTHY.299A New Isomeride of Galactonic Acid andof Mucic Acid. B yE, F~SCHER (Bey., 24, 3622--3629).-When galactonic acid is heatedwith quinoline or, better, with pyridine, it is partially converted into astereochemical isomeride, which bears the same relationship to g&c-tonic acid as gluconic does to marinonic acid ; this new componn(],which the author names talonic acid, yields, on reduction, a, syrupysugar (talose), which is converted into talomucic acid, the stereo-chemical isomeride of mucic acid, on oxidation with nitric acid.Tnlonic acid is prepared by heating a 50 per cent. aqueous solutionof pure galactonic acid (125 grams) with pyridine (125 grams) andwater (1 litre) for two hours atl 150" in a closed vessel; the filteredsolution is boiled with crystalline barium hydroxide (125 grams) untilfree from pyridine, mixed with a quantity of sulphuric acid exactlysufficient to precipitate the barium, treated with animal charcoal, neu-tyalised with cadmium carbonate and cadmium hydroxide, and filtered.On cooling, the sparingly soluble cadmium salt of gslactonic acid isdeposited in crystals ; after separating this compound as completely aspossible, the diluted mother liquors are treated with hydrogen sulph-ide, and the tnlonic acid in the hot, filtered solution precipitated withhasic lead acetate.The colourless basic salt obtained in this way isdecomposed with hydrogen sulphide, the filtered solution, which stillcontains galactonic acid, boiled with brucine and evaporated to asyrup ; the brucirie salt of talonic acid, which is deposited in crystalson cooling, is washed with a little alcohol and t'hen dissolved in hotmethyl alcohol, from which it separates in slender crystals melting a,t1:30-133", and readily soluble in water.The yield of the pure saltis 23 per cent. of the galactonic acid employed, which is equivalent to7 per cent. of talonic acid. The free acid is obtained by boiling anaqueous solution of the brucine salt with barium hydroxide, evaporat-i n g the cold filtered solution to dryness, and extracting the residualb;irium'salt with boiling alcohol to free i t from brucine ; if now thebarium salt is decomposed with sulphuric acid in the usual way, andthe filtrate evaporated, there remains a syrup which consists of amixture of tnlonic acid and its lactone ; this syrup is strongly dextro-rot,atory, and is readily soluble in hot alcohol.The caZcium, strontium,barium, and zinc salts of the acid are very readily soluble in water,and do not crystallise. The cadmium salt, (C&,,O,)&d + HzO, is acolourless, crystalline compound, very readily soluble in cold water.The hydrazide, C6H,106*NzH2Ph, crystabes from hot alcohol in small,colouriess prisms, melts a t about 155" with slight decomposition, andis much more readily soluble in water than the corresponding deriva-tive of galactonic-acid.Talose, prepared from the mixture of the acid and its lactone in theusual manner, is a colourless syrup ; its hydrazone differs from that ofgalactose in being very readily soluble in water, but its osnzone cannotbe distinguished from the corresponding galactose derivative.When talonic acid is heated with pyridine under the conditionsdescribed above, it is parhially converted into galactonic acid.TaZomucic.acid, G6H,oOR, is obtained when talonic acid is evaporatedwith dilute nitric acid, and is purified by means of its calcium salt.It crystallises from acetone in colourless, microscopic, quadratic plates300 ABSTRACTS OF OHEMLCAL PAPERS.melts at about 158" with decomposition, and is very readily Roluble incold water and warm alcohol, but only sparingly in warm acetone, andalmost insoluble in ether, chloroform, and benzene ; its specific rota-tory power is [a]D"' = + 29.4' (approximately), but this value rapidlydecreases on boiling the solution, owing to the formation of thelactone; it does not reduce Fehling's solution even on boiling.Aqueoiis solutions of the acid give colourless precipitates with leadacetate and with barium hydroxide, and in neutral solutions, cadmiumsulphate produces a colourless precipitate.The s?:Zver salt is insoluble,and is decomposed by boiling water. The potassium hydrogen salt is acolourless syrup, very readily soluble in water. The calcium sa,lt,CsH,O,Ca, separates from hot water in the form of a colourlesd, crys-talline powder; when boiled with water, it changes to a paRty mass,and only dissolves to a slight extent, but it is =ore readily so!uble inhot, very dilute acetic acid. The phenyZhydrazide crystallises inalmost colourless plates, melts at 185-190" with decomposition, andis much more readily soluble in water than the dihydrezide of mucicacid. When talomucic acid is heated with concentrated hydrochloricand hydrobromic acids a t 150", i t is converted into dehydromucicacid j on treatment with pyridine and water at 140", it gives, mucicacid.F. S. K,Constitution of the Hydroxamic Acide. By F. TIENANN (Ber.,24, 3447--3453).-The reactions by which the hydroxamic acids areformed suggest at once that they are hydroxamido-derivatives of thegeneral formula R*CO*NH(OH) ; the hydrogen of the hydroxyl groupbeing displaceable by alkyl and alkoyl radicles. Lossen at first putforward this viow, but he has since expressed the belief that they areoxinlido-derivatives of the general formula R.C (N0H)nOH on theground that they are convertible into compounds containing either anoximido-group or an alkylated or alkoylated oximido-group.' Thus,when treated with silver nitrate in alkaline solution, silver derivativesare formed which, on subsequent treatment with alkyl iodides, yieldthe compounds R*C(NOR')-OR', but Tafel and Enoch have shown(Abscr., 2890, 491) that certain aromatic amides, under similar con-ditions, yield compounds analogous to the last mentioncd, thus,RC(NH).OR', from which it might with equal force be urged t h a tthese amides had the constitution R-C(NH).OH.The author isinclined to ascribe these phenomena to tautomerism, and he holds tbeopinion that t,he hydroxamic acids have the constitution R-CO.NH-OH.A.R. L.Alkyl and Acidyl Sulphides. By S. H. DAVIE~ (Ber., 24, 3548-35521.-A compound of the composition MeJS is obtained whenmethyl bisulphide or methyl tersulphide is heated at 100" for 3-4hours with methyl iodide ; it crystallises in colourless needles, and,after having been converted into the corresponding chloride, giveR aplatinochloride of the composition (Me3SC1),, PtCld.Acetic sulphide (thiacetic anhydride). SAC,, prepared by heatingacetic acid with phosphorus pentasulphide, boils at 66-67' under apressure of 20 mm., and ut 156-158" under a pressure of 747.5 mm.ORGANIC: OHEXISTRY. 301with park1 decomposition ; when heated with water, i t is decompo3edinto acetic acid and thiacetic acid.F. S. KThio-derivatives of Furfuraldehyde. By E. BAUKWN and E.FROMM (Bet-., 24, 3591-3599 ; compare Abstr., 189 I, 1008).-z- Trithiofurfi~raEdeIL~dd, (C,H,S and the /$compound desc1.i bedbelow, are produced when an alcoholic solution of furfuraldehyde isc:Lrefully mixed with alcoholic hydrochloric acid a t -so, and thensaturated with hydrogen fiulphide in the cold ; after keeping for 24hours, excess of sodium carbouate is added, the precipitate separatedby filtration, dried in a desiccator, and dissolved in benzene or chloro-form ; on adding alcohol to the solution, the /?-compound is for themost part precipitated, the a-compound remainin: in solution.a-Tr.ithiofurfur;tldehydt: is obtained in colourless crystals when thebrown alcoholic benzene mother liquors are shaken with animalcharcoal.the so111 tion evaporated, arid the residue repeatedly recrys-tallised from dilate alcohol; it melts a t 1B0, turns yellowish-brownon exposure t o the air, arid is very readily soluble i n benzene andchloroform, but rather more sparingly i n alcohnl, and insoluble inwater. Molecular weight dettmninations by Baoult's method iiinaphthalene solution gave results agree ng with those required bya cornpound of the mol Acular formula given above.B- T,-itlril,fiLrfur.nldehyd~, (C,H,SO),, is obtained i n co'onrless needleswhen the precipitate referred to above is repeatedly re jrystallisedfrom benzene, using animal charcoal; it is formed when the a-corn-pound, in benzcne solution, is treated with ethyl iodide cqntaininga trace of free iodine. It melts at 229' with decomposition, turnsyellow on exposure t o the air, and is readily soluble in chloro-form, but more spiiringly in benzene, axid almost insoluble in alcohol;molecular we'ght determinations showed that the compmnd hAs themolecular formula a3signed to it above.The polymeride of thiofurfnraldehyde described by Cahours(Aiinalen, 69,55) is deposited in colourless crystals when t m alcoholicsolution of furfuraldehyde is treated with alcoholi: ammonium sulph-ide a t the ordinary temperature ; it softens at 80°, melts completelya t 9U-9l0, and has the empirical formula C5H,S0.Its molecularweight was determineJ by Raoult's metohod i l l naphthalene solution,and found t o be about 2200, a result which corresponds approximatelywith th 1 molecular formula (C,H,SO),, ; a<, however, the depressionof the freezing point of the naphthalene increases continuously withthe time during which the solution is heated, it seems likely that theinoleoule is even greater than that given above, probably (C4H5SO)2,.It is readily soluble in benzene, and i f ethyl iodide containing freeiodine is adJeLi to the solution, 13-trithiofurfuraldehjde is depositedin crystals after Some time.When heated a t a temperature justbelow 160 fur 10-12 hours, it yi2lds large quantities of the furfuro-stilbene described by Cahours and Shwnnert ; this cornpound is alsoobtrtined when either of the trithiohrfuraldehydes is heated a t about230" ; it melts a t 101", and hasthe molecular formula Cl0H8O2, a s wasprvved by molecular-weight determinations in glacial acetic acidsolution.F. S. K.Y VOL. LXII302 ABSTRACTS OF CHFFI'VIICATI PAPEhS.Constitution of Tetrole Nuclei. By G. CIAMICIAN and A .ANGELI (Gazzetia, 21, ii, 109--133).-The authors' views of the con-&rution of tetrole nuclei have been lately expoundcd by Ciamician(Abstr., 1891, 1195), and in the case of thioplien are greatly sup-ported by the following experiments, showing that. derivatives of thatsubstance on oxidation yield open chain compounds containing theSynthetical tetrabromothiophen (1 part), on treatment with nitricmid (AP. gr. 1.52, 10 parts), cooled in a mixture of snow and salt,is converted into a brown, semi-solid substance ; o n withdrawing thecooling mixture, this dissolves with development of heat, brominebeing liberated, and on pouring the product into cold water, awliite, ci-ptalline compound separates which, however, soon redis-solves.After being nearly neutralised with caustic alkali, extractedwith et'lier, and the latter evaporated, dibromomaleic anhydride isleft, the Tield being almost theoretical. It melts at 117-118", audnot at 114-115" as previously stated.Tetrabrornothiophen (3 grams), on oxidation in boiling acetic acidsolution (50 c.c.) with chromic anhydride ( 5 grams), gives off bromineand yields a yellowish product which is insoluble in most of the ordin-ary solvents. On boiling with alcohol, and crystallising from boilingxylene, yellow scales are obtained which darken at 240°, and do notmelt a t 310" ; this compound probably has the compoc;ition C9Br,SpOz.It dissolves in boiling caustic potash, yielding a brown soh-tion, and with alcoholic potash gives a solution which is yellowwhile hot, and brown when cold.On heating the cornpound withphenylhydraeine, either directly o r in solution in xylene or acetic acid,aniorphoufi, highly-coloured products are obtained. On concentratingthe xylene mother liquors from the crystallisation of the substance,a yellow, amorphous substance is obtained which is soluble in Iienz-ene, and melts a t 220" ; it is possibly a decomposition product of theless soluble substance.Synthetical a-methyltribromothiophen (1 part) is gradually intro-duced into nitric acid (sp.gr. 1.52, 10 parts) cooled in snow andsalt ; it immediately dissolves t o a reddish-browE liquid, but broniineis not evolved. If the solution is now poured into water (60 Farts),the excess of acid partly neutralised by an dkali hydroxide, andtbe solution extracted with ether, the ether on evaporation leaves anoily residue ; when this is suspended in water, and again extractedwith ether, a yellow oil is obtained which solidifies after a time ; bydlssoiving the product in warm benzene, precipitating by light petr-oleum, and crystallisiiig i t from benzene, colourless, orthorhombicprisms, a : b : c = 0.6381 : 1 : 0.4670, of dibromoacefylacrylic acid areobtained melting a t 78-79". This acid dissolves in solutions of thealkali carbonatleg with effervescence, is very ~oluble in hot water,ether, and alcohol, sparingly in cold water and benzene, and insolublein light petroleum ; on reduction with 2.5 per cent.sodium amalgamin dilute sulphuric acid solution, it yields dibromolevulinic acid.With phenylhydrazine in amtic acid solution, a deposit of yellowneedles is obtained ; this, after crjstallisation from dilute alcohol,melts at 84-10U". and is probably a mixture.I Igroup -co.c: c*co--303 OROANIC CHEMISTRY.p-Methyltrihromothiophen (1 part'), when dissolved in nitric acid(sp. gr. 1-52, 10 parts), and treated in a manner similar to the above,yields a yellow oil which soon solidifies. If t h i s is dissolved inbenzene, decolorised by animal ohrcoal, and precipitated severaltimes by light petroleum, bromoci trnconic anhydride is obtainedmelting a t 100-lOl", a slightly higher temperature than has pre-viously been given.Experiments on the oxidation of 2 : 5-dimethyldibromotl1 iopllenand 2 : 5-methytphenyltribromothioplien led to no positive result, t,heoxidation products being badly characterised.The above experiments show the great analogy existing betweenthe thiophen.pyrroline, and furfurnn nuclei, and also afford a methodof determining the position of the alcohol radicles in substitutedthiophen derivatives.The speed a t which the oxidation proceeds was determined byallowing iiitric acid of knqwn strength t o act on the thiophen deriva-tive for a fixed time, interrupthg the reaction, and estimating thesulphnric acid produced.Nitric acid of sp. gr 1.47, acting for 18minutes, decomposed 2.92 per cent. of tetrahromothiophen, 84.62 percent. of a-methyl tribromothiophen, and $2.00 per cent. of P-methyl-tribromothiophetl ; acid of sp. gr. 1.45, acting for 51 minutes, con-verted 24-14 per cent. of a-methyltribromothiophen and 31.12 percent. of p-methyltribromothiophen. W. J. P.Derivatives of Ethyl 1-cetothienoneoxalate. By S. SALVATORI(Gazaetta, 21, ii, 268-294) .-Acetothicnoiieoxalic (thenoilpyruvic)acid, obtained hy Angeli (Abstr., 11191, 550) by the action of sulph-uric acid on the ethyl derivative, may conveniently be prepared bytreating a mixture of acetothienone and ethyl oxalate with sodiumethoxide, proceeding according to Rromme and Claisen's method ofpreparing benzoylpyruvic acid (Abstr., 1858, 691).The ethyl de-rivative, C,SH,.CO*CH,.CO.COcl)Et, described by Angeli, gives rise toa series of metallic mlts ; the copper salt, (CloH80J2Cu, forms a veryinsoluble, pale-green mass ; the ammonium salt, C,,H,,S 04,2NH3, isobtained afi a pale salmon-coloured, crystalline powder soluble inalcohol, benzene, and ethyl acetate. It melts at 125" with decomposi-tion, and its solutions evolve ammonia on heating to 60-70". Nonitrofio-derivative could be obtained either from the acid or from tbeethyl derivative by V. Meyer's method, the product consisting ofative of this acid is formed by the- condensation of a molecule o€ ethylacetothienoneoxalate with a molecule of phenylhydrazine with elimina-t,ion of 2 mols.H,O. It crystallises from alcohol i i i colourless, mono-clinic prisms, a : b : c = 1.177 : 1 : 0.716 ; p = 64" 10'' melts at &lo,dissolves in most solvents, Lut not in water. The acid is obtainedfrom the ethereal salt by hydrolysis. It separates from alcohol intriclinic crystals, melts at 195", and decomnoses a t a slightly highertemperature ; the silver salt, C,rH,AgSNzO2, forms a white, curdyy 301 ABSTRACTS OF C IEMICAL PAPERS.mass; salts of copper, mercury, zinc, lead, barium, and iron have;ilsn been prepared. On heating i t above its melting point, it losescarbonic anhpdride, and yields the corresponding thieiay?phen.ylp?ll.az~le,C,,H,,SN,. The latter crystallises from alcohol in white needles,melts at 54", and distils unaltered above 300".It is freely soluble inalcohol, ether, and benzene, and sparingly in water; it is dissolved byconcentrated mineral acids, and reprecipitated on dilution ; it givesKnoi-r's reaction for pyrazoles.The ethindide, ClaHl,SNz,EtI, cr,vstallises from water in colourlesspristris melting a t 175-1 74" ; the platiwoclrloride, ( C,3H,J3N2)z,H2PtCI,,separates in dark orange-yellow flakes. I - ->N.-The ethyl derivative$HC(COOH)Thienylisoxnzolic Acid, C (CASH,) -0of this acid was prepared by Angeli by tlie condensation of ethyl:Lcetot,hienoneoxalate with Ilydrr)xylamirie. The free acid may beobtained in colourless crystals melting a t 177" with decomposition,:)nil readily soluble in alcohol, ether, and water.The silver salt,C8HJAgSN0,, separates in white flakes ; salts of copper, lead, mer-cur-y, barium, and iron were also prepared.A h-jdrated oxime of acetothienoiieoxalic acid, CSHiSN04 + H,Omay be prepared b.y dissclring the acid in a slight excess of sodinacarbonate, and adding the theoretical quantity of hydroxylamine, alsodissolved in sodium carbonate, the solutions being kept so dilute that30-40 C.C. of the liquid only contain 1 grain of acid; the mixtureis then allowed to remain for some time. On acidifying with hydrci-chloric acid, the oxime gradually separates in minute crystals. Itmay be obtained pure by ~llowing a cold ethereal solution to evapor-ate spontaneously, and collecting the first crop <if prismatic crystalsdeposited.It melts with decomposition at 110-112", and dissolresi n most colvents, but is partially converted into thienylisoxazolic acid.The conversion is niore speedily effected by the action of aceticRnhydride, no acetyl derivative being formed. This compound is ofinterest as being the first of the monoximes of the /3 diketouic acidswhich has been isolated.C?ynnacetothienone, C4H3S.CO*CHz.CN, is preparcd by heating smallquantities of thienylisoxaxolic acid in a, narrow tube until the evo-lution of carbonic anliydride ccasm, and treating the residue withsodium carbonate. When pure, i t cr-jstallises from alcohol in colour-less, lustrous plates, and from water in large needles, melts a t 1 3 7 O ,aiid does not decompose at 200".It resembles cyanacetophenonegenerally in its properties.An oxirne of lne~izoylpyruvic acid, ClnH,NO4 + HzO, may be obtainedby the method adopted for the preparation cf acetothienoneoxalicnxime; but if the digestion with hydroxylamine is prolonged f o rmore than three hours, the oxime formed a t first is gradually con-verted into phenylisoxazolic acid. It bears a general resemblanceto the preceding oxime, but is even more unstable; i t melts a t98-100° with decomposition, and crystallises from its cold etherealsolution in prisms.When phenylisoxazolic acid is heated above its melting point iORGANIC CHEMISTRY, 305the manner deqcribed for the preparation of cyanacetothienone, theproduct is identical with the cyanacetophenone described by Haller(Abstr., 1856, 440).The formation of these nitriles sliows that theconstitution of the oximes may be respectivelv represented bv theformu]= C,SH,*CO.CH,*C (NOH).COOH and CH,DzC (NOH)-COO H.The author believes that the behaviour of these oximcs, and especiallythe high temperatures necessary for the formation of the nitriles,indicates that they are =I-monoximes, and hence form a11 exception toHantzsch's hypothesis.Use of Sodium Hypophosphite in Sandmeyer's Reaction.By A. ANGELI (GazzPtta, 21, ii, 258-!261).-Sandrneper's originaliwction has the disadvantage of involving the use of cuprous saltswhich are not very stable and must be fresbly prepared. Gatter-mann's modification (Abstr., 1890, 970) involves the preparation offinely-divided copper perfectly free ft om zinc, and necessitates theconstant agitation of the liquid, especially a t the comniencement ofthe reaction.The following process obviates these difficulties ; i tdepeuds on the circumstance that when a solution of copper sulphateand sodium hypophosphite is acidified with hydrochloric acid andgently warmed, cuprons chloride speedily separates according to theequation 2CuC1, + HJ?O, + H20 = H,PO, + 2HC1 + Cu,CI,(Abstr., 1886, i 7 1 ) . A mixture of copper sulphnte and sodiumhypophosphite may therefore he added to acid solutions instead ofcuprous salts 01- metallic coppei-. Aniline is, for example, conrertediiito chloro-, homo-, iodo-, and nitro-benzene as follows :-Ch1orobenzene.-A solution OF aniline (9.3 grams) in hydrochloricacid (40 grams) and water (60 grams) is slowly mixed with a.solu-tion of sodium nitrite (7 glams), and then with a solution of coppersulphate (12.5 grams) and sodium hypophosphite (7 grams), when ah i s k effervescence ensues, owing to the evolution of nitrogen; assoon as this is over, the product is steani-distilled, and the chloro-benzene separated and rectified. It passes over almost entiiely a t132", and is converted by concentrated nitric acid into parachloro-nitrobenzene melting a t 183".Bromobenzene can be prepared in like manner by treating asolution of aniline (9.3 grams) in sulphuric acid (40 grams) andwater (90 grams) with a solution of sodium nitrite ( 7 grams),allowing the mixture to remain for a while, tlien adding sulphuric acid(20 grams) diluted with water, and solutions of potaseium bromide(36 grams), copper sulphnte (12.5 grams), and sodium hypophos-phite (7 grams).S. B.A. A.Iodobenzene may be prepared in like manner.Kitrobenzene is obtained by mixing a fiolution of dinzohenzenenitrate acidified with nitric acid with solutions of copper sulphateand sodium hypophosphite, and gently warming.The yields are very good, and the operations speediiy performed.The reaction is also available for the preparation ol cuprous bromideand iodide in a state of parity.Displacement of the Nitro-group by Chlorine or Bromine.By C. A. LOHRV DE BRUYN (Ber., 24, 3749--3750).--When theS. B. A. A306 ABSTRACTS OF CHEMICAL PAPERS.dinitrobenzenes are treated with chlorine or bromine in the absenceof any substance that can act as a carrier of t4he halogen, the reactiondoes not begin until the temperature of 'LOO" is rcached.With chlorine, orthodinitrobenzene yields dichlorobenzene ; exceed-ingly little, if any, orthochloronitrobenzene is formed.Metadinitro-benzene yields metachloronitrobenzene and dichlorobenzene. Para-dinitrobenzene yields parachlororiitrobenzene only.With bromine, the three dinitrobenzenes yield the correspondinghromonitrobenzenes ; the further action of bromine leads to the substi-tution of bromine for hydrogen. An oxychloride or oxybromide ofnitrogen is always formed in the reactions described.By G. DACCOMO (Chem. Centr., 1891, ii,532-533 ; from Ann. Chim. Fui.m., 13, 273-280).-Bearing in mindtlic fact that potassium ethoxide and carbon bisulphide react withformation of potassium xanthate, the anthor studied the reactionbetween potassium hydroxide and carbon bisulphide.Solid potas-sium hydroxide, l e f t in contact with carbon bisulphide, rtactsgradually ; tho bisulphide becomes coloured a t first yellow, whichdeepens into red, and, finally, a reddish-brown mass is produced.After washing with alcohol and drying over sulpliuric acid, a crystal-line, reddish-brown powder is obtained, which is readily soluble i nwater. With dilute acids, it is decomposed with formation of hydrogensolphide, carbonic anhydride, carbon oxysulphide, and sulphur. W it11mlts of the metals, precipitates are formed ; and with diazo-deriv-a tives, compounds are produced similar to those obtained by Leuckartwith potassium xanthate.With diazobenxene nitrate, two newcompounds, the one crystalline and the other liquid, are formed.Both have the empirical formula COSLPh2, and are phenyl clithio-carbonates. In order to determine which has the formnlaOPh-CS-SPh, and which the formula CO( SPh),, the author treatedboth with alcoholic potash. The following reaciions would take place:-C. P. 13.Dithiocarbonic Acids.OPh-CS-SPh + 2KOH = PhSH + PhOH + K,CO,S.CO(SPh), + 2KOH = 2PhSH + KZCOs.In neither case, however, was the formation of phenol observed,nor was there any carbon oxysulphide liberated from the prodnct bytreatmenti with acid ; only tliiophenol and potassium carbonate couldbe detected.It is suggested, therefore, that a molecolar changetakes place in the one or the other during hydrolysis, as Solomon hasalready noticed in the case of the hydrolysis of ethyl xanthate.By treating the crystalline product of the action of potassium hydr-oxide on carbon bisulphide with mctachlorodiazobenzene, a reddish-brown oil, c7ilorophenyl dithiocarbonate, is obtained which also graduallyseparated into a crystalline and a liquid portion, and these both reactwith alcoholic potash, forming potassium carbonate and meta-chlorothiuphenol. Paradiazotoluene behaves in an exactly siniilal-m anne r . J . W. L.Metachlorothiophenol. By G. DACCOMO (Ohem. Centr., 1891, i i,533-534 ; from A m . Chim. Farm., 13, 343--352).--The author haORGANIC C HEMISTRT.307carefully examined the metrtchlorothiophenol mentioned in the pre-coding abstract, since it differs from the one obtained by Otto fromchlorobenzcnesiilphonic chloride. The method of preparation was asfollows :--Nitrobenzene was treated with chlorine in presence ofiodine, according to Laubenheimer's method (Ber., 8, 1621). Itwas reduced with fuming hydrochloric acid and tin, and a very puremetachlorauiline boiling a t 230-232" was obtained. From this,the corresponding diazochlorobenzene was formed by the action ofpotassium nitrite. Lastly, the metachlorodiazobenzene was treatedwith potassium dithiocarbonate, yielding chlorop henyl dithiocarb-onate, from which metachlorothiophenol was obtained by hydro-lysis.Ch Zorop7aenyZ dithiocarbonate is a dark-coloured oil, readily solublei n ether, benzene, chloroform, and carbon bisulphide, sparingly solu-ble in alcohol, and insoluble in water.It may be distilled in ncnrrentl of steam, but it is readily decomposed by heating. Potassiumxanthate reacts wi t,h metachlorodiazobenzene in a similar maiiner t othe dithiocarbonate.Metachlorothiophenol is a colourless, limpid liquid which refractslight strongly, aiid has an especially penetrating odour. It is in-svlublo in water, but readily soluble in alcohol, ether, chloroform, andcarbon bisulphide. It is readily soluble in alkalis, and is precipitatedfrorri the solutions by acids. Theethereal solution reacts with mercuric oxide, and a thick, crystallinemass of the mercury salt is formed.The neutral solutions of thepotassium or sodium salts precipitate solutions of lead salts, lightyellow ; copper salts, dirty yellow ; mercury salts, white ; silvernitrate, yellow. With concentrated sulphnric acid, no reaction takrJsplace in the cold, but, on warming, a beautiful, l i g h t violet colora-tion suddenly appears.With chloral, a chemical change is indicated by the development ofheat, but no defiuite product could be separated. The potassiumsalt, C,H,ClSK, consists of small, prismatic, colourless needles,readily soluble in water, sparingly so in alcohol ; the barium salt,(C6H:aC1S)2Ba, consists of shining scales, little soluble in water ;the mercury salt, (C,H,ClS),Hg, pearly scales, almost insoluble inwater and alcohol.,111 the salts have the characteristic odour ofmetachlorotliiophenol.With acid chlorides, metachlorothiopbenol reacts readily, hydrogenchloride being liberated, and the corresponding salt produced. l'hcacetyl derivative, C6114ClSAc, is a culoourless, strongly refractiveliquid which distils between 255" and 26d". The b e m o y l derivative,C6H4C1SBz, forms triclinic prisms mcltiiig at 72.5".Its sp. gr. is 1.2637 a t 12.5".J. W. L.Ortho- and Para-chlorothiophenol. By G. DACCONO (Chem.Cerh-., 1891, ii, 656-657 ; from Ann. Chim. Furm., 14, 1--13).--'l'h3author has obtained ortho- aiid para-chlorothiophenols by the sntiiemethod as that employed for the preparation of the meta-derivative.Parnchlortiphenyl dithiocarbonnte, obtained from diazochlorobenxeriechloride, prepared from parachloraniline, forms white, pearly scales,which are readily Hobble in most organic solvents, but the compoun308 ARSTRACTS OF CHEMICAL PAPERS.does not melt a t a definite tempmatnre.The author conwidem itToPsible that it i s a mixture of the isomerides co(k+c6&cl), andC,H,Cl-S*CS*OC,H4C1. If diaznbenzene chloride is added to ptaRsiumua,ntha t e instead of t o the di thiocarbonate, the chloro~~heirylxanthate,OEt.CS~YG,H,Cl, is obtained ; this forms white crystals which melta t 124-126" to a colourleas liquid. By hydrolysing each of f.hesecompounds wi th alcoholic potash, parachErothir,phe?zol, C,H,Cl.SH,is obtained, which possesses all the characteristics of Otto's cornpound(Annalen, 143, 109).With sulphuric acid, it produces the sameviolet coloration as the meta-compound does.Acefylpm-achlorothiophenol, obcained by the action of acetic chloride,is c r j stalline, readily soluble, and hoils at 255" under ordiiinry atmo-spheric pressure. The benzoyl dcriva-tive forms large crystals, and melts a t 75.5".OrthochZol.othiopheno1 is prepared in a n exRctly similar manner fromorthodiazochlorobenzene. It forms R cnlourlew, strongly refractiveliquid, of penetrating, but not disagreeable, odonr; boils a t 204-2206',and has sp. gr. 1.2i52 a t 19.5". I t resembles the meta-derivative inits reaction,s, but is less stable, and gradually evolves hydrogen salpliidewith formation of chlorophenyl sulphide. The ncetyl compound bi~ilsat 254-258"; sp. gr.1-2659at 19.S". The benzoyZ compound boils a t335--340", sp. gr. 1.2785.For the sake cif compmiaon, the author prepared the three corre-sponding chlorophenols ; the ortho- and para-compounds, by the actionof dry chlorine on pheiiol a t the ordinary temperature; the meta-compciund according to the methods of Beilstein and Knrbatoff, andof Utilemann. The follawing derivatives are described : acefylorfho-chlorophenol, liquid, boiling point 20.1.2(18" ; sp. gr. 1.1709 at 19.5".RenzOyEor2hochlor~phenol, liquid, boiling point 308-312" ; sp. gr. 1.19 74at 19.5". Acetylmetach lorophenol, liquid, boiling point 226-2523" ;sp. g r . 1.2165. Benzoylm~tach7o~-o~hFno1, solid, melting point 71".Ar,etyZparachEnrophenoZ, liquid, boiling point 23U-232 ; sp.gr. 1.2404at 19.5.Action of Methylchloroform and E thylchloroform on AlkalineSolutions of Phenols. By F. HEIBER (Ber., 24, 3677-3687).-Yhenyl orthacetate, CMe(OPh),, ifi obtained when methylchloroform(16% parts) is gr~dually added in the course of sever;l days to a hotsolution of phenol (38.4 parts) and sodium hydroxide (22.6 parts) inwater (22.6 parts). It crystallises from hot alcohol in transparentplates, melts a t 98--98.5", and is readily soluble in ether, chloroform,and benzene, but almost insoluble in water ; it dissolves in concentratedsulphuric acid with a red coloration, and on prolonged boiling withal(.oholic potash, i t is decomposed into phenol and acetic acid. Thetribrnmo-derivative, C,,H,,O,Br,, is formed when phenyl orthacetateis treated with bromine in cold glacial acetic acid solution ; it crystal-liFes from hot alcohol in transparent plates, melts a t 132-13~3", isvery stable towards acids and alkalis, and is moderately easily solublein ether, chloroform, and benzene, but insoluble in water.OrthonitrophenyE orthncetrde, C&1e(O*C6H4aN0,),, prepared fromniethylchloroforni and orthonitrophenol in like manner, melts a tIts sp.gr. is 12629 at 19.5".Benzoylparachlorophenol., solid, melting point 8i".J. W. TJORGANIC CHEMISTRY. 309167-168", and is only sparingly soluble in most ordinary solventswith the exception of boiling benzene ; it is veiny stable towards diluteacids and alkalis.ParacresyZ orthacetate, CMe ( O-C6H,%~e),, crystnllises from alcoholicether in rhombic plates, melts a t 135.5" (?), and is soluble in all theoydinary organic solvents, but insoluble in water ; i t ia only slowlyacted on by boiling acids and alkalis.The tribromo-derivative,C23Hz10,Br3, separates from boiling acetic acid in crystals, melts a t160-161", and is insoluble in water, but more 011 less readily solublein all the ordinary organic solvents.Metncresyl orthacetate, C23H2403, crystallises in needles, melts a t99-100", and is insoluble in water, but readily soluble in ether,chloroform, and boiling alcohol ; the tribromo-derivative, C231€2103Br3,melts at 151.5-153".Orthocresyl orthacetate, C2:3H2403, forms transparent crystals, meltsa t 87.5--89", and is readily soluble in all ordinary organic solvents,but only sparingly in water.ResorcinyZ orthacetate, CMe(O-C6H,*OH),, is a yellow powder, meltsa t about 155-159" with decomposition, and is readily soluble in coldalcohol, ether, and glacial acetic acid, but only sparingly in hotwater, and insoluble in benzene.Hlldrozybeiazo~henon~, COPh*CaH,*OH, is obtained, together withphenyl benzoate (m.p. 70.5-71.5') and a yellowish-red, resinoussub-tance, when an alkaline solution of phenol is warmed with benzo-trichloride (phenylchloroform) ; it crystnllises from dilute alcohol incolourless plates, melts a t 41.", and is readily soliible in alcohol, ether,glacial acetic acid, and alkalis, but insoluble in water.F. S. K.Derivatives of Carvacrol. By G. MAZZARA and G. PLAECHER(Gazzetta, 21, ii, 155-157) .-Patern6 and Canzoneri obtained nitroso-carvacrol by the action of potassium nitrite on carvacrol, b u t theyield was very small ; 70 per cent.of the theoretical may be obtained,however, by slowly dropping amyl nitrite (35 grams) into an ice-cold solution of carvacrol (50 grams), and soda (15 grams) in thesmallest possible quantity of alcohol. The ethyl alcohol is eliminatedby spontaneous evaporation, the solution diliited with much water,separated from the precipitated amyl alcohol and resin, and acidifiedwith sulphuric acid. The nitrosncarracrol, which separates, is dis-solved in ammonia, reprecipitated with sulphuric acid, axid finallycrystallised from benzene.Diacetylwmidoetlaenylarnidocarvacrol, N A c ~ - ( & H M ~ P ~ < ~ > C B ! ~ , isobtained by heating ace tic anhydride with monacety lnrnid oe then yl-amidocarvacrol in molecular proportion a t 180-190" ; the excessof acetic anhydride is evaporated off, the product cooled to 60", andwashed with water.After recrystallisation from boiling alcohol, it isobtained in transparent tables which melt a t 123-125", and losetheir transparency on exposure to light.Acetyldinitrocaruacrol, C6H (NO&PrMe.OAc. is prepared by heat-ing a mixture of dinitrocarvacrol with acetic chloride f o r some houmin a reflux apparatus. The product is washed with dilute sodium310 ABSTRACTS OF CFfEMICAL PAPERS.carbonate solution, and dissolved in boiling Rlcohol ; on cooling, itseparates as an oil which soon solidifies.By ci~ystallisation fromlight petroleum, it is obtained in yellowish rhombohedra, which turnred on exposure to light, ; it melts a t 72-73".The acetyl and benzoyl derivatives of dinitrothymol melt a t highertemperatures than those of dinitrocarvacrol, whilst the ethenyl andbeneenyl derivatives of carvacrol melt a t higher temperatures thanthe isomeric thymol derivatives.- Action of Dinitrochlorobenzene on Polyhydric Phenols. ByR. N~ETZKI and B. SCH~NDLLEK (Her , 24, 3j85--3589).-~'etral./,itr.o-diphenylresorcinol, C6H4 [0.C6H.,(N0,)a]2, is formed when niolecularproportions of resorcinol, sodium ethoxide, and chlorodinitrobenzene[Cl : (NO,), = 1 : 2 : 41 interact in alroholic solution at the ordinarytemperature. It crystallises from glacial acetic acid in almost colour-less plates, melts a t lb4", and is insoluble in alkalis, and only verysparingly solnLle in most ordinary organic solvents ; it seems 'to becompletely decomposed by reducing agents, and when boiled withaniline, i t yields dinitrodiphenylamine.On treatment with coldf nrning nitric acid, it is converted into pentanitrodiphenylreuorcinol,C1BH9N5012r but with a warm mixture of nitric and sulphuric acid, ityields the /iezanitro-derivat,ive, C,sHaN,Oi, ; the former melts at 68",the latter a t 220", and both compounds are decomposed by boilinganiline with formation of dinitrodiphenylamine.Il'etranitrodiy hen y lquinol, C 1aH ,,N40 10, prepared from q ui no1 inlike manner, crystallises from glacial acetic acid in lustrous plates,melts a t 24O0, and is very sparingly soluble in most ordiiiaryorganic solvents ; i t is not decomposed by boiling aniline.Itsdinit.r.0-derivative, CleHsNsOlr, cry~t~allises from glacial acetic acid iiialmost colourless plates, and melts a t 130" ; its trinitro-derivativemelts at 220'; both these compounds are decomposed by boilinganiline with formation of dinitrodiphenyltimine.Hydromyrlinit~odi~Iien~larnir~e, C,,HgN,05, is obtained by treatingorthamidophenol with chlorodini trobenzene in presence oE sodiumacetate ; it crystallises in brownish-yellow needles, and melts a t 190'.Di~liydro.eydinit~~odipAerLylamii~e, C 12H9N306, prepared from amido-resorcinol in like manner, crystallises iu brown needles, and melts a t163". F.a. I(.W. J. P.Oxidation of Aromatic Compounds containing the SideChain C,,H,. By G. WACKER (Uer., 24, 3488--3491).---Wheusnfrole is oxidised in the cold with a 1 per cent. solution of potassiumpermanganate, it yields the corresponding glycol, CIOH1204, whichcrystallises from ether in prismatic .needles, melts a t 78.5", and givesa diacetyl derivative boiling a t 262" under a pressure of 90 mm.(compare Tiemann, this 1-01,, p. 47). Resides the glycol, which,oontrai-y to Tiemann's statement, is more soluble in cold alcohol thani n boiling ether, piperonal, piperonylic, a-homopiperonylic, formic,and other acids are produced, but not acetic. When jsosafrole isoxidised, i t yields a glycol crystnllising in thick prisms and meltingat 101-102".The glycol obtained from xnethyleugenol crystalliseORGAXIC OHENISTRT. 311in prismatic needles, melts at 68-69', and gives a diacetyl derivatireboiling at 268" (35 mm.) ; whilst the glycol from methylisoeugonolcrysta.llises in rhombic plates and melts at 88".Myristicin and its Derivatives. By F. W. SRMMLER ( R e r . , 24,3818-3823).-1n a previous communication, the author has shownthat myristicin has the composition C12HL10J,, and is a derivative ofbenzene containing an unsaturated Bide chain (Abstr., 1890, 1150).To obtain further information as to its constitution, it was subjectedto the action of oxidising agents ; nitric acid and chromic acid act intoo violent a manner, but the oxidation may be readily carried out bymeans of dilute potassium permanganate. The liquid is filtered hotfrom the manganese precipitate, allowed to cool, and the white,crystalline compound which separates collected and recryatallisedseveral times from water.I t has the composition C9HB04, melts a t130" (uncorr.), boils at 290-295', reduces silver solution, and com-bines with hgdroxylamine and phenylhydrazine. It i N , therefore, analdehyde C8H,03.CH0, and may be termed myristicinaldehyde ; it i.9also found to contain one methoxyl group, and, as already stated, is Rderivative of benzene ; the formula may therefore be further resolvedinto CH302:C6H2(OMe).CH0. The oxygen must; be present in theform of an oxymethylene group, for neither myristicin nur myristicin-aldehyde behaves as a phenol ; hence myristiciiialdehyde has the con-A.R. L.-stitutional formula, CH,<~>C,Hz(OMe)mcHO, and occupies an inter-0 mediate position between piperonaldehyde, CH,<O> CGH3*CH0, and0 apionaldehyde, CHz<O>C6H(OMe),.CH0. The constitution ofmyristicin itself is, themfore, CH,<O>C6H,(Onle)*CIH,, 0 and itmay be termed oxy m ethylenemethoxybuteny lbenzene.The filtrate from myristicinaldehyde contains the correspondingmyristic acid, C HS<O> C,H,( OMe)-COGH, which separates in white,crystalline fla)kes on the addition of phosphoric acid, and, afterrecrystallisation from hot water, forms lung, yellowisli-white needles.It melts a t 208-210" (uncorr.), does not boil without decomposition,even in a vacuum, and is only sparingly soluble in water.I n order to ascertain the positions occupied by the side chains inthese compounds, myristic acid was heated with phosphorus andhydriodic acid i n a sealed tube ; the product of the reaction was foundto be gallic acid, showing that the methoxyl and oxymethylene groupsmust occupy the positions 3 : 4 : 5, the carboxyl, aldehyde, or butenylgroups occupying the position 1.When myristicin is treated wit.h bromine in acetic acid solution,carbonic a,nhydride is evolved, and a voluminous precipitate sepa-rates ; this, after recr-y st allisation from alcohol, forms slender, snow-white needles, and melts a t 159-160" (uucorr.). It has the composi-tion C,H,O,Br,, and appears to be methyZoxymethyZenetribroniop?jro-yallol. H.G. C.312 ABSTRACTS OF CHEMICAL PAPERS.Action of Carbonyl Chloride on Benzylamine.By B. K ~ H Nand J. I t r E s E N F E r a (Ber., 24, 3815-3818).-Hitherto, benzyl iso-cyanate has not, been prepared in the pure condition, the productobtained by acting on silver cyanate with benzyl bromide or chloride(this Jcurnal, 1872, 446 ; Ber., 10, 46) always containing chlorineor hromine. $The authors have endeavoiired to prepare i t by theaction of carbonyl chloride on benzylamine hydrochloride ; the pro-duct is, however, a mixture of varying quantities of benzyl isocyanateand be~izylchloroformamide, CHI,Ph*NH.COCI, which cannot beseparat,ed by fractional distillation, nor can the latter derivative, likemethylchloroformamide (Abstr., 1887, 569), be converted into theformer by distilling with potash, benzyl cyanurate being thus ob-tained.The same compound is precipitated when a large quantity oflight, petroleum is added to the mixture of beiizyl isocyanate andchloroformamide. When the mixture is treated with aniline, the soleproduct is phenyl benzylcarbamide ; methylanilin e converts it intobenzylphe?zylmethyZcai.bamide melting at 84", metanitraniline into benz y l -met~nnitrophennylcarbamide melting a t 188", a-naphthylamine intohenzy 1-a-naph thylcw*banlide melting a t 203', is0 butylamine into berrzyl-isobutylcarbamide melting a t 78-79", and piperidine into beneyl-piperid y lcarbamid e me1 t ing a t 10 1-1 0 2 '. H. G. C.Nomenclature of Stereoisomeric Nitrogen Compounds andof Rings containing Nitrogen.By A. HANTZSCH (Bey., 24, 3479-3488).-The author proposes to distinguish the stereoisomeric nitro-gen compounds by the Greek prefixes syit, anti, and aw,phi, thesebeing equivalent to cis, trans, and cistrans, which are eniployed byv. Baeyer for certain other stereoisomeric conipounds. The prefixsyn is used with those compounds containing certain groups whichare capable of inti~amolecular change, whilst, anti is employed witlithe isomeride containing the same groups which are iricapxble of it ;for example, syn is prefixed t o that benzaldoxime from which benzo-nitrile is obtainable, thus :-P h * s * H Ph-5 *HN-OH ' HO-NSpbenzaldoxime. An tibeiizaldoximc.For distinguishing such compounds as the three isomeric benziledi-oxinies, it is necessary to employ also the prefix amphi, as follows :-Synbenzileclioxime.Antibenziledioxime. Amphibenziledioxime.The acthor is of opinion that the term " azo," in its applicationt o closed-ring compounds, should be restricted t o those containingtriad nitrogen, whilst, for such as contain the group NH, the termL 1 imid 3 7 should be employed. He proposes the following alterationsin nomenclature :-Iinidole for pyrroline, tliiole for thiophen, anORGANIC OHNMISTRY. 31 3oaaTe for furfuran ; derivatives obtained by displacing a CH gronpin theHe by N are designated imidnzols = C,H3(NH)N, orazole =C,H,(O)N, aiid thiuzola = C3H3(S)N respectively. The isomerism ofthese compounds may then be indicated by the above-meritioned pre-fixes; thns, the two imidnzolea [NH : N = 1 : 2 and 1 : 33 are callc dsy nirnidazole and anLp?&nidazolr respectively, whilst Wid man's tri-azoles, C,H,(NH)N,, are named imidodiazoles or azirnidazoles, and thethree isornerides [NH, : N, = 1 : 2 : 5, 1 : 2 : 3, and 1 : 3 : 51 are dis-tinguished as synazinziduaole, synimidodiaxole, and arnphimidodiazolc.The three six-memhered ring compounds C,H,N, are designatedsyn dinzine, amphidiazine, and ant idiazine, according as they have theconstitutions [N : N = 1 : 2, 1 : 3, and 1 : 41.A. R. L.Action of Benzyl Chloride on Ortho- and Para-toluidines.tolxidina, C6HIMe*5Me-CH,Ph, is obtained by heating a mixture, inmolecular proportion, of benzylorthotoluidine and methyl iodide for40 hours. The product is heated with dilute s>,diuro carbonate aildextracted with benzene.At 210-215", under 15.2 m u . pressure, ayellowish oil passes over ; this is insoluble i n nater, soluble i u alcohol,benzene, kc., and has no basic character.The sulphonic derivative of benzylorthotoluidine is obtained hyheating benzplorthotoluidine for two hours a t 185-1 30" with sulph-uric acid containing 15 per cent. of anhydride; its lead and bariumsalts are soluble in water and crjstallise well. The acid is a crystal-line powder, fioluble in water. Its aqueous solution, when treatedwith lead dioxide, becomes first green and then blue.Benzy1parntoluidine.-A mixture of parntoluidine (2 mols.) andbenzgl chloride (1 mol.) is maintained at 155-165" for 40 hours. Ayellowish oil is separated, as ahow; this distils a t 205-5215" under10-15 mm.pressure, and darkens in colour on coolitig. It, remainsliquid, even i n melting ice, whereas the dibenxyl derivative melts a t54 5-55', and benzoylorthotoliiidme melts a t 56-57'. The jield inthe case of benzylorthotoluidine is 40 per cent., whilst in the case ofbenzylparatoluidine it is only 30 per cent. A t a temperature higherthan 170", large quantities of a black, resinoils product are formed;this does not distil up to 270" under 20 mm. pressure.The salts of benzylpzratoluidine are white and well crystallised, butlittle soluble in cold water, more soluble in, and readily decomposedby hot water. The methyl and ethyl deyivntives of this base areobtained by heating it with the corresponding alcoholic iodidtis.Benzylethy~uratoluidinn is a jellow liquid boiling at 200-210" under10 mm.pressure. neurylnrethylparatoluidi~re is a slightly yellowliquid boiling at 210-2'20" under 30 mm. pressure. These derivatives]lave no basic characters.Benzoylbenz~lparatoE~~idine.-This compound is formed by the actionof benzoic chloride on benzylparatoluidine. The product, if distilledwhen hydrochloric acid ceases to be disengaged, yields a thick liquid,which passes over at) 2i5--285" under a pressure of 20 mm., and rapidly~olidifies. No salts have been obtained with acids. When dissolvedi n glacial acetic acid and added drop by drop to fuming nitric acid, a,By C. RABAUT ( BuU. SOC. Chim. [3], 6 , 1 3 7 4 4 0 ) .-1C~ethylbeiirylorti~(,31 4 ABSTRACTS OF CHEMICAL PAPERS,nitro-derivative is obtained, which is precipitated by the addition ofwater.It dissolves in alcohol and crystallises in yellow needles, 1 em.long, which melt at about 135-137'. I t appears to cow& of twosubstances, into which it separates on fusion ; that in greater quantitymelts at 135-137". W. T.Action of Benzyl Chloride on Metaxylidine. By JABLIE-GOX'NET (Bull. Xuc. Chiin. [ 3 ] , 6, 2l).-A mixture of benzyl chloride(1 mol.) and metaxylidine (2 mols.) is heated in a, reflux apparatus at160-165" for 50 hours. The resulting crystalline mass is boiled withsaturated sodium carbonate solution, and the oily, brown layer whichseparates is, after extraction with benzene, distilled under reducedpressure.Benzylmefaxylidilze, C,H,Me,*NHBz, passes over at200-210" under a presslire of 15 mm. a s a pale yellow liquid,which is soluble in alcohol and benzene ; with acids, it foyms white,unstable salts, which are decomposed by water. Methyl, ethyl, andacetyl derivatives have been made and will be described later.Action of Hydroxylamine Hydrochloride on Acetomesitylene.By E. FEITH and S. H. DAVIES (Bey., 21, 3546--3548).--Acetyl-mesidine (rri. p. 216-217") is formed, when an alcoholic solution ofacetomesitylene is heated at 160" for six hours with hydroxylaminehydrochloride and sodium acetak, the oxime which is first producedimmediately undergoing intramolecular change.Acetophenone and acetopseiidocymene are not acted on by hydroxyl-amine under the conditions just stated, but propiomesitylene, at arather higher temperature (ISO"), yields, on prolonged heating, a verysmall quantity of a crystalline compound which melts at 154*5",and is insoluble in potash.T.G. N.I?. S. K.Derivatives of Trinitroquinol. By R. NIETZKI and H. KAEFMANN(Bey., 24, 3824--8830).-Twelve years ago Nietzki showed that oneof the nitro- groups in trinitrodiethylquinol may be readily replaced byan amido- or substituted amido-group ; thus aniline yields a diethoxydi-nitrodiphenylamine. The latter, on boiling with alkali, was found toyield a substance having acid properties, which was regarded asdiethyldinitro tri hydroxy benzene ( Abstr., 1878, 866).Further investigation has shown that this supposition is incorrect,the substance having the compoRition C1J3,,NzO6, instead of ClOHl2O7N2;i t must, therefore, be formed by the hydrolysis of one of the ethoxy-groups, and is an ethozy h y d r o z y d i n i t r o d ~ h e ~ y l a ~ ~ i n e ,OE t*CsH (OH) (NO,) ,*NHPh[OEt : NHPh : NOz : OH : NO, =1 : 2 : 3 : 4 : 51.It crystallisesfrom alcohol in yellow needles, and melts at 152".When diethoxydinitrodiphenylamine is reduced with tin and hydro-chloric acid, it yields the corresponding diethoxydiamidodi~~~~e~~ ylaniinr,CsH(0Et),(NH,),*NHPh, which crystallises in almost colourlessneedles, and melts at 77" ; its hydrochzoride, C16Hz,Ns0,,2HC1, formscolourless needles, which become blue on drying, and are less stablethan the free base. On boiling with acetic anhydride, it yields a derivaORGANIC CHEMISTRY.315tive which is simultaneously an acetyl compound and an anhydro-base, and h a s the constitution N H ~ C ' C ~ H ( ~ C , H , ) , < ~ ~ ~ ~ - ; i tforms colonrless needles, melts a t 162", and is readily soluble in hotwater, alcohol, ether, and dilute acids.T rinitrodiethylyuinol also readily reacts with an excess of dimetbyl-paradiamidobenzene, the reaction proceeding in the same manner a swith aniline ; the nitro-group is evolved as nitrous acid, and convertsR portion of the diamine into dimet,hylaniline. The chief product ofthe action, which has the constitutionC6H( XO,), ( oEt),*NH*C6H4*N&fe2,has distinctly basic propert?ies, and crystallises from alcohol in beauti-ful, red needles nielting a t 148".I t s hydrochloride forms needles whichhave a green surface lustre, and are decomposed by water. It isreadily reduced by tin and hydrochloric acid, but the resulting tri-amido-compound cannot, be isolated, as i t rapidly undeygocs oxidation ;if manganese dioxide be added, and the mixture boiled till theoriginal blue colour has changed to brown, the residue, 011 extractionwith boiling alcohol, yields the product of oxidation in beautifulneedles havirtg a green lustre. The analysis showed that it has thecomposition ClsH2?N4O2, and i t is, therefore, a s would be expectedfrom its mode of formation, a dietho1:ydimethyldia?.ilidophenazine,NH,-C,H(OEt),<.&>C,H,*NMe,, and has all the properties of a,eurhodine.It dissolves in concentrated sulphuric acid with a preencnlour, which, on dilution, passes through blue into red, and colourssilk with a slightly violet-red nuance.crystalIises in needles having a green lustre ; the acetyl derivative,ClaHz,N402Ac, crystallises in pale red needles melting at 179", andyields red salts wit12 acids.Paradiamidobenzene does not undergo condensation with hinitrodi-ethylquinol so readily, but, its acetyl derivative gives more satisfactoryresults ; the product of tlte reaction forms pellow, silky needles, meltsa t 199", and has the constitution C,H(O Et)2(N0,)2.NH.C6H4*NHAc. Onboiling with dilute alkali, the acetyl group is not eliminated, butinstead one of the etbpl groups is removed, with formation of a sub-stance having the constitution OH.C,H(OF:t) (N02)2*NH*CsH4.NHAc,which forms yellowish-brown crystals, readily soluble in alcohol, andmelts a t 206".More concentrated alkali converts it into a dinityo-eth y Ztrih y drox y benzene, OE t*C6H (OH) (NO,) 2, which forms ye 110 wneedles, and melts a t 210" ; it is not identical with the dinitroethyltri-liydrox ybenzene obtained by Nie teki from diamidodinitrophene toil(hbstr , 1883, 466).TrinitrodiethylquinoI also undergoes condensation with dim ethyl-metadiamidobenzene and a-naphthylamine ; the first yields a com-pound of slightly basic properties, having the constitutionC,H (OE t),_( NO,),*NH- CsH4*NAfs2,NThe p i c m t e ,C1~H22N402~ C6H3N307,1 316 ABSTRACTS OF CHEMICAL PAPERS.which crystallises i n orange-yellow needles and melts at 106".compound obtained from a-naphthylamine,fwms yellow needles melting at 128", and may 'be separated from thea-arnidoazoniiplithaleiie siriiultaneously formed by tzLkiiig advantageof its Iesser solubility in alcohol.Diazobenzene Perbromide.By C. E. SAUNDERS (Amer. Chem. J.,13, 486-490).-0n treating an aqueous solution of diazobenzenesulphate, best prepared by Knoevenagel's method (Abstr., 1891,54), with an excess of cold solution of bromine i n moderittely stronghydrobromic acid, diazobeiizene perbromide separates as a dark,pasty mass, which, when repeatedly washed with ether and driedbetween filter paper, loses most of i t s colour, and almost ceases tosmell of bromine. The liquid product o~iginally obtained by Griess( P h i l .Trccr,s., 1864, 673), which was probably a mixture or compoundof the perbromide with free bromine, mas be fortried by exposing thedry solid to bromine vapour, of which i t absorbs a very large quantity ;the perbromide may be recovered by treatment with ether. In t h epreparation of the perbromide, symmetrical tribromobenzene occursa s R bye-product ; i t is dissolved, however, by the ether.When diazobenzene perbromide is treated with bromine-water, it,yields tribroniophenol, and when boiled with water alone, it yields i naddition phenol, hydrogen bromide, and bromine. When boiled withalcohol, i t gives, not bromobeiizene alone, as stated by Griess (loc. cit.),but a mixture of this substance with parabromophenetoil, melting a t4" (compare Remsen and Orndorff, Abstr., 1888, 268).With boiliiigetEer and wit.h glacial acetic acid, it yields bromobenzene, mixed, iuthe latter case, with another compound of much higher boiling point.Intramolecular Formation of an Azo-group. By E. LELLMANNTheC,H( OEt), (N O,),.NH*C,oH,a,H. G. C.JN. W.and R. ARNOLD (Ber., 24, 3557-3.560 ; compare Tauber, this vol., p.1 1 , is obtained when an 183) .- Oyt hazodibenx y lamine,CH2*CF,H,-N "< c H,*c,H,-Nalkaline solution of t h e theorctical quantity of stannous chloride isgradually added t o a hot alcoholic solution of orthodinitrodibenxgl-amine; i t crystallises in small, orange needles, melts at 230", and isonly very sparingly soluble in dcoliol, but, more readily i n benzene.The hydrochloride, C,,H,,N,,HCl + H,O, crystallises i n slender,orange needles, and is converted into the base when heated at SO".tained from orthodinitrodibenzylparatoluidine in-like manner.F.S. K.Alkyl Derivatives of Hydroxylamine. By R. KOTHE (Annulen,266, 310-323 ; compare Behrend ai~d Kijnig. Abstr., 1891, 1032).-When a-benzylhydroxylamine is oxidised w i t h potassium dichromateand glacial acetic acid, it jields benzyl alcohol and traces of benzylnitrite and benzjl acetate, nitric oxide being evolvedORGANIC CHEMISTRY. 317When a-dibenzylhydi.oxgls.nine is treated with potassium dichrom-ate and sulphuric acid, it yields benzylbenzaldoxime and small quan-tities of benzaldehyde and benzoic acid ; if the potassium dichromateis added very gradually to a very dilute sulphuric acid solution of thea-dibenzylhydroxylamine, the yield oE benzylbenzaldoxime is niuchsmaller, but benzyl alcohol and other compounds are formed i n itsplace.Tribenzylhydroxylamine is not acted on by potassium dichromateand sulphuric acid under the conditions employed by the author.When tribenzylhydroxyiamine is distilled under reduced pressure,it is decomposed into P-dibenzylhgdroxylamine, stilbene, benzylamine,p-benzg lhydroxylamine, and ammonia.Amidoximes and Azoximes.By I?. T~EMANN (Be?., 24, 3648-3650).-General remarks on the papers of Marcus, Goldbeck, Paschen,and Richter. (Compare following abstracts.) F. S. K.F. S. K.Nitrogenous Derivatives of some Aromatic Dihydroxyalde-hydes.By E. MARCUS (Ber., 24, ~650-~~657).-~-ResorcylaZdoxime,CsH,(0H),*CH:NOH [CH : (OH), = 1 : 2 : 41, prepared from/3-resorcylaldehyde, crystallises in colourless needles, me1 ts at 191",and is readily soluble i n alcohol and ether; it gives with ferricchloride a brownish-red coloration, and with Fehling's solution agreen precipitate. The corresponding hydrazone (111. p. 158-159')was also prepared. (Compare Rudolph, Abstr., 1889, 251.)Diacety Z-P-resor~yZonitr~Z~, CN.C6H3( OAc),, is formed when thealdoxime is boiled with acetic anhydride ; it crystallises from alcoholin colourless prisms, melts at 72", and is readily soluble in alcohol,ether, chloroform, and benzene./3- Resorcy lonitvile, C7H5N02, i n produced when the diacetyl deriva-tive is hydrolysed with dilute potash.It separates from a mixture ofether and light petroleum in crystals, melts at 175', and is readilysoluble in water, alcohol, and ether ; its aqueous solution gives a redcoloration with ferric chloride.p-IZesorceny lamidoxime, C6H3( OH) 2*C ( NI12):NOK, prepared bytreating the nitrile with hydroxylamine a t the ordinary temperature,turns brown at 160", melts at 166", and is reedily soluble in water,alcohol, and ether ; it reduces Fehling's solution, and gives a browncoloration with ferric chloride.The dioxime, (OH),C6H2(CH:NOH), [ (CH), : (OH), = 1 : 6 : 2 : 41,is obtained when resorcyldialdehjde is tibeated with hydroxylnmine ;i t melts at 209", and is readily soluble in alcohol, ether, and potash,but only sparingly in water ; in its aqueous solutions, ferric chlorideproduces a black, and copper sulphate a blue, precipitate.Orthornethoxyparahydmxybenzoplwaylhydrazone, Cl4H,,N20,, preparedfrom the corresponding aldehyde, is a yellow, crystalline substancemelting at 151-152" ; it is readily soluble in alcohol, ethei-, benzene,and chloroform, but insoluble in water.The corresponding aldoxime,C,H,NO,, melts a t 171", and is soluble in water, alcohol, ether, andsoda, its solutions giving it brownish-red coloration with ferricchloride.YOL Lxzr. 2318 ABSTRACTS OF CJEMJCAL PAPERS.Acet~lvaiza'ltonitriZe, CN.C6H,(OMe)*OAc [CN : OMe : OAc =1 : 3 : 41, prepared by heat,ing vanillinaldoxime (m. p. 117") withacetic anhydride, crystallises from hot watcr in colourless needles,melts at 110", and is soluble in alcohol, ether, and benzene.Vanillonitrile, C8H7N02, i s formed when t'he acetyl derivative is dis-solved in cold, dilute potash ; i t crystallises from hot water in colour-less needles, melts at 87", anfd is soluble in alcohol, ether, and benzene.3n its aqueous solution, ferric chloiide produces R blue coloration, and,on warming, a crystalline substance is precipitated.VuniZlan?jZamido~:i?lze, CpHloNz03, prepared f rorn the nitrile just de-scribed, crystallises from water i n prisms, melts below loo", and dis-solves freely i n alcohol, hydrochloric acid, and soda, but is onlysparingly soluble in ether, and insoluble in benzene ; i n its aqueoussolntions, ferric chloride produces a reddish-violet, and Fehling's solu-tion a green, coloration.Piperonalaldoxime, CH2< o> C6H3*CH:NOH, cry stallises from hotwater in lustrous needles, melts a t l l O o , and dissolves freely i n alco-1101.ether, benzene, chloroform, and carbon bisulphide. The corre-sponding nitrile, C8H,NOZ, is readily solub!e i n alcohol, ether, andbenzene, and crystailises fibom water i n lustrous needles melting at95'. The anzidoxime, CHH8N203, melts at 151", and is soluble i nh o t water, alcohol, ether, acids, and alkalis ; i t s hydi.ochloride,C,€T,N,03,HC1, is a colourless, crystalline compound- melting at 193".E t h e n y l p i p e r o n m ylaxoxiine, CH,<, >C6H3*C<- X->CMe, is formedwhen piperonenylamidoxime is heated with acetic anhydride ; i t meltsa t 110", and is readily solulde in alcohol, ether, and benzene, but in-soluble i n water.F. s. K.00 NONitrogenous Derivatives of Parahomosalicylic Acid. By0. GOLDBECK (BAT., 24, ~658-~667).--Parahomosalicyl~~Zdoxi~i,t.,OH-CoH3Me*CH:NOH [Me : CH : OH = 1 : 3 : 41, crystallises i n long,colourless needles, melts a t 105", and dissolves freely in hot watei.,nlcohc;:, ether, chloroform, and benzene, b u t is only sparingly soliiblei n light petroleum and cold water ; its aqueous solution gives a dirtyviolet coloration Kith ferric chloi+le.Acet~j~~arahomosal&cylonitri~e, CloH,NO,, prepared by boiling t h ealdoxime with acetic aiihjdride, melts at 56-57', and is readilysoi nble in alcohol, ether, benzene, acetone, chloroform, and hot lightpetroleum, but only sparingly in water.Ya.l-ahomosalicylamide, CPH9NO2, obtained by heating ethyl para-honiosalicylate with concentrated amrnonin, crptallises from dilutealcohol in coloarless needles, melts at 177-1 78", and is readilysoluble in alcohol and ether, b u t more sparingly in benzene andchloroform ; its aqueous solution gives with ferric chloride a dark-violet coloration.The cori esponding thiamide, CsHSNOS, wasobtained in an impure condition by melting the amide with phos-I horus pentasulphide ; it dissolves freely in alcohol, ether, chloroform,benzene, alkalis, and h o t water, melts at 126-127", and gives withferric chloride R dark-violet coloration, with copper sulphatle a greenORGANIC CHEMISTRY.319and with silver nitrate a reddish-brown, precipitate. The nitrile,CRt17N0, is formed, with evolution of hydrogen sulphide, when thethiamide is snbmitted to dry distillation. It melts a t lOO--lUl", dis-Iqolves fineely in alcohol, ether, benzene, and chloroform, and is clecom-posed by boiling alkalis ; in its aqueous solution, ferric chloride pro-duces a violet coloration.Parahomofinlicenyla~~~o~;me, CsH,,N2Os, prepared by heating thethiamide with hydroxylamine in dilute alcoholic solution, crptt"l1isesfrom hot benzene in plates, arid from hot, waker in needles, melting at123-124"; it is readily soluble in ether, alcohol, hot water, aidchloroform, and in its aqueous solution ferric chloride produces areddish-violet coloration, and copper ~ i i l phate a light-green precipi-tate.The I,~/lldrachlorirle nielts at 215" with decomposition. Tlielrenr0~2 derivative, C,sH14N,03, obtained by triturating thc arnidoximew i t h benzoic chloride, melts a t 181--152", and is readily soluble inaretone, but otily sparingly in alcohol, ether, and benzene, and in-siil~rble in water and light petroleum ; its alcoholic solution gives a,green coloration with ferric chloride.Benieny~al.aho?izosaZicenylazoaime, OHC6H3MemC< - N>CPh, isformed when t h e benxoyl derivative (m. p. 181-183") is heated.withwater at 100'; i t melts a t Id", dissolves freely in ether, alcohol,~!~1oi-oform, benzene, ligii t petroleum, and alkalis, and gives w i t hferric chloride in alcoholic solution a green coloration.Dib~~~zoylparahomo.salicenyl~~naiJoxime, C2zHlsN,0i,.prepared by shak-ing the amidoxime with potash and benzoic chloride, melts a t l43".,and is readily soluble in hot aicohol, ether, chloroform, and benzene,b u t insoluble iu water, acids, and alkalis.Acetylpa~ahonzosulicenylanz~rlox~me, C,,,H,,N,O,, is obtained when theamidoxime is treated with acetic anhydride a t t h e ordinary tempera-tiire ; i t crjstallises from hut benzene in plates, melts at 148-149",and dissolves frrely in alcohol, ether, cliloroform, benzene, diluteacids, and alkalis ; its dilute alcoholic solution gives a violet colora-tion with ferric chloride.Etheii~~lpnruhomosaliceizylazozime, ClnHION202, separates from etheri n prisrnahic crystals, melts a t 45", and is readily soluble in etliei.,alcohol, benzene, chloroform, and alkalis, but iiisoluble in water anddilute acids j i n its alcoholic solution, copper sulphate produces areddish-brown precipit,ate, and ferric chloride a blue coloration.NOYrop~n~lparahomosalicenylaaoxime-w-carboxyl,ic acid,can be obtained by heating t h e amidoxime with succinic anhydride at&bout 115".It crystnlliszs from dilute alcohol in slender, colourlessiieedles, melts at 103", aud is readily soluble i n ether, benzene! and hotwater, but more sparirigly in cliloroform, and insoluble in light petr-oleum ; its Rqueous solution gives a viulct coloration with ferricchloride, and in its neut,ral sJutioiis silver nitrate produces a colo~ir-less, ci-jstalline precipitate.F. ,S, K.a:320 ABSTRACTS OF CHEMICAL PAPERS.Derivatives of Orthohomosalicylaldehyde and of Ortho-homoparahydroxybenxaldehyde. By E. PASCHEN (Bw., 24,3667-3675) .--tholLomosnlic~~henylh~Jdraaone,OH.C6H3Me-CH:NzHPh [Me : OH : CH = 1 : 2 : 31,crystallises from alcohol in colourless, rhombic plates, melts at 95",2nd turnfi greenish on exposure to the a i r ; i t i.9 readily soluble indcohol, ether, and chloroform, but more spaririglv in hot water, andiiisolublo in light petroleum. The aldoxinte, CEHgNO,, crystallise~ inlong, colourless needles, melts a t 99", and dissolves freely in hotwater, alcohol, ether, benzene, and chloroform, but is insoluble inlight petroleunl and cold water; in its aqueous sdutiom, ferriccll loride produces B violet coloration, and Fehling's solution abro wnish-red precipitate.Orthohomosal;icyZonitrile, CBH7N0, is obtained when the aldoxime isboiled with acetic anhydride, and the oily product decomposed withcold, dilute soda ; it crystalliseR from hot alcohol in colourless plates,melts a t 88.5", and is readily soluble in alcobol, ether, benzene, chloro-form, and hot water, but insoluble in liqht petroleurn.Ortho/, c712osaZiceiiyZamii.loxime, CEHJT202, crystallises from alcoholin large, colourless plates, melts a t 126.5", and is insoluble i n lightpetroleum ; it dissolves freely in alcohol, benzene, chloroform, andhot water, and gives a dirty-preen precipitate with Fehling's solution.The diberazoy Z derivative, C23H,6Nz04, separates from alcohol in small,colourless needles, melts at 164', and is readily ~oluble in ether,benzene, and chloroform, but insoluble i n light petroleum and coldwater.Benzeizylorthohomosa7icenylazoxhne, C15HlzNzOz, prepared by boilingthe dibeuzoyl derivative (m.p. 1 6 4 O ) with soda, forms colourlessneedles, and melts a t 150" ; it is insoluble in light petroleum, but dia-bolves freely in most of the other ordinary organic solvents.Orthohomoparah ydrozybenzophenyl}~ydrazone, C14H14N,0, melts at 151",and is readily Moluble in alcohol, ether, benzene, and chloroform, b u tonly sparingly in hot water, and insoluble in light petroleum, Thenldozime, CBHgN02, ci-ystallises in colourless needles, and melts a t143.5" ; it gives with ferric chloride a dark-green, and with Fehling'ssolution a light-green, coloration.Acetylorthohomoparah~drox~jber~zonttri~c, CIOHgNOZ, is formed whenthe aldoxime (m.p. 143.5") is boiled with acetic anhydride; itcryvstallises in colourless plates, meits at 75-76', and is irisoluble inlight petroleum, but readily soluble in ether, alcohol, benzene, andchloroform. The nitrile, CBH7N0, prepared by hydrolysing t8he ncetg 1derivative with dilute soda, crystallises in colourless needles, melts a t93", and resembles the preceding compound in its behaviour withsolvents.Ort hohoinoparn h ydToxyb enzeny lanaidoain I el C,H,,NzO,, forms colour-Irss scales, meltB a t 152" with decomposition, and turns bluish-greyon exposure to the a i r ; i t is readily soluble in alcohol, but moresparingly in ether and hot water, and insoluble in benzene and lightl~etroleum ; it gives a.bluish-green coloration with Fellling's solution.'Ihe hydrochloride, CBHloN,Oz,HCl, crystalliees in needlesORGANIC CHEXISTRY. 32 1Ethenylorthohoiiioparahydroxybenxenylazo~~~e, C,,R,,,N,02, .preparedby heating the amidoxime with acetic anhydride, crystallises fromIiot, dilute alcohol in small, colourless needles, melts a t 89", and is i n -solubie in water and light petroleum, but readily soluble in alcohol,ether, benzene, and chloroform.p-Trichloro-a-hydroxypropenylamidoxime. By E. RICHTER(Rer., 24, 36'76-367 7) .-p- TrichEoro-a-hydroxypropen~lamidoxi.nL,(:CI,-CH(OH)*C(NH,):NOH, can be obtained by treating the nitrilc:oE trichlorolactic acid with an aqueous solution of hydroxylamine atthe ordinary temperature ; it crystallises from hot wat,er jii plates,melts a t 145" with decomposition, and is almost insoluble i n benzeneand ether, but more readily in alcohol.C3HE,N2C1302,HCl,cryxtallises in plates.F.S. K.The hydrochloride,Et hen y Z- P- trich toro-a-hy drox ypropeny lazoxirne,prepared by warming the amidoxime with ace tic anhydride, crystal-lises from hot water in needles, melts at 160-161", and is readilysoluble in alcohol and ether, but only sparingly in benzene.F. S. K.Phenylglyoximes. By A. RUSSAKOW (Ber., 24, 3497-3511).-is best prepared by treat-Ph* C --C*H##OH #.OH1 Ant kp hen y lamp hig l y ox inae ,Ing sodioisonitrosoacetophenone (1 mol.) with hydroxylnmine hydro-chloride (1 mol.) and sodium hydroxide (1 mol.) in aqueous solutionat the ordinary temperature (compare Scholl, Abstr., 1891, 28i) ; theproduct is precipitated with acetic acid, washed with chloroform, andrecrystallised from ether.It melts a t 168", is almost insoluble inchloroform, and is identical with the phenylgl yoxirne previouslydescribed by Scliramm (Bey., 16, 2186) and by Strassmann (Abstr.,1889. 610). , r Ph*E-EmH is precipitated, as hydrochloride, PheNy la& iglyoxime,0H-N NmOH'when hydrogen chloride is passed into an ethereal solution of thepreceding compound ; this salt is stable in dry air, but in a moistatmosphere i t is quickly converted into the glyoxime with elimina-tion of hydrogen chloride. This glyoxime is also formed when iso-nitrosoacetophenone is treated with hydroxylnmine hydrochloride indilute alcoholic solut,ion ; it crystallises in well-detined prisms meltingat 180".It is stable in acid solution, but it is very readily con-verted into its isomeride (m. p. 16Sa) by most ordinary neutralsolvents, except ether, from which it cr~stallises unchanged ; itrefiernbles its isomeride very closely in appearance and in properties,but differs from i t as regards melting point.The diacetyl derivative, Cl5Hl2N2OJ, is formed when either of thoglyoxirneb: described above is treated with acetic anhydride at O", buta slight difference in the behaviour of the two compounds, as regard322 ABSTRACTS OF CHEMICAL PAPERS.the rapidity of solution, is observed. It cryFtallisea in well-defined,highly refractive prisms, melts at 93", and is readily soluble in mostordinary organic solvents, except etlier.?H:N>O, is formed when theCPb:NPJt en y 1 azoxazol e ( p heny lfurazan),diacetyl derivative is kept in contact with sodium carbonRte until i tis completely converted into an oil, and also, but only slowly and to FLlimited extent, when either of the glyoxirnes or the diacetjl deriva-tive is distilled with steam ; i t is best prepared hy precipitating a nalkaline solution of the glyoxirne with carbonic anhydride, andextracting the precipitate with cliloroform (see below).I?i crystal-lises from dilute alcohol in needles, melts a t 30" (36"?), is volatilewith steam, and volatilises very readily at the ordinary tempernt ure -it is insoliible in water and cold alkalis, b u t very readily soluble inether, chloroform, and benzene, end it dissolves unchanged in concen-trated sulphuric acid.Phenylvximidoacefonitrillp, NOH:CPhGN, is formed when phenyl-nzoxazole o r the diacetyl derivative (m.p. 92") is warmed with sodaor sodium carbonate, and also when phenylglyoxime is boiled withsodium carbonate ; when the glyoxime is boiled with soda, i t is onlyvery slowly converted into the nitrile. Phenyloxirnidoacetonitrile isalso the principal product (50 per cent. of the theoretical) of theaction of hydroxylamine 011 dibromacetopheiione in alkaline solution,a fact which was overlooked by Strassmann and by Schramm. Itci-ystztllises in plates, melts a t 128", dissolves freely in hot water andiu the ordinary organic solvents, arid is not volatile with steam; it isnot hydrolysed by boiling, concentrated hydrochloric acid, and whenheated with concentrated soda, it is only very slowly converted intophenyloximidoecetic acid, with evolution of ammonia.The a c e q lderivative, NOAcXPh-CN, prepared by boiling the nitrile, or eitherof the gljoximes, with acetic anhydride, separates from dilute alcoholin well-defined, rhombic crystals, melts a t 68", dissolves freely in allordinary solveiits, and is decomposed by soda, yielding the nitrile.The following observations Doint to the existence of a third u I R'H. Ph- c ----&OH OH-Nglyoxime, which is probably pkenylsynglyolm'me,When eit,her of the qlyoximes described above is dissolved in Podn,and carbonic anhydride passed through the solntion cooled to -lo",a precipitate, containing about 3:3--3t3 per cent. of the theoreticalquantity of phenylazoxnzole, is produced ; after extracting t,his COT-pound by shaking with chloroform, there remains undissolved a sub-stance which melts at 148-154"; this, on being dissolved in a verysmall quantity of acetic anhydride, yields an oily product.Whenthis oil is distilled with water, it yields in the first few minutes a farlarger quantity (above 51 per cent. of the theoretical) of phenylazox-u o l e than is obtained in the same time from either of the glyoximes,or from the acetyl derivative (m. p. 92") described above, and thenthe rate of formation of this compound quickly diminishes ; this oilis also very quickly converted into phenylaxoxazole on treatment withcold soda, whereas the diace tyl derivative yields phenyloximidoacetoORGANIC CHEMISTRT.323nitrile under the same conditions. These facts seem to show that theprecipitat,e produced with carbonic anhydride consists principally o Ephenylrtxoxa~zole, and contains, in addition, a plienylglyoxime whichdiffers from the other two compounds in properties, and probablyhas the configurahion given. above.No evidence of the existence of the fourt,h theoretically possibl,:isonieride was obtained. I?. S. K.Action of Nitrous Acid on Bensenylamidethoxime. By F.TIEMAKN (Bey.. 24, 3453-3433 ; compare Tiemann and Kruger,Abqtr., 1884, 1325 ; 1885, 790).-The author finds that when sodiumnitrite is added in molecular proportion to a solution of benaenylamid-(.thoxime acidified with a mineral acid or a strong organic acid, thecharacter of the product depends on the acid employed.Benzenyi-et,hoxime chloride (Zoc. cit.) is formed in tho presence of hydrochloricacid.Benspnylethorinze bromide, CPhBr:NOEt, is obtained by dissolvingthe smidethoximc (1 mol.) in liydrobromic acid (2 mols.), cooling,crtutiously adding a solution of sodium nitrite (1 mol.), gently heatinga t 40" until the evolution of nitrogen cexses, extracting with ether,and, after evaporating the solvent, distilling in a partial vacuum ; i tis an oil, insoluble in water, but readily soluble in alcohol and ether,and boils a t 150" (45 mm.).Beizzenylethoxinze nEtrtfe, NO,*CPh:NOEt, is formed when a solutionof the arnidethoxime (1 mol.) in dilute snlphuric acid is treated withsodium nitrite (2 mols.) in the cold.It is an oil of little stabilitj,which dissolves in hot alkalis with decomposition, and is quickly con-verted into benzoic acid and ethoxylamine by hydrochloric acid ;when i t is sbaken with cold potassium hydroxide solution and cnrh-onic anhj dride passed through the solution, ethyl benzhydroxamaLe isf orrried.Beiizen ylethoxime acetate, OA c*CPh:NOE t, is prepared by dissolvingbenzenj lamitiet hoxime in conceri trated acetic acid, adding sodiu i t 1nit1 itc solution a t the temperature of the room, carefully neutralising,and extracting with ether ; it is an oil which does not solidify decom-poses into phenyl isocyanate on distillation, undergoes partial decom-position OIL boiling with water, and is readily soluble in alcohol andether; when carefully warmed with a solution uf potassium hgdroxidein dilute alcohol, the potassium derivative of ethyl benzhydroxamatcis obtained.A. B. IA.Dyeing with Aniline-black in the Dry Way. By S. GRAWITZ(Compt. rend., 113, 746--747).-1t is well known thRt dyeing withaniline-black in the dry may seriously weakens the fibre, and thatthis resuit cannot be avoided by using a neutral salt of aniline.According to Nietzki, aniline-black is a monobasic tetramine, and,if this be so, its formation will be represented by the equation4CsH,N,HCl + 4 0 = C24H20N4,HC1 + 3HC1 + 4HE,0.The hydro-gen chloride liberated in conbact with the dry cellulose converts iti n t o hydrocellulose and weakens the fibre. The remedy lies in addingacetates, o r other organic Palts of the alkalis o r alkaline earths, t 324 ABSTRACTS OF CHEM[CAL PAPERS.the mixture for producing the black. Roechlin has stated that thepresence of acetates prevents the formation of the black, but theaiithor finds that this is not the case wheu the quantity of acetateadded contains less than one equivalent of base for each equivalent OEacid present in the form of aniline salt. Half an equivalent givescomparatively little protection, Gut the maximum benefit is obtainedwith a quantity of acetate equivalent to three-fourths of the anilinesalt present, a result which supports Nietzki's view, according towhich three-fourths of the acid in the aniline salt is liberated in theprocess of oxidation.Thiophenylcarbamides.By S. PASCHEOWEZKY (Ber., 24, 3492).-The author has received a private communication from Bernthsen,in which he points out that the differences in the melting points1 ecorded for thiodiphenylcarbamide chloride and dithiotetraphenyl-carbamide by Paschkowezky (this vol., p. 164)) and by Frankel(Abstr., 1885, 1130), are due to the latter having neglected to correctthe values he obtained.C. H. B.A. R. L.Action of Potassium Cyanide on Halogen Derivatives ofKetones, By A. OBR~GIA (AnnaZen, 266,324-358) .--The potassiumderivative of cyanacetophenone is formed, with evolution of hydrogencyanide, when bromacetophenone (1 mol.) is treated with potassiumcyanide (2 mols.) in dilute alcoholic solution ; after evaporating thealcohol and taking up the residue with water, the filtered solution isacidified, and the precipitated cyanacetophenone recrystallived fromboiling water.The yield of pure cpnacetophenone (m. p. 8O-8lY)is 64 per rent. of the theoretical; its aqueous solution has a.n acidreaction. The sodium derivative crystallises i n small, nacreous plates,is readily soluble in alcohol, and is only slowly decomposed by carbonkanhydride ; the ammonium derivative is unstable ; on treating a solu-tion of the sodium derivative with metaliic salts, the correspondingmetallic derivatives are precipitated. The hydrazone separates fromalcohol in almost colourless crystals, melts at 134-135" with previoussoftening, and is very readily soluble in ether and chloroform, but onlymoderately easily in cold alcohol, a d insoluble in cold water.A compound of the composition C9H,N20 is formed when an alkalinefiolution of cyanacetophenone is treated with hydroxylamine at theordinary temperature ; it crystallisev in colourless, lustrous, rectangularplates or short needles, melts a t 110-112", and is readily solnble inchloroform, alcohol, benzene, ether, and acetone, but almost insolublein light petroleum, cold alkalis, and conceiitrated ammonia ; it has aneutral reaction, and crystallises uncbanged from hot soda.'I'hehydrochloride melts at 98-100" ; the sulphate decomposes at 169-173",and is resolved into its components by cold water. When boiled withdilute acids, it yields ~cyanacetopher~one and phenylisoxazolone ; thelast-named compound is also formed when an alcoholic solution ofcyanacetophenone atid hydroxylamine hydrochloride is kept for R longtime. It will be seen that the conipound just described does not showall the properties of a true oxime ;*its coktitution is probably repre-sented by the formula >NH.?H,-COCPh : OHQ AN10 CHEMISTRY.32 5Benzoytacetantide, CH, BzCOmRH2, is ohtained when cyanaceto-phenone is treated with concentrated sulphuric acid at the ordinarytemperature, and, after keeping for about 48 hours, the product pre-cipitated with ice ; it crptallises from hot water in lustrous needlesor prisms, melts a t 111-113", and is almost insoluble i n lightpetroleum, and only moderately easily soluble in benzene and ether,but readily in alcohol, chloroform, acetone, alkalis, and ammonia ; ithas a neutral reaction, and its solutions give an intense violet colora-tion with ferric chloride.It is decomposed by boiling alkalis withformation of ammonia, acetic acid, and benxoic acid, and when heatrdalone or with water, it yields carbonic anhydride and acetophcnone,The hydrazone crystallises from dilute alcohol i n yellowish neediep,melts a t 128-130", and is soluble in ether. When benzoylacetamidais treated with hgdroxylamine hydrochloride in alcoholic or ammonia-cal solution, it is converted in phenylisoxazolone.The crystalline compound (m.p. 179-180") obtained by treatingchloracctone with potassium cyanide in aqueous solution (compareHantzsch, Abstr., 1890, lU94) has the molecular formula C,H,,NaOz,as was proved by molecular weight determinations, by Raonlt'smethod, in glacial acetic acid solution, and its constitution is prob-ably that of a p-)neth~lhydroxy-y-cyanacetobutyronitrile,CN GHAcm CMe (OH) .CHX.CN.C Me (0 H) . $: H,Hy &ox y h y drocy ano nze8itenelacton e, C N-CGCMe- o- , thed r i l e of hydroxylhydroisodehydracetic acid, is obtained when the crystal-line compound (m. p. 179-180') just mentioned is dissolved in verxdilute sulphurio acid ; it crystallises from hot water in colourless,lustrous needles, melts at 65", and is very readily soluble in alcohol,chloroform, benzene, acetone, and boiling water, but only moderatelyeasily in ,ether, and almost insoluble in light petroleum.Its aqueoufisolution gives, with ferric chloride, first a brownish, and then tt violet,coloration ; the freshly prepared solution in dilute alcohol has only avery feebly acid reactiou, hut after keeping for some t,ime the acidityincreases very considerably. It dissolves unchanged in cold, con-centrated acids, and also i n alkalis, ammonia, and alkali carbonates.The bromo-derivative, CBH6BrNO9, can be prepared by treating thelactone or the crystalline compound (m. p. 179-180") with brominein alcoholic solution ; it crptallises from dilute alcohol in slender,lustrous needles, melts at 98-100", and is readily soluble in benzene,chloroform, ether, alcohol, and boiling water ; its aqueous solutionhas an acid reaction, and only gives a slight violet coloration withferric chloride after having been boiled.6-Hy drox!/-y-acetoisoual~r~c acid, C HzAcm CMe( 0 H) GHz- C 0 0 H, isformed, with liberation of carbonic anhydride, when the lactone isboiled with barium hydroxide until the evnlution of ammonia is a t auend ; it irc a thick, yellow, odourless liquid, readily soluble in water,alcohol, and ether.The phenylhydrazone is an oil; the paratolyl-hydrazone is a yellowish, very unstable substance, and decomposes a t81-85". The barium salt is a yellowish, amorphous powder, readilysolubh in water and alcohol; it seems to have the compositio32 6 ABSTRACTS OF CIEMICAL PAPERS.(C7Hl,04),Ba + C7H,(,0,Ba.The silver salt, 2C,H,,O,Ag + Ci.H,,,04Ao, + H20, is very unstable, and very readily soluble in cold water. Thecopper s d t is a green, vitreous, hygroscopic s i i bstance.A compound of the composition C,H,,N,O, + SH,O is obt,ainedwhen hydroxjhydroc-jxmomesitenelactone is treated with hydroxyl-ainine in very dilute alkaline solution, and the precipitate recqst a'-lised from boiling water, from which it separates in colourless, lustrousneedles; it slowly loses the whole of its water over sulphuric acid,the anhydrous crystals decomposing a t 184-185". I t is very spar-ingly soluble in ether, acetone, light petroleum, and cold water, butmore readily in alcohol, chloroform, benzene, and boiling water ; it3aqueous solution has a pronounced acid reaction, and gives, withferric chloride, a brownish-violet coloration.This compound is prob-nbly the lactam of P-methjlhydroxy-yacetoxitne-A-isonitrosoamido-valeric acid. and its constitution may be rewesented bv the formula YF. S. K.Action of Amrr onia and Aniline on Halogen-substitutedNitrobenzoic Acids. By A. G ROHMBNN (Bey., 24, 3808-3815).-I n a previous communication (Abstr.: 1891,305), the author has skownt h a t the halogen in, the etliyl salt, amide, and anilide of 4 : 3-bromo-nitrobenzoic acid may be readily replaced by the amido- and anilido-groups ; in the present paper h e describes similar experiments madewith 2 : 5-bromonitrobenzoic acid.2 : 5- Brornonitrobenzoic chloride, NO2*C6H,Br.COCI, is readily ob-,tained by the action of phosphorus pentnchloride on the acid, andcrystallises from alcohol in greSish crystals melting at 63".l'hca x i d e , No2*C6H3Br*CONH2, is prepared from the chloride by warm-ing wit8h ammonium carbonate on the water-bath, and crystallisesfrom alcohol in white, lustrous needles which melt at 197-198 ;the anilide, Ko2*c6kT3Br*cO*NH Ph, obtained by gently warming tlwchloride with aniline, forms yellowish- white, acicular crystals, andmalts a t 166"; both compounds are soluble in alcohol and acetonc,and insoluble in water and benzene.When ethyl 2 : 5-bromonitrobeneoate is heated i n a sealed tube withalcoholic ammonia, i t is converted into ethyl 'L : 5-nniidon.;trobenroate,NO,*C,H,(NH,)*COO~t, which crjstallises from alcohol in pale-yellow needles melting at 148".If aniline be substituted for ammonia,the corresponding ethyl 2 : 5-anilidoi~itrobenzoate is obtained ; it sepa-rates from alcohol in small, yellow plates, and melts a t 118". Thcamide and anilidc above described also readily react with ammoniaand anilire respectively, forming the cori*esponding amido- a danilido-compounds. 2 : 5-Amidonit.1.obenztlmide,NO,*C,H,(NH,)*CONH,,crystallises in orange-yellow needles, and melts at 230" ; 2 : 5-andido-nitro benzanilide, N 0,*C6H3( N H P h) *CO.NH P h, separates from alcoholin tuf'ts of very slender, yellow needles, resembling silk fibres, andmelts a t 159".ft : 4-Chlol.onitrobeizzo;c chloi-ide is prepared from the acid in thORGANIC UHENISTRT, 32 7usnal manner, and is a yellowish-brown sabstance melting a t 115".I t is converted by ammonium carbonate and aniline respectively intothe arnide and anilide; the former crystallises from alcohol in greyscales, and melts at 172", whilst the latter is a white, amorphons snb-stance melting a t 168".In these compounds, unlike the 4 : 3- an(12 : 5-compounds, the halogen cannot be displaced by further heatingwith ammonia or aniline. The same is also true of 4 : 2-chEoroizitro-benzoic ucid, which was prepared by displacing the amido-group in3 : 2-amidonitrotoluene by chlorine and oxidising the chloronitro-toluene thus obtained.From these resuits, it appears that when the nitro- and carboxyl-groups are simultaneously in the ortho- and para-position relatively tothe halogen, the latter.may be readily displaced, but that this isno longer possible when one of these groups takes up the metit-position.To his preyious commniiication on 4 : 5-bromonitrobenzoic acid(Zoc. cit.), the author adds that this acid is converted by alcoholicrimmonia a t 170" into fhe 4 : 3-arnidonih*obenzoic acid described byGriess (Ber., 5, 855) and Salkowski (Annalen, 173, 53).H. G. C.Oximes of some Ketonic Acids. By F. GARELLI (Gazzefta, 21,ii, 173-188).-1n a previous memoir (Abstr., 1891, 711), the authoryeported his inability to prepare the oximido-compounds of dioxy-nietJh~lenephenylglyox~lic acid, apionylglyoxylic acid, and para-methoxpglyoxylic acid ; he has, however, since succeeded in preparingthem, and finds them to be very unstable, readily losing the elementsof water and carbonic anhydride, and yielding the correspondinkiiitriles.Methyl diozyrnet7~ylenephenylglyox~late, CH2<O>C6H,-CO*COOMe, 0is prepared by saturating a solution of dioxymethylenephenylgly-ovylic acid in methyl alcohol with dry hydrogen chloride.Thoalcohol is distilled off and water added ; the salt sephrates as an oilwhich soon solidifies, and is crystallised from dilute alcohol. Smallcolourless needles, melting at 66", soluble in alcohol an4 ether, and:tlmost insoluble in water, are t h u s obtained. The alcoholic solutiono f this ethereal salt is treated with a slight excess of hydroxylaminehydrochloride and heated in a reflux apparatus on the water-bathfor t w o hours.The alcohol is distilled off, the residnal oil dis-solved in dilute potash, filtered from a small quantity of piperonyl-nitrile, and the solution saturated with cwbonic anhydride ; methyldioxynzethylenephemjloximidoacetate is. then 'thrown down, and OTIrepre~ipitation from its solution in benzene, by the addit.ion of lightpetroleum, is obtained in tufts of small crystals melting withoutdecomposition :it 102". This substance is soluble in water andnlcohol, and on hydrolysis with dilute potash a t a temperature belowGOo, yields diozymethylenephenyloxinzidoacetic acidas a whiteish mass ; on precipitation from its acetic solution by ligh328 ABSTRACTS OF CHE-\IICAL PAPERS.petroleum, it may be obtained in minute rrystals, soluble in sodiumcarbonate solution, alcohol, ether, benzene, and water.It melts wit t:decomposition a t 150-151", and its aqueous solution gives whiteprecipitates with lead and mercury salts and a green precipitate withcopper acetate in concentrated solutions. This acid may also be pre-pared by heating a dilute solution of dioxymethylenephenylglyoxylicacid at 60-70" with the calculated quantity of hydroxylaminehydrochloride. It, is readily converted into piperonylonitrile by pass-ing a, current of dry hydrogen chloride into its ethereal solution ; theconversion also proceeds spontaneously in dilute aqueous solutions,and is hastened by the presence of acids or of hydroxylamine hydro-chloride. The acelyl derivative is obtained on heating it with aslight excess of acetic cliloride ; on cooling, colourless, rectangularprisms separate, melting with decomposition at 139-140".Whenhydrolysed at 0" with dilute potash and extracted with ether, theoxime is regenerated; at. higher temperatures, the nitrile is theprincipal product of the action.Compounds analogoils to those of dioxymethylenephenylglyoxylicacid may be prepared from apionylglyoxylic acid by the same0 met hod s . Met h y Z apiony Zg I! y ox y late, c H,< > C6H ( OMe) 2* C 0 C 0 0 Me,crys t.allises from dilute alcohol in needles melting at 62" ; it is very sol-uble in alcohol and ether, sparingly in benzene, and insoluble in water.minute, colourless crystals melting at 129" without decomposition ;on hydrolysis, it yields opionyloximidoacetik acid in splendid, whitescales, very soluble in alcohol, spariiiglp in boiling water, less so inbenzene, and insoluble in ether. I t s aqueous solution gives no pre-cipitate with salts of lead, copper, or mercury.No acetyl derivativecould be prepared.Yuramet huxyp hevr ytoxirnidoacet ic acid, 0 Me* CsH,*C (KO H ) fi*C 0 0 H,is prepared from pa~*amethoxyphei~ylglyoxylic acid in the manneritidicated above, and separates from ethyl acetate in large, colourlesscrystals, very soluble in water, alcohol, and ether; it melts a t145-146" with couiplete decomposition. T tie a-oximido-acid cannotbe prepared by carrying out the reaction a t 0". On Iieat,ing withacetic anhydride or acetic chloride, a small quantity of an acetylderivative is obtained.It me1 ts with complete decomposition a t118", is decomposed with formation of anisonitrile by cold solutionsof the alkali carbonates, and on hydrolysis a t U", yields only theoriginal p-oximido-acid.Giarnician aud Silber (Abstr., 1890, 965) found that isosafroleyielded piperonylic acid and dioxymethyleriephenylgljoxylic acid onwxidation with perrnanganate, the author finds that a small quantityof dioxymethylenephenylglycollic acid is also produced (30 grams ofisosafrole yield 0.5 gram of the acid). This acid is separated bymeans of its solubility in water, and melts at l56", not a t 152-153',as found by Lorenz (Abstr., 1881, 727).The ketonic acids obtained from safrole, anetho'il, metbyleugenol,and apiole, when dissolved in benzene and treated with thiophen iORQANIC CHEMISTRY.329concentrated sulphuric acid solution, impart an intense red colora-tion to the thiophen, the benzene solution remaJning colourless ; ondilution, the solution becomes successively violet, and dirty green.The solutions of these acids in phenol, when heated with conccntratedsulphuric acid on the water-bath, soon t n r n blue ; gas is then abund-antly evolved and the solution becomes r e d ; on pouring the productinto water, the colouring matter separates as a floccnlent precipitateinsoluble in water, but readily soluble in soda, arid in solutions of thealkali carbonates. A preen colouring matter is produced on heatingthe acids with dimethylaniline and zinc chloride.Derivatives of Mesitylene.By E. FEITH (Ber., 24, 3542-3545 ; compare Claus, Abstr., 1890, 979, and Dittrich and Mejer,Abstr., 1891, 12d4).-The air-dried barium salt of mesi tylglyoxylicwid contains 3 mols. B20, of which it loses two over sulphuric acid.The zinc salt, with 4H20, crystalliscs in lustrous plates and loses3 mols. H,O over sulphuric acid. The methyl salt, C12Hlr03, hoils a tabout 170" iinder a pressure of 1GO mm. When mesitylglyoxylic acidis heated, it is decomposed into trimethylbenzaldehyde and trimethyl-benzoic acid, the methyl salt of which crystallises in colourless platesmelting at 139-140".~rimeth?/Zben~atdehyde, C6HzMe3*CH0, is an oil, boils at 235--240",and gradually oxidises on exposure to the air ; its oxime,C6H&f e,*CH:NOH,crystallises in small needles, melts at 127", and dissolves freely inalcohol, ether, and alkalis ; its hydrazone, C,H,Me,*CH:N,HPh,separates from dilute alcohol in colourless crystals, and is very un-stable.MesityZgZyco7Zic; acid, C6H,Me3*CH(OH)*COOH, prepared by re-ducing mesitylglyoxylic acid with sodium amalgam in alkaline solu-tion, crystallises from water in large, well-defined, transparent plates,melts a t 147", and is readily soluble i n alcohol and ether, but onlysparingly in cold water.The silver salt, CI,HI3O3Ag, is amorphous.The nzethyt salt, C,2H1603, prepared from the silver salt, separatesfrom light petroleum in colourless, - nodular crystals, and meltsW. J. P.when the acid is heated a t 120-130" f o r two days with anhydrouschloral ; it crystallises from light petroleum in well-defined plates,nielts a t 125", and is readily soluble in benzene, chloroform, andether, but more sparingly in alcohol.By F.ALDKIxGEN (Bey., 24,3 i.jg-3466).-'l'ieniann has shown (Abstr., 1886, 880) that tbio-cournarin is formed when coumarin i s fused with phosphorus penha-sulphide. The object of the present work was to examine thebehaviour of certain homologues of coumarin and of some otherF. S. K.Thiocournarin and its Analogues.6- lactones.CH'CMecr-JIet7c ylthioeoumarin, CGHH,<oibs is prepared by heatin330 ABSTRACTS OF CREYICAL PAPERS.a-methyl-coumarin (m. p. 90") with phosphorus pentasulphide, boilingthe melt with benzene, crystallising from absolute alcohol, and washin<the crystals with carbon bisulphide ; i t forms yellow needles, melt3a t 12i?", sublimes without decompositlion, and is insoluble in wateiaand light petroleum, b u t xadily soluble i n alcohol, ether, antibenzene ; it yields m-met,hylcoumarin on boiling with alcoholic pot,ash.CH:FMea-lkIethylcoumaroxime, c~H4<<0--c:.0H7 is formed when the a-methylthiocoumarin is boiled with hgdroxylamine i n alcoholic solo-tion ; i t crystallises from water or dilute alcoliol in coluurless needlw,and melts at 166".Ferric chloride does not. give a coloration as withcoumaroxime (see Tiemann, Zoc. cit.), atid t h e same is true of thehomologous compounds to be described ; they are also without acttionon Fehling's solution.It dissolves in alkalis amd acids, is stabletowards the former, but yields a-methylooumarin when boiled withconcentrated hydrochloric acid ; the acetyl derivutive,CH:? MeC6H'<O-N~OAc,obtained by dissolving t h e osime in an excess of warm acetic chloride,is produced by melts at 56". The hydrazone,CH:yMeC"H'<O-C:N,HPh,boiling a-methylthiocoumarin with pbenylhydrazine in alcoholicsolucion for about a week; i t crystallises from alcohol i n yellowi,eedles, melts at llG", is irisoluble in water, and dissolves in con-centrated salphuric acid with an inteiise green colour.The following derivatives of a-ethylcoumarin (in. p. 71") wereprepared in a similar manner t o the methyl compounds :-u-Eth!/l-ihiocounlal.i?z forms small, y.ellowish-red plates, and melts at 93-94O ;a-ethyZcoumai.oxi~ze crystallises i n long, white needles, melts a t 157",and yields an acetyl dericatise melting a t 61" ; whilst a-ethy1coumai.o-phenylhydi*azone melts a t 115".Derivatives of a- Isopropylcoumarin (m.p. 54") .-a-TsopmpyZt!iio-eoumarirc forms reddish-yellow needles, arid melts at 81" ; a-isopiwpyl-ihiocoz~ircaroxime crjstallises in white prisms, melts at 171", and yieldsan acety 1 derivative mrlting at 85" ; whilst a-isop~o~ylcoz~nzarop~~en~l-hydraxclne melts at 7 12".Derivatives of Metlrylumbellifei*one (m. p. 7 14").-Urnbelliferoneis not readily converted into the thio-derivative by fusion withphosphorus pentasnlphide, whereas the niethjl derivative exhibitsthe same behaviour as coumarin. , 1Methylthioumbell~fe~one, OMe*CGHZ< CH:FH, forms yellow needles,4 0-cs 3melts at 114", and dissolves in boiling alkalis with decomposition.N e t h yluiii brlliferonozin? e crys t alli ses from water i n long, feltedneedies, melts at 138", and gives a brownish-red colour with ferricc h 1 o r i d e ..Me f h y Zu 11 I be 11 lye r o ti ep he 11 y 1 h y d r a x I ) ne i s obtained by b o i 1 i 11 gjor a fortnight a mixture of methyl thioumbelliferone with pbenjl-hjdrazine in molecnlar proportion, dissolved in alcohol ; it cryst alliseORGANIC OEE3IZSTRY. 331fiom alcohol in thick, yellow needles, melts at 115", and dissolves i ncoucent rated sulphuric with a bluish-green colour.Action of Ammonia and Aniline on Negatively-substitutedHalogen-benzenesulphonic Acids.By P. FISCIIER ( B e y . , 24,3785-3808).--lt was found t h a t in the case of the two chloronitro-benzenesulphonic acids NOz*C6B3C1*S0,H [Cl : NO, : SO,€€ = 1 : 2 : 4and 1 : 4 : 2 respectively], the two bromosulphobenzoic acidsCOOHmC6H,Br*SOJH [Br: COOH : S03H = 1 : 2 : 4 and 1 : 4 : 2respectively], and bromobenzenedisul phonic acid, C,H,Br( SO,H),[ H r : (SO,H), = 1 : 2 : 41, the action of ammonia or aniline is tod i s p l a ~ e the halogen by the amido- or anilido-group. I n all of theseacids a para- and an ortho-position, relatively to t h e halogen atom,aye occnpied by negative groups.2ll~tnnitro~aramidobenzenesul~~~onic acid, NHZ.C6H3(NOL)*SO3H[I 1 : 2 : 41, is obtained as the ammonium salt by heating metanitropam-c*hloroberizenesulphonic acid with alcoholic ammonia at 120-140".The barivnz salt, (C6H,N,SO,),Ba + 2$H20, forms yellow crystals ;the acid itself forms an amorphous, yellow precipitate.When heatedwith concerltrated hydrochloric acid at 150", t h e sulFhonic groiip isremoved, and orthonitraniline is formed ; this proves that the NO,group and the chlorine atom in the original nitrochlorosulphonic acidoc.cupy the ortho-positions relatively to each other. Paramidometa-1~1frol,enzenesiiZp~onamide, NII,.C,H3(N0,).SOz.WHz [ 1 : 2 : 41, is ob-t ;tined by heating paraclilorometanitrobenzen esulplionamide mi t tialcoholic ammonia at 120". It crystallises from alcohol or water iudeep yellow needles or lustrous, golden plates, melts at 2Oti-207",and is such a feeble base that i t forms no salts with acids.Metatiitro-orthamidobenzenesulph~~~ic acid [NH, : NO, : SO,R =1 : 4 : 21 was obtained in the same way a s the isomeric acid.Thebarium salt, ( C6H,N,S05),Ba + H,O, forms yellow crjstals. The acidit,elE crystallises from water in sinall, yellow crystals, and yield3)mraphenylenediaminesulphonic acid, C,H,( NH2),.SOJH, on reductionby CIaisen's method. Its sulyhonnmide forms yellow needles or platesmelting a t 210".With parachlorometanitrobenzenesul phonic acid, aniline jieldsa11 aniline salt, NO2.CbH3CI*SO3.NH3Ph [= 2 : 1 : 43, in lustrous,white crj-stals. Tklis, when heated with excess of aniline, yields theanil iite salt of nzetaiaitro~aranilidobenz~nesul~honic acid,N0,*C6H3(NHPh)*S03*NH3Ph [= 2 : 1 : 41,which forms large groups of yellowish- brown needles, and dissolves inalcohol, acetic acid, acetone, and hot water, but not in ether or benzene.The bariiinz salt, (C,,HSN,SO,),Ra + H 2 9 , forms lustrous, dark golden])kites. The acid forms orange-coloured crystals, decomposing at 200"without melting, and dissolves readily in water, alcohol, acetic acid, andacetone, but not in benzene and ether.The alkali salts, C,,H,N,SO,Na, + HzO, kc.. are 01-ange-yellow, but at 110" lose wbter and becomcbrick-red ; tlip anhydrous sHlt$, however, take up water from the air,becoming again orange-yellow.A. R. L.The ammonium salt,C12HgX\TZ$Oa*NH* + +HAO332 ABSTRACTS OF OHEMIOAL PAPERS.forms lustrous, yellow plates.By the action of phosphorus penta-chloride on the acid, the sulphochloride is obtained ; it crystallises fromether in yellowish-brown needles, aiid with ammonium carbonate yieldsthe sulphonamide, RS lustrous, red crystals melting a t 162". The yulph-nnilide is best obtained by the action of aniline on the chloronitro-benzenesul phonic chloride ; it forms long, orange-yellow needles, meltsat 157", and dissolves readily in alcohol, acetone, and acetic acid.Paranilidometaniidobenzenes2dlphonic acid, NHPh*C,H,(NH,)-SO,H[=1 : 2 : 41, is prepared by reducing the barium salt of the corre-sponding anilidonitro-acid by Claisen's method ; it forms a crystallineprecipitate, which darkens in the air and gives a violet-red colourwith ferric chloride.The barium salt, (C12H,,N2S0,)2Ba + 2Hz0,forms tiny, brownish needles. The sulphanilide, prepared by re-ducing the corresponding nitrosnlphanilide with alcoholic ammoniumsulphide, forms colourless, lustrous needles melting at 157", and givinga, deep violet colour with concentrated snlphuric acid. The hydro-chloride forms white needles melting at 181-182" with decomposi-tion. Metanitroparanilidobenzenesulphonic acid yields orthodinitro-d iphenylamine when heated at 130-1 40" with concentrated hydro-chloric acid. By adding potassium nitrite to an acetic acid solutiono€ this base, orfhoizitrodiplzenylniti.osamine, N02*CsH4.NPh*N0, is ob-tained. It forms nearly colourless plates melting at 99-100"; i tdoes not give Liebeymann's nitrosamine reaction with phenol andsulphnric acid, but yields a deep violet, and not a deep blue, colour.Ort hochlorom et ani tro ben zenes ul ph onic acid yields.with aniline, theaiziline salt, which forms long, lustrous, white needles, decomposingabove 200" without melting. When heated with aniline, this yieldsmrtanitro-ol.tha?zilid~ benzsnesulphonic acid, as the aniline salt, in large,brown needles with zt violet lustre ; i t dissolves in water, alcohol, andacetone, but not in cther or benzene. The barium salt,forms lustrous, orange needles. The acid itself crystallises in small,lustrous, olive-green plates. The potassium salt forms anhydrous,orange needles, and with phosphorus pent>ach loride yields the sulph-onic chloride, as greenish-yellow needles melting a t 102-104" andreadily soluble in ether, benzene, and chloroform. With ammoniumcarbonate, it yields the szdphonamide, which separates from alcoholi n reddish-yellow crystals melting a t 173", and insoluble in water.The sulplinnilide was obtained from aniline and the chloi*onitrosulph-onic chloride ; it crystallises from alcohol in lustrous, greenish-yellow11 eed 1 es melting a t 164".Orth anilidometamido benzcnesulp/ionic acid,NHPh*C6H3(NH2)*S03H [= 1 : 4 : 21, is obtained as the barium salt,(CI,H,,N2SOa)2Ba + HyO (lustrous, silver-grey plates), by reducingthe barium salt of the corresponding nitro-acid by Claisen's method.I t yields highly-coloured oxidation products ; for example, with ferricchloride, it gives a red colour passing into violet.The acid formsdark-coloured plates. The sulphnnilide, obtained by reducing t h ecorresponding nitrosulphanilide with alcoholic ammonium sulphide at1.10-130", forms lustrous pIates melting a t 171", and gives a violetcolour with strong sulphuric acid. I t s hydrochloride blackens a t 200°ORGAN I0 0 H EBIISTRY. 333rind melts with decomposition a t 215", niid gives an olive-green colourwith ferric chloride.P a r a m idomet asiclphobenzoic acid,NH2*C6H,(S03H)*COOH [l : 2 : 41,is obtained as the diammonium salt by heating the correspondinqhromosulphobenzoic acid with alcoholic ammonia at 160- -180". Tliebnrizbm salt, C,H,NSO,Ba + 2H20, forms large, colourless cr.ysta1.1,the pofassium salt anhydrous, transparent needles. The acid itselfcrystallises from water in slender needles.Parabromometasulplio-berizoic acid yields with aniline the aniline salt, which crystallisesfrom wat,er in long, lustrous, white needles, decomposing above 200"without melting, and when heated with aniline yields the aniline saltof paranil icEumetasulph,,henzoic acid, N H Ph.ChH3 (S 0,H) * C 0 O*NLT,Ph.The barium salt, C,JHgNSO,Ba + 3$H20, with sulphuric acid, yieldsthe free acid as small, lustrous, nearly colourless plates,Orthohromoinetasulphobcnzoic acid, S03H-C6H3Hr*COOH [ A : 1 : 21,was prepared by treating orthobromobenzoic acid (obtained by oxidis-ing orthobromotoluene) with fuming sulphuric acid. When heatedwith xlcoLlo1ic ammonia at 160-180", it yieltls the amrrionium mlt ofthe amido-acid.The barium salt, C,H,NSO,Ba + 2$H20, formscolourlejs crystals. With aniline, the bromo-acid yieltls an anilinesalt, and this, when heated with aniline in glycerol solution, yieldsthe aniline sctlt of orthadidometasulphoberlzoic acid,NHPh.CsHf,(S03H)*COO*NH3Ph [I : 4 : 21,in brownish plates.lustrous, yellowish plates.needle3 which decompose w itliout melting.The hnriunz suh, C13H,NS0,Ba + 5H20, forcrisThe acid crystallises irom water in fineAmidobenzenemelndistilphorric avid (disullphanilic acid),NH2*CsH.j(SO,H)2 [l : 2 : 41,was obtained as the neutid ammonium salt by heating the corre-sponding bromodisnlphonic acid with alcoholic ammonia a t 160-180".The amidodiszcl~honamide, NH2*C,H,(S0,*NH2)2 [I : 2 : 41, was ob-tained fkom ammonia and the bromodisulphonxmide.It crystallisesfrom water in lustrous, white plates melting at 235". The bromodi-sulphonic acid yields with aniline the diaitiline salt, which formstransparent, colourless plates soluble in water and glycerol, but notin alcohol. When heated with aniline in glycerol solution, it yieldsanilidobenzeneme fadisulyhonic acid ~ ~ ~ ~ p h ~ ~ ~ ~ ~ a r n i n e ~ r ~ h ~ p acid), which is ver.y soluble i n water, and could not be obtained crys-talline. The barium s d t , C,,HgNS,06Ba + 3H20, is a yellowish,amorphous substaiice. The disulphunilide is best obtained by heatiLgthe corresponding bromobenxenedianlphonic chloride with aniline. Itforms large, yellowish crystals melting at 821-222", and dissolvesreadily in alcohol, less readily in acetic acid, spariiigly in glycerol,and not at all in water.c. 1'. B.Acetoximes. By H. WEGE (Bey., 24, 3537--3540).-The acetyland the isobutyl derivatives of acetoxime were prepared from theoxirue by Hinsberg's method (Abstr., 1891, 49) ; they are both oils.VOT,. LXIL. 2 334 AUSTRAOTS OF OHEMIOAL PAPERS.Acetoxheplien y Isulphoize, CMe2:N* 0 S 0,P h, is easily obtained byshaking a concentrated aqueous solution of acetoxime with soda andphenylsulphonic chloride ; it crystallises from a mixture of ether andlight petroleum in long, colourless needles, me1 ts a t 52.5". and explodesa t 128", with formation of phenylsulphonic acid, ammonia, and smallquantities of nitrogen.Acetosimppuru toly lsulphone, C Me,:N.O S O,-C,H,Me, prepared in 1 i kemanner, crjstalliees from dilute alcohol in colourless scales, melts a t89", and decomposes a t 135" with a slight explosion.The correspond-i n g Pnuphth yl derivative, Cy3HYJNO3S, crystallises from alcohol incolourless or reddish plates melting at 87".When camphoroxime is shaken with soda and phenylsulphonicchloride, it seems to be converted into campholenonitrile. Benzo-phenoneoxime, under the same conditions, is converted into benz-anilide; a similar intramolecular change also takes place wheii thechlorides of paratoluenesulphonic acid and naphthalenesulphonic acidare employed in the place of phenylsulphonic chloride.F. S. K.Action of Sulphonic Chlorides on Orthamidobenzamide.By E. FRANKE (J. pr. Chma. [2], 44,417-432 ; compare Abstr., 1887,1043, 1044 ; 1890, 1289) .---Renzenesul phoneorthamidobenzamide(Abstr., 1890, 1289) is insoluble in cold water and light petroleum,but dissolves in alcohol ; it does not yield an anhydride when heatedwith water.Ethyl bewenesulphoneorthamidobenzoate, COOEt.C6H4*NH*SO2Ph,obtained by the action of ethyl orthxmidobenzoate (Abstr., 1885, 665)on beuzenesulphonic chloride, crystallises from aqiieous alcohol inwhite, quadratic prisms, melts a t 92.5", and dissolves easily in absolutealcohol, but not in water.When heated with aqueous ammonia a t140" for seven hours, or with alcoholic ammonia at 160" for 12 hours, itis converted into benzenesulphoneorthamidobenzamide ; with alcoholicmetbylamine at 140°, it yields benzenesulphoneorthamidobenzomethyl-amide (see below).The potassium and siker compounds of benzenesulphoneorthamido-benzamide are described, and the precipitates which the base givc swith several of the salts of the heavy metals are detailed ; the metalsdisplace 1 atom of hydrogen from a molecule of the amide.Theauthor retracts his former statements as to the obtaining of st hydro-chlol ide and methyl derivative melting at 116" from benzenesulphone-orthamidobenzarnide (Abstr., 1890, 1289).The author did not succeed a second time in obtaining an anhydrideby acting on beiizenesulphoneorthainidobenzamide with phosphoricanhydride, or by dissolving it in dilute sodium hydroxide solution andprecipitating by hydrochloric acid, or by heating it in alcohol a t210" (Abstr., 1890, 1289).Anhydrobenzenesulphoneodhamidobenz-is, however, readily obtained by heating amixture of benzenesulphoneorthamidobenzamide and phosphoric chlor-ide in molecular proportion, first at 60-?O", and finally at 175" ; themass is afterwards extracted with benzene, the solution precipitatedco*r;irr.N : SOPh' am&, C,H,OHGANIC OHEMISTRY. 335with water, and the compound recrystallised from dilute alcohol. Iticrystallises in pale yellow needles, melts a t 145", is very soluble it\alcohol and hot benzene, less FO in chloroform, ether, and water ; i talso dissolves in alkalis, and is precipitated unchanged by acids.When heated with concentrated hydrochloric acid, i t is decomposed,Its sodirm, silver, and potassium compounds were prepared.Benzenesub? honeorthnmido benzonz et h y lumid e,NHMe*CO.C,H'r*NH.SOzPh,is obtained as described above, or by heating anhydrobenzenesnlphone-orthamidobenzamide with potmsium hydroxide arid methyl iodide inalcohol iu a sealed tube at 120", or by bringing together orthamido-benzomethylamide and benzenesulphonic chloride i n molecular pro-portion.It crjstallises from aqueous alcohol in white needles,melts a t 114", and is insoluble in cold water and light petroleum, buteasily soluble in hot benzene, ether, and alcohol.NHz*C0.C6H4*NMe.S0zPh,is prepared by heating molecular proportions of orthomethamidobenz-amide (Ahstr., 1887,1044) and benzenesulphonic chloride together 011the water-bath; the new compound is extracted from the productby very dilnte alcohol, and recrystallised from hot benzene.Itforms beautiful, rhombic lamin=, melts at 154Q (uncorr.), and dissolvesreadilyin warm alcohol and in warm, dilute allrdis ; it is precipitatedunchanged from the alkaline solutions on the addition of an acid.Benzenesulphoneorthomet hamidobenzamide,Benzenesulphoneort hamido beiazop hen y lamid e,NH Ph*CO*C6H4*NH*S0,Ph,prepared from benzenesulphonic chloride and orthamidobenzophenyl-amide, crystallises in needles which melt a t 144-144.5". Renzenesulph-oneorthamidobenzoylphen!/lliydrazine, N,H,Pli*CO.C,H,*NH*SOzPh, wasobtained by heating benzenesulphonic chloride and orthamidobenzoyl-phenylhydrazine together a t 130 -140" ; the dirty-white needleswhich crystallised from water melted a t 140-142", but the yield wasvery small, and further investigation is needed.Methylsu7phoneorthamidobenzamide, NH2G O*C6Hd*NH*S0,Me, is ob-tained by the action of methylsulphonic chloride (b. p.160-161')on orthamidobenzamide ; it crystallises from hot, dilute alcohol inalmost white, very slender prisms, which melt at 156-157"; ananhydro-derivative could not be prepared.When sulphuryl chloride and orthamidoberizamide react, dichlor-anthranilamide, NH2*CO*CsHzCl2~NH2, is produced ; this crystallisesin dirty-yellow needles, and melts at 175-176" ; on hydrolysis, ityields Dorsch's dichloranthranilic acid melting at 223-225" (Abstr.,1886, 360). Dorsch, however, gives the melting point of the amidecorresponding with his acid as 284".Displacement of Halogen Atoms in the Benzene Ring.ByM. SCHOPFF (Ber., 24, 3771-3784 ; compare Abst'r., 1891, 304).-The general result of this research may be expressed thus:-If inA. Go B.2 a 336 ABSTRACTS OF CHEMICAL PAPERS.the benzene r i n g in which the halogen atom is contained there arealso t w o negative groups, like or nnlike, in t,he ortho- and para-positions relatively to this atom, then other groups, such as .NH,.NHR, and *OH, can easily be substituted for the halogen; but iFonly one negative group is present, no such replacement occurs,exccpt when this one group is *NO,. The negative groups may be*NO2, *SO,H, *COOH, *CO.R, or *COH.l'a7.abrc,,lornetanitrobenzophenone, NO,*CEH,Br.COPh [Br : NO, : CO= 4 : 3 : 11, is obtained by heating benzene with parabromometa-nitrobenzoic chloride in the presence of aluminium chloride.It formswhite plates melting a t 112-113", and dissolves easily in benzentb,acetone, chloroform, ether, and acetic acid, less easily in light petr-oleum. When heated with alcoholic ammonia a t 130", it yieldsparamidom etnnitrobenzophenoiie, N H2*C6H3 (N O,)*c)O Ph, a s small,yellow needles melting at 135", and dissolving very readily in water.IVith alcoholic cthylaniine, it yields yarethy1rrmidonaetanitrobertz.r~-p'renone, NHEt.C,H,( NO,)*COPh, as yellow needles melting at99-loo", and with aniline, parnnilidometanitrobelLxophe?LoiLe,N PH h*C6H3 (N 0,) *C 0 P h ,as orange-coloured needles melting a t 157".NO2*C6H3Br*CO*C6HIBr [Br : NO, : CO = 4 : 3 : 1 and CO : Br = 1 : 41,is obtained by warming parabromometanitrobenzoic chloride andbromobenzene with aluminium chloride in carbon bisulphide. Itforms needles melting at llS", and has the same solnbility as themonobronio-compound. With alcoholic ammonia at 130", it yiel(1sya?.amidomefanitroparabromobenzoph~none, NH2* C6H,( NO,) *CO*CsHIBr,as a, yellow substance melting a t 171".The corresponding crnilido-derivative, NHPh*CBH,(No,)*CO*C6H~Br, forms yellow needles melt-ing at MU".Diparabrom ometanitrobeizzophe?lolLe,Dzparabromodimetanitrobenzi yhenone,CO(C,H,Bi*NOL)2 [Br : (NO,) : CO = 4 : 3 : 11,is obtained by treating either diparabromobenzophenone or dipara-bromoruetanitrobenzophenone with fuming nitric acid.It formsneedles melting a t 152-155'. With aniline, i t yields diyarardidodi-i,ietanzt?.obenzophenone, CO [ C6H3(NOz)-NH Ph],, melting at 219".Urthobl.omo~ietanitroben zoyhenone, N02-CsH ,Hr- COPh, melting at115", was prepared in a similar manner to the isomeric parabrumo-compound, and resembles the latter in its chemical behaviour ; wit 11aniline, it yields ortlLanilidometanitrobenzoy henniie in lemon-colouredneedles melting at 135O.Parab7.omonnzefariilrobenzaEdehyde, NO,*C,H,Br.CHO [Br : NO, : CO= 4 : 3 : 11 (the aldozime of which, N02.C,H3Rr*CH:NOH, foimsyellow needles melting at 145-146', and dissolves readily in alcohol,less readily in water), when boiled with aqueous soda, yields para-hydroxymetanitrobenz/rldehyde, OH.C6H3(NOz)*CH0, which crjstallisesfrom Mnter in yellowish-brown needles melting a t 139-140 5".Thehydyazune: 0 H*CoH,( XO2)*CH:N2HPh, crys tallises from alcohol i n sruallORQAX IC CH-EAIISTRT. 337dark-red needles meltin,q at 175-1i6°. The aldehyde is identical withthe substance obtained by nitrating parahydroxybenzaldehyde.When asymmetrical bromoxylene, C6H3Me,Br [Br : Me2 = 1 : 2 : 43,is boiled with aqueous potassium permanganate, it is oxidised t otasy/umetricnZ bromisophthnlic acid, C6H3Bi*( COOH),, but a little asym-metrical hydroxyisop h thalic acid, OH*C,&( COOH),, is also formed.To separate these, they are converted into their ethereal salts, ofwhich that of the hydroxy-acid may be removed by dissolving i t indilute aqueous soda, which does not dissolve the other salt.Asym-metrical ethyl broririsophthalate, C,H,Br(COOEt),, is thus obtainedpure ; it is a colouyless oil with an odour like that of rum,; it boils at520-325" under 365 mm. pressure, and, when treated with concen-trated hydrocliloric acid, yields usyrnmetrical bromi.yophtIzalic acid,C6H,13r(COOH)2 [Br : (COOH), = 1 : 2 : 41. This forms whitenoedles melting a t !283", and sublimirig without decomposition ; itdissolves readily i l l alcohol, sparingly in water. It is identical withthe acid obtained by oxidising a- and ,8-bromocymene with nitric acid.The ammorrivm saZt forms fine, colourless, asymmetric cr7stals(u : b : c = 1*50:30 : 1 : 0 9753 ; = 70") which decompose a t 100".The ba&m scllt is white ;.the copper and silver salts form respectivelylight-blue and white precipitates.The acid may also, although lessconveniently, be obtained tiy saponifying parabrcmonietacyanobenxoicucid, CN*C6H313r*COOH, with concentrated hydrochloric acid. Thisacid is obtained from parabi~oinon~etarnidobenzoic acid by the actionof sodiiitn nitrite on an aqueous solution in the presence of coppet-cyanide, It forms white needles melting a t 186", and sublimingwithout decomposition. It dissolves readily in hot water and al(.ohol ;the copper and lead salts foi-m respectively light-green and yellowish-brown precipitates. Asymmeti.ica1 bromisophtltalic acid yields thecorresponding bydroxy-acid with alkalis or alkaline carbonates, andwith ammonia the corresponding amido-acid.Parahi-om o m etusulp ho beizxcdd elL y d e,is obtained as the barium salt, (C,H,BrS04),Ba + 5H20, by heztingpqrabromobenzaldehyde with fuming sulphuric acid at 150".andsaturating with barium carbonate. It does not lose all its water untilheated to 220". When boiled with aqueous sodium carbonate, i tyieldfi the sodium salt of pai*ahydroxymetasuIphobenzaldehyde,So,Na'C6H3( ONa)*CHO. C. F. l3.Friedel-Crafts' Synthesis. By M. S c H i j P m (Ber., 24, 3i66-3770).-When halo'id derivatives of benzene are treated with aceticor benzoic chloride in the presence of a.luuiinium chloride, the acetylor benzoyl group takes the para-position relatively to the halogen,forming respectively parabromacetophenone, C6HI,Br*COMe (t,hchydrazone of which, C6H4Br.CMe:N?HPh, forms yellowish platesme1 ting at 126"), and parachlorobenzophenonp, C6H,Cl*COPh.Ifthe para-position is already occiipied, no i*eaction occurs, as in the caseof pnradibromo- and parndiiodo-benzene, and of 1 : 4-dibromo-naph t Lalene338 ABSTRACTS OF OHEMICAL PAPERS,With parabromobenzoic chloride and bromobenzene, the reactiontskes place much less easily, and besides diparabromobenzophenone( ilhe hydrazone of which, C ( CGH4Br)2:N2HPh, forms yellow platesuielting at 1 38"), some monobromobenzophenone is also formed.The homologues of the halogen benzenes react, although lesseasily than these, if the para-position to the halogen is still nn-substituted; in the opposite case, no reaction takes place, as, forexample, with parabromotoluene and unsymmetrical bromometa-xylene, C6H,BrMe2 [Br : Me2 = 1 : 2 : 41.Orthobromotoluene andacetic chloride yield parabromometatoluyl methyl ketone,C6H,BrMe*COMe [Br : Me : COMe = 4 : 3 : I],as a yellowish oil with a feeble-greenish fluorescence boiling a t269-272" ; when oxidised with permnnganate, it yields parabromo-metnt oluic acid. Bromoparaxy lene and acetic chloride yield a smallquantity of bromoparaaylyl methyl ketom, C6H2BrMe2*COMe[Br : Me2 : COMe = 4 : 3 : 6 : I], which melts at 39".Deoxybenzo'ins. By H. W EGE (Ber., 24, 3540--3542).-Benzybortholcry ZyZ ketone, CH2Ph-COC6H,Me2, prepared by Friedel and Crafts'method from orthoxylene and phenylacetic chloride, crystallises i nyellow plates, melts a t 95", and boils at 210-220" under apressure of2.5 mni.; it is soluble in alcohol, ether, and light petroleum, and itso;~ inze crystallises from light petroleum in lustrous, colourless needles.The henzyl derivative, CH2Ph*CHPh*C0.C6H,Me2, obtained by boilingthe ketone with an alcoholic solution of benzjl chloride and sodiumetboxide, crystallises from light petroleum in lustrous needles meltingat 75". The isobutyl derivative, C4H,-CHPh*C0.C,H,Me2, formscolourless or yellowish crystals, and melts a t 91.5".Ilenzyl metaxylyl ketone is a thick, yellow oil, boils at 206-208"iinder a pressure of 22 nim., and is readily soluble in ether, but moresparingly in alcohol ; its benql derivative boils a t 365-375".Benzyl partrxylyl ketone boils a t 220-250" under a pressure of26 mm.; its ozime, CIGHl,NO, melts a,t 99", its hydmzone a t 96", andits benzyl derivative a t 60.5".Stereochemical Isomerism of Nitrogen Compounds. By A.HANTZSCH and F. &<AFT (Ber., 24, 3511--3528).-The authors haveprepared a number of compoutids, other than oximes, having thegeneral formula $>C:NZ, with the object of ascertaining whethersuch substances are capable of existing in stereochemically isomericforms; if such were the case, there would be strong grounds forthinking that Auwers and Meyer's explanation of the isomerism ofoximes is incorrect, because their hypothesis is based on the supposi-tion that this isomerism is due to the peculiar constitution of hydroxyl-amine.Puramethoxyheizz7tydryZamine, NH2*CHPh*C6HI*OMe, is obtainedwhen either of the stereochemically isomeric paramethoxybenzo-phenoneoximes is reduced with sodium amalgam in the cold; it is athick, optically-inactive oil, yields a sparingly soluble crystallineC.F. B.P. S. KORGANIC CHEMISTRY. 339hydrochloride melting at 191", and a crystalline acetyl derivative whichmelts at 159". The formation of a base isomeric with the above wasnot observed,Imidobenzophenone hydrochloride, CPh,:NH,HCI, is formed whenbenzophenone chloride (1 mol.) is heated with ethyl amidoformate( 3 mols.) a t about 130" until the evolution of hydrogen chlorideceases ; it is a colo~rless, crystalline powder, sublimes when heated,and is insoluble in ether and benzene, and only moderately easilys )luble in chloroform ; it is quickly decomposed by cold water, yield-ing benzophenone and ammonium chloride.Imidobenzophenone, pre-pared by passing anhydiwiis ammonia into a chloroform solution ofthe hydrochloride, is a colourless oil, and is decomposed by water.I'aramethoxyberuophenowe chloride, CPhCI,*C,H4.0Me, can be ob-tained by warming paramethoxybenzophenone with slightly more thanthe theoretical quantity of phosphorus pentachloride. It crystal-lises in colourless plates, melts at 54", and is readily soluble inbenzene, chloroform, and ether ; it is decomposed by warm water andby alcohol into hydrochloric acid and paramethoxybenzophenone.Paramethoxy b~nzophenone~~rachlorariil~ne,OMe*C6HI* C Ph: N* C6H rC1,is formed when the preceding compound (1 mol.) is warmed withparachloraniline (3 mols.) in chloroform solution.It crystallises inyellow plates, melts at 104', and is readily soluble in benzene, ether,and chloroform, but more sparingly in alcohol ; it is quickly decom-posed into its components by hot dilute acids, but is not acted onby boiling water. All attempts to obtain an isomeride of this com-pound were unsuccessful.Yaramethoxybenxophenoneparatohidine, OMe*C,H,*CPh:N*C,H,Me,prepared in like manner, separates from chloroform in yellow crystals,melts at, 96", and resembles the preceding compound in its behaviourwith acids. The chloroform mother liquors obtained in the prepara-tion of this compound yield, on evaporation, not inconsiderablequantities of an oily product which does not crystallise when kept at0" ; it is possible that this oil coutains an isomeride of the crystallineproduct (m.p. 96").Paramst hoxy benzophen 011 e- /3-napht hy lamine, OMe* C6H4*C P h : F C,,,H,,prepared from paramethoxybenzophenone chloride and /3-napht hyl-amiiie, is a crystalline cornpound melting at 132", but the productsobtained in like manner from berizytamine and from pwramidophenol:rre oils, as is also the condensation product of paratolyl phenylketone chloride with paratoluidirie.An additive product of the composition OHGHPh-NH*C,Hk*COOHis obtained, together with the condensation product immediatelydescribed below, when metamidobcnzoic acid is shaken with waterand benzaldehyde; i t separates from ether in crystals, is readilysoluble in chloroform, and is decomposed by warm diliite hydrochloricacid.The condensation product CHPh:N*C,H,*COOH is graduallyJeposited from the mother liquors of the preceding compound ; it is Hyellowish, microcrystalline powder melting at 119" ; the formation ofan isomeride of this condensation product WiL6 not observed340 XB3TRXi;TS OF CHEMCAL PAYERS._Renzop7,enon~aramidobeirzoic acid, CPh2:N*C6H4*COOH. prepared byheating beiizophenone chloride with paramidobcnzoic acid in chloro-form Polution, crystallises frt)m chloroform in yellow prisms, melts a t240°, and is only sparingly soluble in ether, benzene, and cold alcohol,hut inoderately easily in hot C I ~ C O ~ I O ~ , aiid very readily in chloroform ;it is slowly decomposed by cold alcohol, and quickly by boiling diluteacids, yielding benzophenone and the amido-acid.Paramefhoxy benzophen oneparami(?obenzoic acid, CllH1,N09, is formedwhen pwmmethoxg benzophenone chloride is treated with pnramido-benzoic acid in chloroform or toluene solution ; i t crystallises in yellowplates or microscopic needles, melts a t 21G0, and resembles the preced-i n g compoiind in its behaviour with solvents and with dilute acids.The chloroform mother liquors from this compouucl contain a sub-stance melting at about 164O ; this, and the fact that the crude con-densation prodnct has no well-defined melting point', whilst thatobtained from benzophenone chloi ide under like conditions meltsquite sharply a t 240°, lead the authors to conclude that possihly anisomeric paramcthoxybenzophenoneparamidobenzoic acid is praducedin the above reaction.Two isomeric h!ydrazones of the composition C2,,HIRN20, are pro-duced when paramethoxgbenzophenone chloride ( I mol.) is graduallyadded to a chloroform solution of phenylhydrazine ( 3 mols.) ; afterkeeping for some hours, the filtered solution is evaporated a t t h eorditiarg temperature, and the two products separated by fractionalerystnllisa,ti m.The one melts at 132O, crystallises from alcoliol insmall prisms, and is only sparingly soluble in cold alcohol, butmoderately easily in ether, and very rradily in cliloroform anflbenzene ; it is decomposed into its components by concentratedhydrochloric acid. The other hydrazone, which forms at the most,only about 10 per cent.of t,he crude product, is a colonrlem powder,and melts at' 90" ; it resembles its isomeride verg closely i n appear-ance, and has approximately the same solubilities, except, that it ismuch more readily soluble in ether. The only notable difference inchemical properties is, that the rornpound of lower melting point isless stable tjhan the other, and resinifies more readily ; under certainconditions, the componnd of lower melting point seems to be con-verted into tbe isomeride. F. s. K.By B. GOLDBERG (Ber., 24, 3.552-3553).-Bidet's statement (Abstr., 1889, 59.5) that a mixture of pure(thiophen-free) aniline, orthotoluidine, and parntoluidine only yieldstraces of rosaniline on heating with arsenic acid is incorrect; ttieauthor's experiments have showii that, practically, the same qnantityof rosaniline is obtained from the thiophen-free, as from the corn-mercial bases.F. s. K.By V. MEYER andH. WEGF, (Rer., 24. SSS5--3536).-Desaurin can be easily prepare11by mixing deoxyhenzoyn (1 mol.) with finely-divided potassiumhydroxide (4 mols.), and boiling the mixture with carbon bisulphide(15-20 parts) fnr 2 i hours ; t h e carbon bisulphide is then distilled,the residue washed with alcohol and ether successively until theFormation of Rosaniline.New Method of Formation of DesaurinsORGANIC CHEMISTRY. 341washings are no longer coloured red, and then recrystallised fromcehlorofortn or xylene ; the yield of t h e pure product is about 45 percent'. of the deoxybenzoyn employed.F. S . K.Studies in the Induline Group. By 0. PISCHER End E. HEPP(Annulen, 266, 249-263 ; compare Abstr., 1891, 1044) .-Whenphenjlinduline is heated a.t 160-170" for 5-6 hours with glacialacetic acid (5 parts) and 20 per cent. hydrochloric acid (20-30 parts),o r dilute (1 : 5 ) sulphuric ncid, i t yields aniline, a base of t h ecomposition C,,H,,N,O, benzeneindone!, a hydroxy-compound of thecomposition CleB11N202, and a small qusntit$y of a brownish-redsubstance ; these products are isolated as follows :-The brownish-redsolution is filtered from a considerable quantity of a brown, crystal-line substance, which consists essentially of the hydrochloride of thebase C,rH,,N,O, b u t contains also a small quantity of the brownish-red substance ; t h e last-named compound is probably a salt of carb-azolefluorindine (Zoc.c i t . ) , judging from the fluorescence of i t s s o h -tions ; i t can be easily separated from the other hydrochloride, owingto its insolubility. The acid filtrate is then treated with excess ofalkali, the precipitated benzeneindone separated by filtration, thealkaline solution treated with acetic acid, and t h e precipitatedhydroxy-compound extracted by shaking with ether.'l'he base of the composition C2$H ,,N,O, obtained by decomposingthe hydrochloyide with alcoholic soda, crjstallises from hot, benzenei n +mall, brown crystals h a v i n g a steel-blue reflex ; i t melts at about218" with evolution of a, red vapour, and, when heated more strongly,i t is converted into the brownish-red substance referred to above,It dissolves in glacial acetic acid and in dilute niineral acids yieldingbrownish-red, in concentrated hydrocliloric acid and sulphuric acitLyielding dirty-violet,, solutions ; when heated with concentratedhydrochloric acid, it ia decomposed into aniline and t h e hydroxp-conrpound referred t o above, and more fully described below.The hydr-oxy-compound of the composition C,,Hl,N2( l2 is obtainedi n reddish-yellow crystals on evaporating its ethereal solution (seeabove) ; it crystallises from benzene o r alcohol in brownish-yellowprisms o r plates, gives off R brownish-red vapour when heated at230", and melts at about 280"; i t imparts t o textile materials abrownish-orange colour. I t dissolves in concentrated sulphuric acidwith a brownish-yellow coloration ; its hydrochZoride crjstallises inthick prisms having a greenish-blue reflex, and is decomposed by water.Benzetieindone, Cl,-,H12N20, crystallises from alcohol in lustrous,well-defined plates, dissolves in benzene and alcohol with a yellow, i ndilute hydrochloric acid with a rose red, and in concentmted sulph-uric acid with a, green, coloration ; when distilled with zinc-dust, i tyields phenazine (m.p. 171") and benzene.A compound of t h e composition C18Hl5N:jO2 is formed, togetherwith a violet. base, aniline, atid a sparingly soluble, almost black com-pound, when amidophenylinduline sulphate is heated with dilutesulphuric acid for 4-5 hcu1-s a t 160-170"; t h e acid solution istiltered from the sparingly soluble sulphate of t'he violet base,mixed with soda, again fillered, the filt ate acidified with acetic acid342 ABSTRACTS OF OEICMICAL PAPERS.and the precipitate rccrystallised from 70 per cent.alcohol, fromwhich i t separates in small, nodular crystals, or in plates, showing Rgreen reflex. It sinters together a t about 230°, and melts completelyat 270-280" with evolution of brown vapours; it dissolves inbenzene, yielding an orange-red solution which shows a p e e n fluor-escence, and its solution in acetic acid is rose-red, that in concentratedsulphuric acid greenish-brown. The sulphnte crystallises from hot,dilute sulphuric acid in red needles, and is moderately easily solublein water.Phenylarnidophemjlinduline, C3,H2,N4, is formed, together withmuch smaller quantities of anilidophenylamidophenylinduline (seehelow), when amidophenyliriduline is heated with aniline (2 parts) at150-160" for some hours.It crystallises from hot benzene in smallnodules or plates having a green reflex, and melts at 245-250" ; itssolution in benzene is reddish-violet, that i n alcohol, blue, and thati n concentrated sulphuric acid, greenish-blue. The hydrochloride,CmH22N4,HC1, forms lustrous, greenish crystals. This induline canalso be obtained by heating an alcoholic solution of phenylamidoazo-benzene (136 grams) with aniline (140 grams) and aniline hydro-chloride (65 grams) a t 150-160" for a day ; the yield of the hydro-chloride is about 100 grams.AnilidophenylumidopJr,enylinduline, CJ6H27N5, is best prepared bylieating a mixture of azobenzene (12 parts), aniline (48 parts),aniline hydrochloride (24 parts), and nitrobenzene (12 parts) foreight hours a t 170".It crystallises from boiling xylene in nodules orplates having a green reflex, and meltiiig at 286-288"; it is moresparingly soluble than any other known induline. The hydrochloridec.rystallises in lustrous needles, and dissolves in alcohol with a green-is h- blue coloration.The molecular weight of phenylinduline was determined by Raoult'smethod in benzene solution: the results were in accordance withthose required by a compound of the inolecular formula C,,H,,N,.F. S. I(.Homologues of Acridine. By A. VOLPI (Gazzetta, 21, ii, 228-237).-EthyZacridine, C6H4<&->C6H4, is prepared by Bernthsen'smethod (Abstr., 1884, 1356) by the action of propionic acid on amixture of dipheny!aniine and zinc chloride.When pure, it crys-iallises in lustrous, white plates with a yellowish tinge, melts at 11Cjo,and dissolves freely in alcohol, benzene, and light petroleum, formingsolutions with a blue fluorescence ; i t is only very sparingly solublei n water. The dilute solutions of its salts all have a p e e n fluor-escence. The plutinocli loride, (C,,H,,N),, H2PtCI6, forms minute,yellow crystals, which decompose at 215" without melting. Theuurochlmide, CIbHI3N,HAuCl4, crystallises in needles melting at170". The hydrochloride, <116H,3N,HC1, crystallises in yellow, mono-clinic prisms, u : 6 = 1.5199 : 1 ; p = 83' 07'.It dissolves freely i nwater, and the solution is brownish-yellow when concentrated, andjellow, with a green fluorescence, when dilute. It is readily solublein alcohol, and decomposes when heated, without previous melting ;CEORGANIC CHEMISTRY. 343the sulphate, (Cl5HI3N),,H,SO4, is pale-jellow in colour, and melts a t2 10".Propylacridine, C,H4<CPr> CsH4, prepared in a manner similar toN-the previous compound, by the action of butyric acid on a mixture ofdiphenylamine and zinc chloride, crystallises from alcohol in colour-less, monoclinic plates, n : 6 : c = 2.015 : 1 : 1.998 ; p = GI" 07'. Itmelts a t 72-75", dissolves freely in alcohol, and is almost insolublei n water ; its solutions have the characteristic green fluorescence, andin other respects it has the general properties of the acridines. Thek~ydrochloride, CIsH,,N,HCl, forms yellow crystals which, when heated,decompose without previously melting ; the sulphate, C,,H,,N,H,SO,,forms greenish-yellow crystals, readily soluble in water and alcohol,but insoluble in ether.It darkens a t 245', and melts at 249".Pentadecy lacridine, CsH4< c I (C15H31) > C6&, is prepared from palmi- N--tic acid by the same method as the preceding compounds. It separatesfrom alcohol as a crystalline mass of a buttery consistency, but may\ e obtained in white or yeilowish plates by slowly evaporating thoalcoholic solution. It melts a t 65', and dissolves in alcohol, ether,Ineiizene, and light petroleum, but not in water. The alcobolic Eolutionof the base has a blue fluorescence, whilst the alcoholic solutions of itssalts have a green fluorescence, and are decomposed by water.Thej'latin ochloride, (C,,H,,N),, H,Pt CI,, forms minnte, orange-yellowc*rystals melting at 185". The hydroclLZoride, C?8H39X,HC1, is a yellowsubstance which melts a t i9', dissolves in alcohol, and is decomposedwater. The s+hate, C,,H,N,K,S04, crjstallises in tufts of>ellowish-red needles, melts at 150-151", and dissolves in alcoholand beiizene, but is insoluble in ether, and is decomposed by water ;its solutions have a feebly acid reaction.Stearic acid also yields an acridine by Bernthsea's reaction, so thatif the reaction does not apply to the entire series of fatty acids, thelimit must lie beyond stearic acid.Acridines may also be preparedfrom lactic, succinic, and tartaric acids, and will be described hy theauthor in a future paper. S. B. A. A.Methylcarbazacridine. By D. BIZZARRI (Gaxzetta, 21, ii, 1 5 8 -N-C,€I, .I I 163).--~ethyZcarbazucrid~ne, 1 X I , is obtained by a methodMeC-csH3analogous to that used for the preparation of phenylcarbaz-acridine (Abstr., 1891, 219). A mixture of carbazole (8 grams),glacial acetic acid (7 grams), and zinc chloride (15 grams) is heateda t 150-155" in ti sealed tube for eight hours, The bluish-green,pitchy product is extracted with boiling absolute alcohol, the liquidtiltered into concentrated ammonia solution, and diluted with water.The bright-red precipitate is collected, washed, dried, and repeatedlyextracted with dilute alcohol (47 per cent.) ; on cooling, the solutiondeposits a yellowish-white substance, which, after being washed wrthdilute alcohol, dried, and dissolved in the least possible quantity o344 ABSTRACTS OF CH~MLCAL PAPERS.glncial acetic acid, is reprecipi tat ed by ammonia.and finallyfractionally crystallised from benzene and alcohol. Minute, colour-less, uniaxial rhombohedra are thus obtained, soluble in acetic acid,sparingly so in alcohol, benzene, ether, chloroform, and carbon bi-sulphide, and insoluble in water and light petroleum. Whcn heated,the substance shrinks a t 150', softens a t 175', melts at 1i8', anddecomposes a t higher temperatures.When its acetic acid solution istreated with zinc-dust, filtered. and the filtrate precipitated withwater, a white, crystalline powder is obtained, melting with deconi-position a t 206" ; this dissolves in acetic acid, yielding a colourlesssolution, which, on t i eatment with potassium dichromate, gives thecharacteristic cherry-red colour of the original substance. Acidsalso, especially hydrochloric and sulphuric, rapidly reconvert i t intornethylcni*bwzacridine, of which it is, doubtless, the hydro-derivative.The compounds of methylcarbazacridine with acids have the sameinstability as tlie corresponding phenylcarbazacridine compfiunds,being decomposed by water, alcohol, excess of acids, or by drying.The h y d r o c k l o d e fornis beautiful, indigo- blue plates, the sulphategreenish-blue plates, the n i f m t e light-blue plates, atid the chromatebrownish-green plates.Picric acid forms an unstable compoundcrystallising in 1-ubj-red needles. Methylcarbazncridine is obtainedin small quantity by heating acetylcarhazole with zinc chloride fortwo hours a t 150-1.55", and proceeding as above indicated. Theaqueous alcohol used in the preparation cf the substance retains insolut,ion a compound melting a t 137-138", and crystallising iiiminute prisms, soluble in acetic acid. W. J. P.Aromatic Nitriles. 13s F. J. ZIKSSER (Ber., 24, 3556-3557;compare Freund and Immerwalir, Abstr., 18W, 1407).-A more con-venient method for preparing dipheiiylacetic acid than th8t usuallyadopted is to boil benzilic acid with hydriodic acid (b.p. 127') aiitla little amorphous phosphorus for four hours ; the nitrile of this acidis best prepared by quickly distilling a mixture of the amide anclphosphorus sulphide from a small retort.Diphenjlacetonitrile does not react with fatty hfllogen compoundsuuder various conditions ; on reduction with sodium and amyl nlco-hol, i t is converted into diphenylmethane and hydrogen cyanidc.IVhen phenylcinnamonitrile, cHPh:CPh.CN, is treated with sodiumand amyl alcohol, i t yields a large quantity of dibenzyl.1 : 3' : 4-Dichlor~naphthalenesulphonic Acid. B.y P. T. CLEVI:I?. S . I(.(Rer., 24, 3477--347!)).- 1 : 3' : 4-l)ichloronaphthaler/esul~honic acidis obtained by dissolviiig 1 : 3'-dicliloronnphthalene (m.p. 48") in ;Lirlixtnre of fuming and concentmted sulphuric acid (equal parts) anclgently waiming, when a pasty mass is produced, which, on dissolutiotiin wdm, yields microscwpic needles of the acid ; i t is very sparinglysoluble in dilute sulphnric acid. A second product, probably adisulphonic acid, is also obtained in small quantity. The potassiumsalt crystallises in flat, needles and tablets of' a silvery lustre with1 mol. H,O ; the u?nnioniicm salt resembles i t ; the sodium salt formsthin needles with 3 mols. H,O; the silver salt lustrous scales witORGXNTC CHF JI[STRY. 345I mol. H,O; the calciiini and ba&m salts crystnllise with 3 mols.H,O; whilst the ziric salt crystallises with 5 mols. H,O. All thesesalts are readily soluble in boiling water, and, for the most p a r t ,sparingly so in cold water.The lead salt crystallises with 4 mols. H,O ;the noppw salt with 6 mols. H,O ; whilst the niethyl and ethyl salts formdelicate needles arid melt a t 138" and 154" respectively. The sulph-onic chloride crystallises from glacial acetic acid in needles, and melts at151", whilst the ~ulpkonanzi~~e forms long, flat, satiny needles, antimelts a t 217". 1 : 4 : 3'-Trichloronaphthalene (m p. 65") is formedwhen the sulphonic chloride is heated with an excess of phosphoruspentachloride. A. R. L.1 : 2-Amidonaphthalenesulphonic Acid. By P. T. CLEVE (Be?..,24, 3472-3477) .-Landshoff and Meyer (D.-R. P. 56,563) describea naphthylaminesulphonic acid, obtained by heating at 200-250" at1alkali salt of naphthionic acid which contains the amido-group in ana-position.The sulpho-group must occupy the @-position adjacentto the amido-group, as it can be converted iuto 1 : 2-dichloronaphthal-ene (m. p. 34'). The new acid forms long, anhydrous needles orsmall, rhombic cr-ystals, a : b : c = 0 79401 : 1 : 0.36429, and is moresoluble than its isomeride, dissolving in 34 parts of boiling water anrl225 parts of cold; if allowed to slowly crystallise a t the ordinarytemperature, long needles containing Q mol. H,O are obtained. Thepotassium salt, sparingly soluhle in cold water, the sodium salt, dis-solving in 60 parts of cold water, the ammonium salt, readily solublein water, the silver salt, a white, sparingly soluble precipitate, arid thecalcium salt, sparingly in water, are anhydrous, whilst the mrsgnesiumsalt crystallises with 8 mols.H,O, the zinc salt with 5 mols. H20, andthe barium, lead, and manganese salts with 1 mol. H,O. The acetylderivative dissolves easily in water and separates in small, lustroiisneedlrs containing 1 mol. H,O. The diaxosrdphonio acid is a greenish,crystalline powder, and yields a hydrazinesulphonic acid crystallisingin micacous plates. The chlorosulphonic acid, obtained by boilingthe diazo-derivative with cuprons chloride, crystallises in plates of ~tsilvery lustre, and yields a suZphouic chloride me1 ting at 80", anhydrouspotassium, sodium, siluer, and barium salts, a calcium salt containing1 mol. H20, and an ethyl salt crystallising in small, colourless needles,and melting a t 104".1 : 2-Dichloronaphthalene passes over on dis-tilling the chlorosulphonic acid with an excess of phosphorus penta-chloride. 1 : 2-Naphtholsulphonic acid is produced by adding thediazo-derivative to boiling dilute sulphuric acid, and is purified byfirst converting it into the barium salt and then into the lead salt; itforms small, lustrous, rhombic tablets, is readily soluble in boilingwater, sparingly ira cold, and does not melt at 250" ; its solution giveswith ferric chloride an indigo-blue colour, which soon changes todirty red. The sodzum salt is readily soluble i n water; the leod andcalcrum salts crystallise with 1 mol. H20, and are sparingly soluble inwater, wliilst the barium salt crystallises with 1i mols.H20, and isalso sparingly soluble in water. Further experiments are in progress.A. R. L346 ABSTRACTS OF CHEMICAL PAPERS.Nitrosonaphtholsulphonic Acids. By 0. HOFVMANN (Bern, 24,3741--3746).-Sodium ferriizitrosonnphtholsul~hor~afe,Fe(NO*CloH50*S0,Na), [0 : NO : SO, = 1 : 2 : 41,is prepared by adding ferric chloride in excess to nitroso-a-naphtliol-sulphonic acid and treating t.he solution with soda; the compoiindcrystallises from water in dark-green plates. The correspondingpotassium salt, Fe(NO*C,oH50*S03K),, is more unstable t.han thesodium compound, and does not give constant arialyticd results.Cup& Ititros~naphtholsulphonate, C,,H50<"o >Cu + 3H20, is ob-tained from nitroso-x-naphtholsulphoiiio acid and cupric sulphate, andcrystallises in groups of brown needles.Nitroso-/3-naphtholsu! phonicacid gives an insoluble, amorphous precipitate with ciipric sulphate.SO,Cupric anzmoizionitrosonaphtholsulpl~onate,C10H50<so3.NH, N0*NH3>C~ + H20,is formed from nitroso-a-napbtholsulphonic acid and cupric ammonio-sulphate, or by heating tbc preceding copper salt with ammonia, andcryetallises in small, brobn plates, which exhibit an intense, bronzelustre in reflected light: The compound from nitroso-p-naphthol-sul phonic acid resembles the a-derivative in properties and composition.+ + H,O [O : NO : SO, = 1 : 2 : 41, crystallises in lustrous, brownish-red needles, which are somewhat soluble in dilute ammonia. Thecorresponding compound [O : NO : SO, = 2 : 1 : 3'1 is deposited inyellowish-green, lustrous plates.The cadnzium ammo&-salts are crystalline ; the a-naphtholsulph-onic acid derivative is deposited in long, orange-coloured needles,whilst that from /3-naphtholsulphonic acid is obtained in yellowish-green, microscopic plates.All the above ammonio-derivatives decompose, with evolution ofammonia, on heating in aqueous solution.Sodium Izitrosona~hthnlsul~~onute, NONa:C,oH50*S03Na + 2H20[0 : NO : SO, = 2 : 1 : 3'1, is prepared by adding concentrated sodato a hot saturated solution of sodium nitroso-P-naphtholsnlphonate,and orystallises in small, slender, green needles.Hydroxyanthranol. By C.E. LINEBARGER (Bull. SOC. chi^. [ 3 ] ,6, 92-94) .-Benzylhydroxjanthranol,Zinc ammonionit rosonapht hols ulphonate, C ,oH,O<so,.N0.NH,>Zn NH3J. B. T.is best prepared by boiling for three hours a mixture of 5 parts ofsoda, 50 parts of water, 10 parts of zinc-dust, and 3 parts of anthra-quinone, and then adding 3 parts of benzyl chloride in small portionsand continuing the boiling for fivc hours. The product, after b&gpurified by crystallisation from nlcohol, is recrystalhed from benzene.It then forms very pure but small prisms, melts at 60-61", anORGANIC OHEMISTRY. 347begins to decompose at 100". It is insoluble in water, soluble inalcohol, benzene, and chloroform. I t s solutions have a bliiishfluorescence. Anthraquinone is obtained by oxidation with chromicacid in acetic solution. Benzylanthracene is obtained by reductionwith hydriodic acid and amorphous phosphorus.The production ofdiacetylbenzSlhydroxyanthrano1, by boiling 3 parts of benzylhydroxy-antbrano1 with 6 parts of sodium acetate and 20 parts of aceticanhydride for bale an hour, proves the presence of two hydroxvlgroups. The purified product forms small, greenish tables, insolublein water, soluble in alcohol, very soluble in benzene. It melts at126". W. T.Paranthracene. By K. ELM (J. p r . Chem. [Zl, 44, 467-469).-The paranthracene was prepared by exposing a benzene solution of90 per cent. anthracene, saturated at 40-60°, for B week to sunshine,and then gently warmirig it on the water-bath t o dissolve any an-thracene which might have crystallised out together with the par-anthracene. The precipitate was then filtered, washed wi t,h benzene,and crystallised either from boiling xylcne or dimethylaniline.Fromxylene, paranthracene generally crystnllises in colourless, lustronsneedles, and from dimethylaniline in lamine. The crystals melt, butnot sharply, between 272" and 274", and become converted into anthrac-ene. Paranthracene does not fluoresce, whether as 8olid or in eolu-tion; it remains unchanged at 260°, and when a solution of i t indimethylaniline is heated; on the other hand, a solution of it inllaphthalene and in diphenylamine rapidly becomes fluorescent fromits conversion into anlhracene, the former solution when boiled, andthe latter when heated a t 260".The solubility of paranthracene in various solvents at their freezingpoint is very slight ; naphthalene proved the best solvent for det.er-mining the molecular weight of paranthracene by the cryoscopicmethod, and even this only dissolves 0.229 per cent.at its meltingpoint. A large number of determinations were made with the soh-tion in naphthalene, and the results showed values varying between276 and 344 as the molecular weight of paranthracene, whose fortnulamay, therefore, be allowed to be (C,dHlo)Z. Graebe and Liebermannassert that. paranthracene is stable towards bromine in sunlight. Theauthor finds that a mixture of paranthracene (1 part), bromine (10parts), and carbon bisulphide (100 parts), exposed to sunlight, rapidlyevolves hydrogen bromide, and yields dibromanthracene tetrabromide.Anthracene behaves similarly under the same circumstances, althoughstatements as to the bromination of anthracene take no account of thefact.A. G. B.Terpenes and their Derivatives. By J. W. BRCHL (Ber., 24,3701-3737 ; compare this vol., p. 'LOO).--This paper describes someof the physical constants of the compounds described i n the previouscommunication.The specific gravity was determined a t '20" aud compared withwater a t 4". The refractive index (11) was usually determined forthe potassium, sodiuifi, lithium, and tliallium flames, and also for th3 48 ABSTRACTS OF CHEMTCAL PAPERS.lines in the hydrogen spectrum, Hz, HP, H*/, Hfi. The term “specificdispersion ” is applied to the difftwnce in the specific refractive powersof the compounds in the region of the spectrum between Hy and Ha,9 i x denotes the molecular refractive power for the hydrogen line a.The sp.gr. of merithyl ethyl ether, C,,H,,OEt = 0.8513; 93tz = 56.96,and the molecular dispersion = 1.38; these numbers agree closelywith the theoretical values. Ethyl camphor could not he obtainedquite pure ; its sp. gr. = 0.9:372 ; 9tz = 53.4(! ; 9h, = 53.64 ; mole-cular dispersion = 1-29 ; the compound, therefore, contains noethylene li n kaqe.E thy1 cam phocarboxylate, like the preceding compound, containsno ethylene linkage ; the sp. gr. = 1.0563 ; 93tz = 59-48 ; 92-i - 9Ra= 1.45. The molecular dispersion of these compoiinds is thus seento be unaf3fected by the closing of an open chain ; in this respect itresembles molecular refraction, nor is i t influenced by a para-linkagein the benzene nucleils ; that is to say, by the formation of a doubletetramethylene ring.Ethyl cnmphocnrboxylttte ethyl ether isrepresented by the formula alrrady given, and is not a camphordi-carboxylic acid ; its sp. gr. = l.Oi59 ; 9;s = 76.92 ; %-/ - 9ia = 2-20.The theoretical values are 74.61 and 1.177, the difference is probablydue to experimental error.Bornjl ethyl ether, C,,HI7*OEt, was prepared by the mutual actionof borneol, sodium, and ethyl iodide, and also from camphor \)yBsubiqny’s method; the sp. gr. = 0.9008; 9iz = 54.88; 9iy -= 1.31.Bornyl methyl ether, C,,H,,*OMe, like the preceding compound, hasno ethylene linkage, the sp. gr. = 09162; 9b = 50.36 ; %by - 9iz= 1.26.Bornyl methylene ether, ( C1,H,,O),CH,, crjstallises in rhombicprisms, a, : b : c = 0*91:34 : 1 : 0.565; the sp.gr. = 1,0735 ; $ 1 ~ 1 ~ =92.77 ; % l l ~ , , - WH, = 2.16 ; this value was obtained indirectly ; thenumber required by theory is 2.14, and i t appears to be the firstknown example of a compound urystallising in any but the regularsystem, the molecular refraction and ~iiolecular dispersions of whichagree with the values deduced from its chemical composition and con-sritution ; for details of the measurements and calculations, the originalpaper should be consulted.The const ants for diethyl camphorate also agree with theoreticalnumbers; the sp. gr. = 1.0298; $?a = 67.32; 9t-i - ’3ta = 1-57,l’he compound contains TJO ethylene linkage.On Ftc-count of the extreme viscosity of ethyl hjdrogen camphorate,the sp.gr. was determined by means of the vacuum pjknometer(Abstr., 1891,520) ; the sp. gr. = 1.09977 ; 9la = 57.84 ; 9 i y - 9lz= 1.37; the acid, therefore, contains 110 ethylene linkage, and thephysical properties agree with the formula already proposed for it.‘l’he molecular heat of combustion of camphoric acid = 1243.6 cal.and of camphoric anhydride = 1252.4 cal. ; the small difference betweenthese numbers indicates that the carboxyl groups are in the ortho-position.The author considers that the low electrical conductivity ofcamphoric acid is the only fact which can be urged against his formula ORQANIO CHEMISTRY. 349after pointing out that this may be due to the presence of the basicgroup CH2-CH2, he discusses the general effect of substitution onthe electrical conductivity of acid@, and enumerates a number ofapparent anomalies ; since no analogue of cnmphoric acid is known inthe succinic acid series, it is impossible to foresee how the electricalconductivity would be affected- by the introduction of the groupCZH,.J. B. T.Crystalline Products from Lemon and Bergamot Oils. ByL. CRISMER (Bull. Soc. Chim. [3], 6, 30-33 ; compare Tilden and Beck,Trans., 1890, 323).-The residue from the distillation of lemon oil ata pressure of 10 mm. is dissolved in liglit petroleum, and this solutiondeposits nodular crystals of the composition C1OH1OOd, which are puri-fied by recrystallisation from anhydrous ether, and then form a white,inodorous powder which melts a t 144", and neither decomposes norsublimes when heated to 240".Sulphuric acid colours this substance,which is, perhaps, hesporetic acid, golden-yellow : a trace of nitric acidconverts this to green, or a trace of potassium permanganate 80 blue,which subsequently becomes green. On evaporation, the light petr-oleum leaves a butter-like mass, melting about 50°, and this, afterpurification by recrystallisation from alcohol, has a lernon-like odour,and gives a dark brown coloration (this vol., p. 386) with am-moniacal mangnnous solutions, differing in this respect from thesubstance Cl0HI,,O4. Bergamot oil, when similarly treated, affordswhite, crystalline needles which melt at 184O, sublime at 230-240",and have the centesimal composition C 65.24, H 3.78, 0 30.98.This substance does not appear to be the bergaptene of Mulder andOhme, which melts at 206".T. G. N.Action of Hydriodic Acid and Amorphous Phosphorus onPicrotin. By A. OGLIALORO and 0. FORTE (Gazzetta, 21, ii,213--'L15).-~icrotozic acid, Cl6HI8O4, is obtained by warming a mix-ture of picrotin (prepared by the action of potash on picrotoxin),amorphous phosphorus, and hydriodic acid, allowing the brisk effer-vescence which takes place at first to subside, and then boiling for about10 hours in a reflux apparatus. On diluting the product with water,steam-distilling, and filtering the residue, the filtrate, on cooling,leaves a white deposit of picrotoxic acid. This crgstallises from dilutealcohol in lustrous, white needles, melts at 134", dissolves readily inalcohol, but only sparingly in hot water.It bas a feebly acid reaction,and dissolves in alkalis, but is reprecipitated from its solutions onthe addition of an acid. The silver salt, C15Hn04Ag, is a white, crys-talline powder, sensitive to light. The formation of this acid affordsadditional proof of the formula, C16H1807 for picrotin.S. B. A. A.Constituents of theBuds of Chrysanthemum Cinerarizefoliurn.By H. THOMS (Chein. Cent?.., 1891, ii, 670-671 ; Phnrm. C'enkralhulte,32, 471--472).--Continuing his examination of the constituents ofthe buds of Chrysanthemum cinerariEfoliurn (see also Abstr., 1891,333), the author describes one of the new compounds, pyrethrosilb,VOL LSII.2 350 ABSTRACT8 OF OHEMTOAI~ PAPERS.more fully. The light petroleum extract of the buds was cmcen-trrtted, and a golden-yellow, soft residue obtained, which, after beingwashed with alcohol, remained as colourless, bitter crystals. Thecrystals are elongnted, rhom bic octahedrons, me1 ting a t 188-1813’It, is readily soluble in chloroform and in hot alcohol, less soluble inether and light peti*oleum, insoluble in water. I t s formnln isC3,H,,0,, (?). It dissolves in concentrated sulphuric acid with yellowor weak redish- brown coloration. I n 25 per cent. hydrochloric acid,the substance becomes red or violet, and the solution is violet coloured ;water precipitates yellow plates. The filtrate, after treatment withl~gdrochloric acid, does not reduce B’ehling’s solution, so that pyrethro-sin cannot be considered as a glucoside ; but if the yellow compound betreated with concentrated hydrochloric acid, and the solution be neu-tralised.it then reduces Pehling’s solution. The author suggests thatthe yellow substance is nearly related t o phloroglucinol, and thatpyrethrosin is a phloroglucide.Agrostemma Githago (Corn Cockle). By N. KRUSKAL and R.KOBERT (Chem. Centr., 1891, ii, 545-546 ; Arb. pharm. Inst. Dorpat,6 , 89-145, 146-148) -The sapotoxin of Apostemma has the samecomposition as those of radix saponaria a2bm and of quillaja bark, butdiffers from them in its physiological properties. Hydrolysis withacids causes the formation of glucose (4 mols.) and sapotoxin (1 mol.).The corn cockle contains about 6.17 per cent.on the average.4groste?nma-sapotos:in has an irritating action on the mucousmembrane of the nose, mouth, and eyes; it affects the nervessimilarly to that of the quillaja bark. When in solution (1 : 15000),it dissolves blood corpuscles of both carnivorous and herbivorousanimals. It appears to act differently on animals when taken in-wardly, the Herbivow being relativelv unaffected, provided that thedoses are not too large and not taken for too great a length of time,whilst, on the other hand, the CarnivorE are seriously affected andreadily succumb to its action. On man it has an intermediate effect,b u t doses of 0-1 gram are sufficient to cause illness. The authorpoints out t h a t the bread which the Russian military authorities pro-vide for the soldiers may contain as much as 0.5 per cent.of corncockle, and this corresponds with a dose of about 6 grams of corncockle per day, a quantity which may readily produce serious toxicale ffec t s .Kobert poiiits out that the simple term “ ssponin ” is not sufficient,and the source from which it has been obtained should be stated,since the several different snponins have such varying physiologicalactions. The several saponins appear to belong to series of com-pounds which have different generic formulae. Stutz’s saponin,C19H2~~OH)50~, belongs to a series the formula of which would beC,iHZn-eOlo. The lowest member of the series is isomeric withsyringin, and bas the formula Cl,H2M0,0.Constitution of the Ethylpyrrolines.By C. U. ZAYETTI(Gazzetta, 21, ii, 163--173).---The author aspplies the method givenby him (Abstr., 1891, 1387) for the determination of the constitutionJ. W. L.J. W. LORGAXIC CHEMISTRY. 831of pyrroline derivaiives to the case of the ethylpyrrolines obtained bythe various known methods.Ethglpyrroline (1 vol.), obtained by passing a mixture of equalyolumes of ethyl alcohol and pyrroline through a, heated tube con-taining zinc-dust (Abstr., 1890, l4%3), is dissolved in alcohol (10 vols.)nnd boiled with the calculated qufintities of hydroxylamine hydro-chloride and anhydrous sodium carbonate for six hours. The solventis distilled off under reduced pressure, the residue treated with cold,dilute aqueous potash, and the unaltered pyrroline extracted withether.The solution is now saturated with carbonic anhydride, andagain extracted with ether ; on evaporating the ethereal solution, asyrup is left which solidifies almostJ completely after a time. Theresinoiis matter is removed from this by washing with cold ether, andthe residue dissolved in boiling ether; on cooling, the solutioqdeposits a small quantity (0.2 gram from 11 grams of ethylpyrroline)of a dioxime, C6HI2N2O2, which, after recrystallisation from ether,f l ) r m s colourless scales, and melts at 134-135". The ethereal solu-tion, on concentration, yields a quantity (4 grams from 11 grams ofethylpyrroliue) of an isomeric dioxime, \v hich, on being repeatedlyrecrystallised from anhydrous ether, is obtained in splendid, colourlessscales melting a t 84-85" ; this compound is very soluble in water,alcohol, benzene, and ethyl acetate, somewhat less so in ether. Theformation of these two dioxirnes shows that the ethylpyrrolirie is a,mixture of two isomerides.The oxime melting a t 84-85" (2 grams), when boiled with 30 perwnt.aqueous potash (50 c.c.), gives off ammonia; the brownish-redsolution thus obtained is saturated with carbonic anhydride, reppatedlyextracted with ether to remove the unchanged oxime, and decolorisedby animal charcoal. The solution is now exactly neutralised withsnlphuric acid and evaporated t o dryness, first on a water-bath andthen in a vacuum. On ext,racting the residue with anhydrous etherfree from alcohol, and evaporating the ethereal solution, a syrupy acidis left ; this does not solidify, dissolves with effervescence in solutionsof the alkaline carbonates, gives a violet coloration with ferric chloride,and yields an uncrystallisable hydrazone.With lead acetate solution,the ammonium salt gives a white precipitate, soluble in excess ; withmercurous chloride, a white precipitate, rapidly changing to metallicmercury ; with mercuric chloride, an opalescence ; and with silvernitrate, in concentrated solution, a yellow precipitate rapidly changingto metallic silver. The acid is probably normaZ propionylpropionicacid, CH,Me*CO.CH,.CH,-COCH, its d e e r salt having the com-position AgC6H,0,. The dioxime melting a t 84-85" has, therefore,the constitution CH,Me*C(NOH)*CH,.CH,*CH:NOH, and the pyrrol-ine from which it is obtained must be a-ethylpyrroline. The dioximemelting at 134-135" is probably NOH:CH*CH,*CHEt*CH:NOH,and is derived from p-ethylpyrroline.The ethylpyrroline obtained by the action of ethyl iodide onthe potassium compound of pyrroline boils 'at the same temperature(163-165') as the above, but, on treatment with hydroxylaminehydrochloride, yields nothing but a small quantity of the dioximemelting a t 134-135". The pyrroline obtained in this manner is,2 b 352 ABSTRACTS OF CHEMICAL PSPERS.therefope, /3-ethylpJrroline, that obtained from alcohol and pyrrolinebeing a mixture of a- and 6-ethylpyrroline, boiling at the same teni-perhture.The above experiments fully agree with the aiithors' previousobservation, that /3-pgrroline derivatives are much more stable thana-pyrrolines.Diethylpyrroline yields no trace of oximido-compoundon treatment with hydroxy lamine hydrochloride.( B e r . , 24, 3751-3765 ; compare Abstr., 1891, 1162).--Pyridii~ecarboql chloroplatinite, COPtC12,C5NH5, is obtained as a yellow oil l 1 ymixing an aqueous solution of pyridine with a hydrochloric acidsolution of carbonyl chloroplatinite, COPtCI,. It decomposes at loo",forms a hydrochloride, COPtCl,,C5NH5,HC1, and when treated withhydrohromic acid yields, not the hydrobromide, but the compoundCOPtBr,.C,NH,,HBr.W. J. P.Derivatives of Carbonyl Chloroplatinite. By F. FOERSTEEIt also forms a very unstable picrate.-, - - I C OrtC1, C&H5COPtCl,C,NH,'Dipyridine carboql ch loroplatinosite, is obtainedby mixing a fairly concell trxted hydrocbloric acid solution of carbonylchloroplatinite with an alcoholic solution of pyridine, shaking to redis-sol^ t he precipitate first formed, and recrystallising from alcohol thecrystals t,hat finally separilt,e. I t forms, when pnre, yellowish-greenneedles, dissolves readily in methxl and ethyl alcohol, chloroform, andbenzene, very sparingly in ether, carbon bisulphide, and light petrol-eum, decomposes a t 6U", and is decomposed by mere traces of moisture.I n the reaction mentioned above, carbonic anhydride is evolved, andout of the mother liquor from the substance last described there can beobtained, by evaporation at the ordinary temperature, first lustrous,yellowish-green crystals of a double compound,wbich dissolves without decomposition in hot hydrochJoric acid,and can be dried at 100".Then separate large, colourless, obliqiieprisms of ylatodipyridine chloride, PtCI,(C5NH5), + 3H20, and small,yellowish-brown needles, consisting €or the most part of platoso-&pidine chZorids, Pt (C,NH,CI),, but containing also a little plato-semidipyridine chloride, PtCl (C5NH5),C1. Platosopyridiue chlorideforms, with dipyridine carbongl chloroplatinosite, the double COIJI-pound mentioned above, and froni it, with excess of pyridine, theplatodipyridine chloride was doubtless derived. Dipjridine carbonylchloroplatinosite, when treated with chlorine, yields pyridineplatinochloride, (C5NH,),,H2PtCI6, and hydroplatinochloric acid,H,PtCl, ; when it is boiled with hydrochloric acid, platinum separates,and the hydrochlorides of pyridine carbonyl chloroplatinite and ofpgridine are formed.A compound COPtCl,, (C,NH,,HCl), appearst o he incapable of existence.Analogous bromine componnds were obtained in a similar manner.Pyridiize carbunyl bromoplatinite, COPtBr2,C5NHS, forms yellowneedles or plates melting a t 23-79" ; it dissolves readily in benzene,carbon bisnlphide, ethyl acetate, and hot alcohol, more sparingly incold alcohol, other, and light petroleum; it is decomposed by hoORQANIC CHEMISTRY. 353water. I t forms a hydrochloride, COPtBr,,C,NH,,HCl, and a veryu 11 st able pz crate.Dipyridiu e carbonyl brornoplatinosite, (COP tBr),( C5NH5),, is i n -soluble in most solvents, chloroform excepted.It forms triclinicc+ystnls, which are decomposed by water or when heated to 60".With hydrobromic acid, it behaves like the analogous chlorine com-pound with hydrochloric acid. Platodipyridine bromide,forms lustrous, rhombohedra1 crystals, which are soluble in water andalcohol, but not in ether; it decomposes at 130", forming platoso-pyritline &bromide, Pt( C,NH,Br),. This substance, which ia alsoiormed when an aqueous solution of platodipyridine bromide isallowed t o remain, or boiled with hgdrobromic acid, forms needles,or yellow aggregates of microscopic needles ; it is insoluble in water,and nearly so in aqueous ammonia. As in the case of the analogouschlorine compound, small quantities of an isomeric compound,PtBr2( C,NH,),, were also obtained.Attempts to see if the carbonyl group in these compounds willreact with hydroxylamine or phenylhydrazine, as i t does in ketonesand aldehydes, gave negative results.Hydroxylamiiie exercises areducing action. With an acetic acid solution of phenylhydrazine,carbonyl chloroplatinite yields an unst,able phenylhydrazine cccrboizylclt lor( Flat inite, COPtC12,C6H,N2H3, which crystallises from ethylacetate in jellow plates. It is decomposed by hot. hydrochloric acid,but dissolves in a hot hydrochloric acid solution of carbonyl chloro-platinite, and, on cooling the solution, the hydrochloride,separates out in orange-yellow needles, soluble in alcohol and ethylacetate, but not in benzene, carbon bisulphide, or ether; i t is decom-posed by water when heated a t 100'.Action of Bromine on Para- and Ortho-hydroxyquinoline.By A..CLAUS and H. HOWITZ (J. pr. Chem. [el, 44, 433-45lj.-4 : 3-Bromhydroayquinoline hydrobromide separates as a yellow, crys-talline precipitate when bromine (1 mol.) is added to a solutionof 3-hydroxyquinoline in 10-12 times its weight of glacial aceticacid. It is sparingly soluble in cold water, and crystallises from hotwater in siuall, hard, lustrous granules. It has no definite meltingpoint, bat dissociates when heated. When the aqueous solution ofthe hydrobromide is decomposed by potassium hydroxide or am monk,and acidified with acetic acid, 4 : 3-bromhydrosyqiLinoline is pre-cipitated in felted, small, slender needles ; it melts at 186" (nncorr.),and sublimes ; the platinochloride, with 2 mols.HzO, is described. By4 jxidation with permanganate, the base yielded pyridinedicarboxylicacid, which was converted into nicotinic acid (m. p. 227-229") whenheated; this is evidence that the bromine atom is not in the pyridinering. The orientation given is also supported by the fact that thisbromhydroxyq uirioline is one of the products of the quinolisation ofmefabromoparnhydroxaniline by Skraup's method, as will be shownC. F. B8.3 4 ABSTRACTS OF CHEMIOAL PAPERS.i n a future memoir. The hydrobromide is also formed when a solu-tion of bromine in chloroform is added to one of 3-hydroxyqninolinein the same solvent.B u t an intensely reddish-yellow precipitate isformed when the reaction t.akes place in a solution in concentratedhydrobromic acid, or when bromine is added to t-i solution of 3-hydr-oxyquinoline in chloroform ; this compound would appear to containmore hydrogm bromide than the yellow hydrobromide, into which itchanges, after a time, with evolution of hydrogen bromide.When bromine (1 mol.) acts on 1-hydroxyquinoline, a mixture ofthe hydrobromides of the unaltered base, and of bromo- and dibromo-1-hydroxyquinoline is formed. The product is boiled with water,and the solution, either before or after filtration, mixed with sodiumacetate ; the precipitate is dissolved in hydrochloric acid, and againprecipitated by sodium acetate.The bases are next dissolved inhydrochloric acid, and the solution mixed with suEcient water torender it turbid ; after some hours, the dibromo-derivative sepamtm,and is treated by the same process several times to purify it. Thebromo-derivative can be obtained pure from the solution after a very&mall quantity of sodium acetate has been added to precipitate theremaining dibromo-derirative. The two can also be separated byfractional distillation with steam, when the bromo-derivative passesover first .4 : 1-Brornhydroxyquinoline crystallises from hot water in small,colourless needles, melts a t 124" (uncorr.), sublimes in various but ill-defined forms, and is practically insoluble in cold water. The platino-chEoride was obtained.When oxidised by permanganate, the baseFields non-brominated pyridinedicayboxylic acid ; this settles itsorientation.4 : 3 : l-Dib?.om72.ydro;el~qzlinolilze crystallises in lustrous, slender,yellowish needles, melts a t 196" (uncorr.), sublimes in colourltissiieedles when heated, and dissolves easily in chloroform, acetone,benzene, +cia1 acetic acid, and alcohol, but only sparingly i n ether,and not a t all in cold water. When oxidised by permanganate, it yields~>yridinedicarboxylic acid ; this shows that the bromine atoms arenot in the pjridine ring. When the hydrobromide is suspended inc.hlorvform and acted on by bromine, a red additive compound isproduced, which easily decomposes, like that described above.A. G. B.Oxidation of Piperidine and Tetrahydroquinoline Deriva-tives.By C. SCHOTTEN and W. SCHL~~MASN (Ber., 24, 3687-3700).-€'icrylpiperidine (compare Turpin, Trans., 1891, 714) is hardly actedonat all by potassium permanganate, even on long-continued heating; onoxidation with nitric acid or chromic acid, i t yields rcsinous products.S 0, PhSNH [ C H?] 4*C 0 OH, isohtained, together with small quant itks of phenylsi~lphoiiamide, whenphenylsulphonepiperidine (compare Hinsberg, this vol., p. 64) isoxidised with potassium permangarlate. It' crystallises from hotwater in colourless, nacreous plates, melts at 97", and is readily solu-ble in alcohol, ether, glacial acetic acid, and light petroleum, but, onlysparingly in benzene and chloroform ; when boiled with ncrtic anhydl.iclr., i t is converted into a crystalline anhydride.The bn~*i?cnz. saltPhen y ZsuZpIi one- 8-amidovaZe?-ic acidORGANIC CHENISTHY. 355( C,1H,404NP)2Ba, zinc salt, with 2H,O, and copper salt (abhydrous)were prepared. The salver salt,, CI,HI4O,NSAg, crystallises in lustrousplates. When the acid is heated with concentrated hydrochloric acidat 180°, it yields 8-amidovaleric acid phenylsnlphonate,this salt begins to melt at about 1&O, and is not completely liquefieduntil the temperature has risen to ,I 45" ; when, after i t has solidified,the same portion is again heated, it melts quite sharply a t 10i".When phenylsulphone-6-amidovaleric acid is heated with concentrated,hydrochloric acid and barium chloride a t 2-50", it seems to be decom-posed into 6-amidovaleric acid, sulphuric acid, and benzene.Y heny ZsuZp honet et rahy d ropuinoli ne, C9N EX S O,Ph, prepared byshaking tetrnhydroquinoline with potash and phenylsulphonic chlor-ide, crystallises from dilute alcohol in large, colourless plates, meltsat 67", and is volatile with steam ; it is readily soluble in benzene andchloroform, but more sparingly in glacial acetic acid, ether, alcohol.and light petroleum, and insoluble in water.On oxidation withpotassium permangnnate, it yields very small quantities of an acid,the nature of which was not determined, and a little phenylsulphon-amide; with fuming nitric acid, it jields it yellow compound which isinsoluble in soda.MethyZ tetra11 ydroquinolinecnrboxylate, C9NH,,.COOMc, is obtainedwhen tetrahydroq uinoline is treated with methyl chlorocarbonate i nthe cold.It melts a t about 35", and is insoluble in water, alkalis,and acids, but soluble in the ordinary organic solvents ; on oxidationwith boiling potassium permanganate, it gives a substance which crys-tallises in red needles, melts a t 175', and gives the indophenin reaction ;when heated with potassium permanganate in the cold, it yields verysmall quantities of an acid which iiielts a t 155-156". The dinitn,-derivative, CI1 HIIN3Os, prepared by dissolving methyl tetrahydroquin-olinecarboxylate in fuming nitricacid, crystallises fromnlcohol in goldctineedles, melts a t 174" with decomposition, and is not decomposed bgboiling alkalis or acids ; it is insoluble in ether nnd light petroleum,and oclf sparingly soluble in alcohol, but readily in benzene.Synthesis of Phenylpyrazolidine.By A. MICHAELIS and 0.LAMPE (Ber., 24, 3738-3740).-Sodium phenylhydrazine (2 mols.),benzene, and trimethylene bromide (1 niol.) are mixed and allowe tto remain f o r some time a t the ordinary temperature, the reactionbeing completed by heating on the water-bath; the benzene solu-tion is treated several times with water, and fiiially with dilutehydrochloric acid ; the acid solution, alter ueutralisation with alkali, isextracted with ether. After the ether is distilled, and the residueC5H1IN O,,CJ&.S OSH ;P. S. K.fractionated, phenylpyraaolidine,colourless, or pale-yellow, liquid with a faint, charaacteristic odour ; itboils at 210" under a pressure of 165 mm., anti a t 160" under a pre+sure of 20 mm.The compoiznd has well marked basic properties,reduces alkaline copper solutions on warming, and is readily oxidisedeither by exposure to air or on treatment with mercuric oxide3.56 ABSTRACTS OF CHEMICAL PAPERS.forming phenylpyrazoline. The picrate crystallises in short, yellowneedles. The above synthesis probably proceeds in two stages, anin ternrediate compound, CH2Br-CB2*CH2-NPh*NH2, being first formed ;this is then condensed by the excess of sodium phenylhydrazine : thereaction is therefore analogous to the formation of pyrrolidine fromL-chlorobutylamine by the action of alkalis.A technical product, termed " phenylpyrazine," which is formed bythe action of ethyl f3-bromoyropionate on phenglhydrazine in alkalineco *yH2 The compoundNH*CH2'solution, is 1 : 5-phenylpyrazolidone7 NPh<C9H8N202, prepared by Michaelis and Burmeister from ethyl chloro-malonate and phenylhydrazine (compare Abstr., 1891, l068), provesto be 1 : 3 : 5-phenylpyrazolidone, NPh < J.B. T. CO -?HZNH. OH2'The Osazone of Hydroxypyruvic Acid, By W. WILL ( B e y . ,24, 3831--3834).--In a previous paper (Abstr., 1891, 542), theauthor described n substance obtained by the action of hydrogenchloride on an alcoholic solution of the osazone of hydroxypyruvicacid, which he regarded as its ethyl salt. After dissolving in alkaliand reprecipitating with acid several times, and finally recrystallkingfrom alcohol, it is obtained in reddish-yellow aggregates of needles,which, from the analysis and molecular weight determination, havethe composition C15H12N,0.It is therefore not the ethyl salt, asformerly supposed, but is obtained from the osazone by loss of theelements of water, and is iden tical with the pbenylhydrazineketo-phenylpyrazolone obtained by Knorr by heating the osazone withacetic anhydride (Abstr., 1888, 724). Its formation is represented asfollows :-It is insoluble in water, readily soluble in alcohol and ether, sublimesin small quantities, and colours wool and silk yellow in alkalines o h t i on.The osazone of hydroxypyruvic acid differs from the similar com-pounds investigated by Knorr, inasmuch as the solutions of its saltsdo not yield the pyraxolone directly on acidification.The osazoneitself yields a sodium salt, as already found by Nastvogel (Abstr.,1889,237). The pyrazolone, however, also yields a sodium compound,which crystallises in slender, yellow needles, and melts at about 300"with decomposition. It also forms a silver conzpound, C15H11AgN40,which crystallises in reddish-yellow plates, becomes brown at 206",and melts at 215".The etbyl salt of the osazone may be obtained by the action ofmethyl iodide and alkali on its alcoholic solution. It is a yellow,microcrystalline powder which melts at 222-223", and is insoluble inalkalis and dilute acids. H. G. C.Phenylguanazole. By G. PET~LIZZARI (Guzzetta, 21, ii, 141-154).-Phenylguanuzole is prepared by heating a mixture of dry dicyanoORGFANlC: CHEMISTRT. 357diamide with phenylhydrazine hydrochloride, in molecular proportion,at 150"; much ammonia is evolved during the reahon, and, asspontaneous heating occurs, the mixture must be cooled if the tempe-rature rises above 180". The vitreous, yellow product is crystallisedfrom dilute hydrochloric acid, dissolved in water, and decomposed byconcentrated caustic potash, when the base separates in red needles;on recrystallisation from alcohol, it is obtained in large, hard, slightlyyellowish crystals melting at 174+--175".It is very soluble i n alcoholand water, but only sparingly in chloroform, ether, or benzene ; i t isprecipitated from its aqueous solutions by caustic soda and causticpotash.The molecular formula, as determined by the cryosoopicmethod, is C8H,N,. The aqueous solution is neutral to test-paper.q'he hydrochlo~ide, C8HgN5,HCl, crystallises in thin, white scales, verysoluble in water and alcohol, and melts at 240". Theylutinochloyide,(C,H,N,),,H,PtCl,, forms' yellow, prismatic needles. The aqueoilssolution of the base gives a white, flocculent precipitate with silvernitrate, soluble in hot water, nitric acid, and ammonia; it is a mole-cular compound of phenjlguanazole with silver nitrate,Silver sulphate and mercuric chloride give white precipitates withaqueous solutions of the base ; mercurous nitrate gives a white pre-cipitate soon turning yellow ; and copper salts give a yellowish-greenprecipit,ate. These precipitates are all molecular compounds.Thereaction between dicyanodiamide and phenyl hydrazine hydrochloridemay be carried out in alcoholic solution by heating for eight hours ina closed tube at 100".C€B9N5,AgN03.The reaction is represented by the equationNHPh*NH, + ~H*C(:NH)*NH*C(:NH).NH, =$I (:NH)*NHNH*C(:NH) >NPh + NHpAnilbiguanidine is probably an intermediate product of the reaction,for if anilguanidine hydrochloride (1 part) and cyanamide (1 part) beboiled with water (8 parts) for six hours, and treated with potash,ammonia is evolved and phenylgumazole separates. Pheny lguan-azole is also obtained by heating together at about 160" eqnalparts of anilguanidine hydrochloride and guanidine carbonate ; jargequantities of ammonia are evolved ; the product is dissolved in diluteIiydrochloric acid, and filtered ; on treating with solid potash,crude phenylguanazole separates, and is purified by repeated extrac-tion with chloroform.A mixture of biguanide wit.h phenylhydrazinein molecular proportion, when heated at 120-160", evolves muchammonia, and, on extracting the product with alcohol, evaporating,dissolvirig in water, treating with a little potash, filtering, and addingexcess of potash, pheriylguanazole is obtained. The yield by thelast two methods is small, but they show the very great analogywhich exists between phenylguanazole and phenylurazole (Trans.,1888, 550).Ethylanilbiguanidine, NH,*C(:NH)*NH-C(:NH)*NH-NEtPh, is pre-pared by heating unsymmetrical ethylphenylhydrazine hydrochloridewith dicyanodiamide in molecular proportion, at 160-170", for hal858 ABSTRACTS OF CHEMICAL PAPERS.an hour.No ammonia is evolved. The product is dissolved in water,filtered, and treated with caustic potash ; the base separates as an oilwhich is extracted by agitation with ether, and the residue left onevaporating the ethereal solution is boiled for some time with waterto eliminate unaltered ethylphciiylhydraxine ; caustic potash is theriadded, and the precipitate again extracted witlh ether ; on evaporatingthe ether, the base is obtained as a vitreuns, friable mass whichsoftens a t about. 50". It is very soluble in alcohol, ether, and benzene,less so in water ; i t has a strongly alkaline renction, and absorbs carh-onic anhydride. When boiled with potash, it yields ammonia and ethyl-phenyl hydrazine. The sulplznte, ClnH16Ns,H,S04, is obtained in small,colourless crystals which are very soluble in water, but only sparinglyin alcohol.w. J. P.Tropine. By G. MERLING (Bey., 24, 3108--3126).-The experi-ments to be described, taken in conjunction with the facts alreadyknown, prove that neither the formula, proposed by the author, nrlrt h a t of Ladenburg, which Liebermann has already shown t o be un-tenable (Abstr., 1891, 749), represents the constitution of this com-pound. In the present research, the author commenced his experi-ments with Roth's methyltropidine (Abstr., 1884, i S l ) , a compoundwhich proves to have properties entirely different from those ascribedto it by Ruth, and piocec,ded on the lines laid down by him Tor the in-vestigation of certain bases allied to piperidine ( A m d e n , 264, 310 ;Abstr., 1891, 1.506).z-Methyltropidine (A8 "-dihydrobenzyZdimethlJlamine, see below),C6Hi*CH2NMe,, is prepared by distilling a dilute aqueous solutionof tropidinemethylammonium hydroxide until it reaches a conccntrii-tion of 1 : 10, and then driving the base over with a current ofsteam ; i t is a colourless, mobile oil, of a faint ammoniacal odour, andcannot be distilled, as it changes into /3-methyltropidine on heating ;the yield is equal to that, of the tropidine employed.The p f u t i n c -chlol-ide, (C,H,,N),,H,PtCI,, cr.ystallises from boiling water in orange-yellow prisms, and melts at 173-174" ; the aurochloride,is a golden-yellow, crystalline precipitate sparingly soluble in water,and decomposing when boiled with i t ; the methiodids, C6H9NMe31, isreadily soluble in hot water, sparingly in cold, and melts a t 162" withthe evolution of gas.Hydrochluru-a-methy Etropidine,C,H,H Cl-CH,*NMe,,is obtained as the hydrochloride, when a-methyltropidine is allowedto remain for some days at the ordinary temperature with a solutionof hydrogen chloride saturated at 0" ; the azwochloride,CgH ,~CIN,HAUC~~,separates as a yellow, crystalline precipitate on adding auric chloride,and the free base as a colourless, mobile oil on adding sodium hj-dr-oxide to the solution; the latter changes slowly a t the ordinal-gtemperature, or quickly a t the temperature of the water-bath, into ORGANIC CHEMJSTRY.359viscid syrup which consists essentially of t~ropidinemethylamnioniumchloride. It is poured into water and distilled in a current of steam,when a small quantity of a-methylpiperidiue passes over; the residueis shaken with ether to remove the resinous snbstances, solutions ofsodium hydroxide and potassinm iodide added, and the prcci pitatedtropidinernethylttmronium iodide orystallised from boiling alcohol ;it is next converted into the chloride by silver chloride, and this saltyields tropidine and methyl chloride on dry distillation. Thesereactions are analogous to the conversion of pentallylcarbindiniethyl-nmine into methyl-a-pipecoline, and indicate the presence of thegroup iC*NMe*CH(CH,R)- in tropidine.The formation of a-ethyl-pjridine from norhydrotropidine (Ladenburg) shows that the a-carbonatom carries an atom of carbon not belonging to the hydrngenisedpyridine nucleus; whilst that of the bibasic tropic acid, by theoxidation of tropine with chromic acid, proves that the second carbonatom of the side chain is also in combination with one of the nuclealcarbon atoms. When a-methyltropidinemethylsmmonium iodide isconverted into the hydroxide, and this is boiled with water, it decom-poses into tropiiidene, C7HS, trimethylamine, and water, a reactionwhich points to the presence of the group =CH.CH,*NMe, i na-methyltropidine. These facts are only to be accourited for byadopting the following formulae :-Tropine.,CH2 CH2CH-CHzCHLCH ; C O O H * C H < ~ ~ : : ~ ~ ~ > C H * C O O H .'CH,.N Me'Tropidine. Tropic acid.Methyltropine is, therefore, As-hydroxytetrahydrobenzyldimethyl-smine, and a-methyltropidine is As : 5-dihydrobenayldimethylamine.Tropilidene, C,H8, when dissolved in carbon bisnlphide and treatedwith brdmine, forms a dibromide which is an oil miscible with et,herand having a camphor-like odour ; when kept in a desiccator, it. resini-fies hy degrees, and, when heated on the water-bath for some hours,Iiydrogen bromide is evolved, and it is converted into a crystallinemixture of benzyl bromide and a substance separating from alcoholin yellow tablets, which is perhaps an isomeride of the dibromidc.When tropilidene (1 gram) is heated in a reflux apparatus for anhour with sulphuric acid (5 grams), water (20 grams), and potassiunidichromate (3.2 grams), a mixture of benzoic acid and benznldehydeis formed with evolution of carbonic anhydride. Tropilidene is,therefore, probably CH,:C<CH CH*:CHZ, -CH>CH.p- Methyltropidine, C7HaNMe2, is prepared a9 follows :-a-Met<hyl-tropidine is heated at 140-15d" in a reflux apparatus; on now re-moving the source of heat, the temperature rises to 190" ; the liquidis maintainell at this f o r boiut: miiiutes, a i d is then distilled, lie360 ARHTRACTS OP CHEJIICAL PAPERS.s v a l l quantities of di- and tri-methylamine pnss over, and at 200' afew drops of tropylen; whilst 13 methyltropidine passes over at204-205" (757 mm.), and a small quaritityof a base boiling at a veryhigh temperature remains behind as a thick, brown oil. It is acolourless, highly refractive oil, having a characteristic odour, and asp. gr. 0.922 at 15". When 13-methyltropidine is dissolved in hydro-chloric acid and the solution heated, tropylen separates as an oil andis driyen over with a current of steam ; whilst dimethylamine hydro-chloride remains behind. The fact that Ladenburg obtained tropylenand dimethylamine by heating tropidine methiodide with potash is,therefore, explained as follows :--a-Methgltropidine is initiallyformed, and this changes into the @-compound, which then decom-poses into fopylen and dimethylamine. When P-methyltropidineand met,hyl iodide are mixed in molecular proportion in methylalcoholic solution, tetramethylammonium iodide separates : thequicker if heat is applied ; whilst after removing the iodine fromthe solution by silver chloride, platinic chloride precipitates a pZatino-chloride, ( C,H,Me)2,H2Pt,(>16, as a bright-yellow, aniorphous precipitate,zind on evaporating the filtrate, an oily compound at first separates,R nd, later, lustrous crystals of the platinochloride, C,H1Me,,H,PtCl6.The author finds, contrary to TAadenburg's statement, that tropylenforms a crjstalline compound with potassium hydrogen sulphite, andit, must therefore be an aldehyde or a ketone ; since it gives an acidof the composition of adipic acid on oxidation, it is probably tetra-hydrobenzaldehyde, and in concordance with the above formulce, theA5-derivative. Ecgonine arid anhydroecgonine must, in conformitywith the above-given formula for tropine and tropidine, be repre-sented as follows:-,CHZ- CH2, CHZ- CH2,CH-CH(OH)-CH(COOH)-C ; CHLCH:C(COOH)-CH.'CH,--- NMe' 'C'H,----NMe/Ecgonine. Anh y droecgonine.The formation of dihydrobenzaldehyde from dibromanhydroec-gonine (Eichengrun arid Einhorn, Abstr., 1891, 65), then, admits ofsimple explanation. The dihydrobenzaldehyde must be the A3' 5-de-ri vative. A. R. L.A Violet from Codejlne. By P. CAZENEUYE (Conzpt. rend., 113,747--749).-10 grnms of codei'ne is heated with 10 grams of para-nitrosodimethylaniline i n presence of a litre of ethyl alcohol of 9 3 Ofor 300 hours. When tho liquid cools, i t deposits tetramethyldiamido-azobenzene. The alcohol is distilled off and the residue boiled withwater; after cooling, the liquid is filtered and agitated with amylalcohol, which dissolves out the violet colouring matter, whilst abeautiful blue colouring matter remains i n the water. When theamyl alcohol is evaporated, the violet, compound separates in amorph-ous, lustrous flakes, somewhat soluble in water, but especially solublei n ltlcohols and in ether, forming dichroic solutions. When theaqueous solution is poured on to strong sulphuric acid, it gives, likethe safranines, a green zone, changing to blue, and then to violetORGANIC CEEMISTRY. 361which indicates the presence of poly-acid combinations. The morph-ine violet gives a similar reaction.Codeine violet dyes silk, wool, and gun-cotton directly, but thecoloar alters somewhat when exposed to light.When the amyl alcohol solution of the compound is mixed withalcohol and ether, and treated with platinic chloride, a platino-chloride is obtained with a pder colour than the platinochloride ofthe analogous morphine compound.Nkfe$C6Hd*n: C17H18MeNOd, H2Pt CI,,NMe,*C6 H4*N :C17H,,MeNOd.It has the compositionand hence codeine violet has the composit’ionThe yield is small, but better results were not obtained by vary-Heating in a sealed ing the proportions uf tlhe reacting substances.tube gave a smaller yield (compare Abstr., 1891, 1220).C. H. B.An Alkaloid from Javan Coca Leaves. By F. GIESEL (Chem.Centr., 1891, ii, 488, from Pharrn. Zeit., 36, 419--420).-From 20kilos. of a smnll-leaved Javan coca, the author obtained 1 kilo. ofcinnamylcocaine, whilst about three times this amount, besides somecocaine, remained uncrystallisable. Prom the mother liquors analkalo’id was separated as hydrobromide, which resembled dextro-cocaine.The hydrochloride is more readily soluble i n water, and lesssoluble in alcohol, than is the hydrochloride of dextrococaine. Thesalts of the new alkaloid are precipitated crystalline from quitedilute solutions by potassium dichromate, which is not the casewith the salts of cocsi’ne or dextrococayne ; moreover, the polarisedray is not perceptibly deyiated.Concentrated hydrochloric acid splits it u p into benzoic acid andecgonine hydrochloride, without the formation of an intermediateproduct, as in the case of dextrococayne.The alkaloid could not be detected in the leaves of Americantruxillo ; a t the same time, an alkaloid, somewhat resembling Hesse’shygrine, but different from it., was obtained from them. It differsfrom Hesse’s hygrine in its solubility in solutions of the alkalis,and is destroyed by potassium permanganate ; whilst Hesse’s remainsunchanged. It occurs in the leaves in quanbities up to 0.2 per cent,and is 8 constituent of the plant, and not a product of decomposition.The hydrobromide melted at 49’.J. W. L.Cyanmethaemoglobin ‘and Detection of Hydrogen Cyanide.By R. KOBERT (Chem. Centr., 1891, ii, 501, from Apoth. Zeit., 6, 386).-Researches carried out by the author indicate that hydrogmcyanide forms with methEmoglobin a red compound cyan0m.t-hmnznglohin, which differs from oxyhmmoglobin and its modificativrisin that its spectrum is n o t characterised specially by any band.The remarkably bright-red colour of the blood, after poisoniiig withhydrogen cyanide, in places where the formation of methsemoglobi362 ABSTRACTS OF CHEMICAL PAPERS.has taken place, is caused by the formation of the cjanogen corn-pound.Blood which contains the cyanogen compmnd may be detectedilius:-l C.C. of the blood is dilutecl with 99 C.C. of water and n 1 percent. solution OF potassium ferricyanide is added drop by drop. I fcyanogen is absent, the colour of the solution passes from red toyellow, owing to the formation of methremoglobin, and it shows thecorresponding spectrum. In the presence of cyariogen, the colouronly becomes brighter red, and shows no absorption band. Hvdrogencyanide may be deteched by means of this test. Healthy blood isemployed, and, after diluting with water (1 C.C. of blood to 99 C.C. ofwater), it is shaken with a small crystal of potassium ferricyanideuntil the red colour has just changed to yellow, and it little of theliquid undei*.investigation is poured on to the surface. The presenceof hydrogen cyanide causes a bright-red coloration to form. Thesolutions must, nob be alkaline, b u t stionld be just acid.If blood contains cyanogen, a 1 per cent,. solution retains its colourfor some time ; whereas healthy blood becomes darker at the end ofa few hour6 or days, and shows the spectrum of hremoglobin.J. W. L.Transformations of Albumins. By G. PATEIN (Cornpi. rend.Snc. Bid., 1891, 207--212).--Brom experiments on egg-.albumin andserum-albumin, it is shown that the action of acetic acid and alkalisproduces changes in the albumin which render it 110 longer coagulableby heat or precipitable by certain reagents. The same sometimesoccurs in the albumin which passes into the urine in cases of disease.W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8926200285

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

362 ABSTRACTS OF UHEhIICAL PAPERS. P h y s i o l o g i c a l C b e m i s t r y . Digestive Ferments in Crustacean Eggs. By J. E. Amr,ous and I!. HEIM (Compt. Tend. Xoc. Biol., 1891, 273--275).-Various crustacean eggs were found to contain an amylolytic, an inverting, and a tryptic ferment. Their amount and activity probably varies with the degree of maturity of the eggs. These are regarded as enzymes, not as orgnnised ferments. Formation of Sugar in the Organism when Oxygen is deficient. By A. DBSTKE (Compt rend. SOC. R i d , 1891, 681 -684). -The recent experiments of Amki (Abstr., 1891,1125-1392) and by Zillessen (ibid., 1126) are merely confirmatory of some of fi more corn- W. D. H.PHTSTOLOGICAL GHEXISTRT. 3 6.3 plete nature made by the author some years ago (GZyc6mie asphyzique, 1879) ; these are not dluded to b y the authors j u s t mentioned. Gases of Peptone Blood.By RLACHSTE IN (A&. f. Anat. U. P h y ~ i d . , Ph?ysioZ. Ahth., 1891, 3!kh-401) .-In dogs, Labousse (Abstr., 1889, 5:31) has shown tbat injection of “ peptone ” lessens t h e amount of carbonic anhydride in the blood, whilst the oxygen reniains normal, or rather over the normal. It is now shown t h a t in the rabbit, a n animal whose blood is not rendered incoagulable by peptone, the same change in the blood gases occurs. Moreovei., t h e amount of carbonic anhydride in the lymph is not lessened, and so t h e diminution is not explicable on the ground of lessened metiibolism. The Specific Gravity of the Blood of Europeans living in the Tropics. By M.GLOGNER (Virchow’s Archiv, 126, 109-1 13). -The specific gravity of the blood was estimated by Hammerschlag’s method. A drop of blood is placed in a mixture of benzene and chloroform, and then benzene or alcohol, as the case may be, is added iintil the drop of blood swims. The mixture is filtered through l i ~ e n , and its specific gravity, taken with the hydrometer, gives that of the blood. The persons, 20 in number, on whom the observations were made were Europeans who had lived for varying periods in the East India Llands (six months to 29 years), and were suffering from varying degrees of “ tropical anEmia.” The average number of corpuscles was found to be normal ; but the sp. gr was 1.0% instead of the normal 1.062. The anpmia thus appears to be due to loss i n the constit,uents (probably prote’ids) dissolved in the blood plasma.By C. EIJKMBN (Virchow’s Archiv, 1 2 6 , 113- 124) .--This iiivestigation resembles that in the preceding abstract, hnt is rather more extensive. The specific gravity of blood was esti- mated by Schmaltz’ capillary pycnometer (Arch. KZin. Med., 1890) ; the corpusciilar richness by counting ; t h e percentage of hemoglobin by Flcischl’s haemometer. Observations were made both on Malays and Europeans, t h e latter being classified according t o their length of residence in the tropics. The blood on t h e average. gave throughout practically the same number of corpuscles, and the same percentage of hemoglobin. The average specific gravity was 1,057, length of stay in the Indies making no difference.Schmaltz gives t h e normal specific gravity as 1.059 ; so there is a slight fall, but nothirig like so great as in the more familiar forms of anemia. By V. HARLEY (J. PPhysioZ., l2,391--408).-In view of Schenk’s statement ( A bstr., 1891, 350, 504) that a considerable amount of sugar is lost when it is esti- mated in albuminous mixtures such as serum, a number of investiga- tions were made on this subject. A known amouiit of dextrose was mixed with defibrinated calf’s blood, the prote’ids removed by acetic acid, heat, and filtration, and the sugar estimated in the filtrate and washings ; t h e loss varied from 0 to 4.8 per cent. The reason of the W. D. H. W. D. H. W. D. H. Tropical Anemia. W. D. H. Disappearance of Sugar from the Blood.364 ABSTRACTS OF CHEMICAL PAPERS.variation appears to be the behaviour of the prote‘id on heat coagulation ; if the coagulum formed is dense and firm, the loss of sugar is great. If the proteid separates in loose, flocculent curds, the precipitate is more readily washed, and the loss of sugar reduced to a minimum. Similar results followed experiments made with blood drawn directly from an artery in a living animal, and also when other met,hods of precipitating the proteids (potassio-mercuric iodide, mercuric chloride) were employed ; and the general conclusion is drawn that the loss of sugar is due to mechanical retention by, not chemical combination with, the coagulated prote’id. In addition to this, however, the element of time has to be taken into account; the longer the blood, if fresh, and sugar solutions are mixed, the greater is the loss of the sugar ; this is not due to bacteria. The glycolvsis is of a progressive character.W. D. H. Glycolytic Power of Blood and Artificial Production of Diabetes. By R. LBPINE and BARRAL (Compt. ?-end., 113, 729-730). -Moderate bleeding of a dog at first (after a short time) increases the glycolytic power of the blood, but repeated bleeding reduces it,. Ligature of Wirsung’s canal causes a great increase of the glycolytic power of the blood. Giiitzner found that under the same conditions there was an increase in the saccharifying power of the urine, and the authors find that this is true also of the blood. Section of the nerves of the pancreas is followed by a great increase in the glycolytic and saccharifying power of the blood. Electrification of the lower end of the pancreatic nerves produces diabetes after a short time.C. H. B. Influence of Muscular Work on the Elimination of Creatinine. By J. MOITESSIER (Compt. rend. Soc. Rid., 1891, 573--574).-After muscular work (walking), no increase in the amount of weatinine in the urine was observed. The experiments were made on t.he author’s own person. W. D. H. Xanthocreatinine in the Urine. By G. COLOSANTJ ( Gazzetta, 21, ii, 188--192).-The urine of the lion is very rich in urea, which, when extracted by Hoppe- Seyler’s method, crystallises in thin, snow- white scales, not i n needles as does that obtained from the urine of the dog. The alcoholic mother liquor from the crystallisation and washing of the urea when concentrated is of a sjrupy consistency, and bas an aromatic odour; i t contains, besides much creatinine, xanthocreatinine, which may be separated as ’ a yellow, crystalline powder.Monari (Abstr., 1886, 613) has shown that if large quantities of creatine, or creatinine, are introduced into the circulation, either by intravascular injection o r as the result of excessive muscular effort., t,he bases are partly eliminated as xanthocreatinine. As bhe rich meat, diet of the lion introduces into the system large quantities of crea- tine, the author supposes that part of the base is secreted a s xautho- creatinine. w. J. P.PHYSIOLOGIC A L OHE3IISTRY. 365 IS Alcohol Eliminatsd by ths Milk? By F. R L i N G E m x N ( V~TC~LOW’R Archie, 126, 72--80).--Hy administering fairly large doses of alcoholic liquors to nursing women, none was ever f o u n d in the milk.I n animals in which proportionally larger doses were given, minute traces were occasionally found. Action of Pilocarpine on the Excretion of Milk. By. C. CORNEVIN (Compt. rend. SOC. Riol., 1891, 6%-630).-Pilocarpine IS a drug which increases the amount of many secretions, such as sweat and saliva. By experiments on cows, it was, however, found that it does not increase the amount of milk secreted. Analysis of the milk showed a slight increase in the amount of lactose. There is no gig- cosuria. W. D. H. W. D. H. Excretion of Uric Acid and Urea. By W. P, HERRINGHAM and H. 0. DAVIES (J. Physiol., 12, 475--477).-Haig states that the pro- portion of uric acid to urea varies inversely with the daily total acidity of the urine.Haig estimated uric acid by Haycraft’s method. In the present research, uric acid was estimated by Ludwig’s modifica- tion of Salkowski’s process, and urea by the hypobromite method. Two experiments were made, one of 16 days on a mixed diet, onc of eight days on a vegetable diet. The proportion of uric acid to urea varied, but bore no fixed relation to the total acidity of the urine. Excretion of Uric Acid, Urea, and Ammonia. By W. P. HERRINGHAM and E. W. GROVES ( J . Physiol., 12, 478-484.)-A series of experiments similar to the preceding, but performed more carefully, the composition of tbe diet being noted. The results obtained showed that the excretion of uric acid does not vary inversely with the daily acidity of the urine, aad that uric acid may be passed to the amount of .‘,t,h of the urea without bad effects.On three occasions sodinrn salicylate was given; these coincided with large excretions of uric acid. This may, however, have been due to the salicyluric acid in the urine ; or i t may have been accidental, as on other days, when no drug was given, the excretion was as large, W. D. H. W. D. H. Heat Production in Nerves during Excitation. By G. N. STEWAW (J. Yhysiol., 12, 409--425).-1n the nerves of rabbits and dogs there is not even a rise of temperature of the general nerve sheath of H$aat,h of a degree during excitation. On theoretical grounds, the statement of Rolleston CAbstr., 1890, 536), that a frog’s nerve gives off heat when i t dies, is considered to be erroneous.W. D. H. Physiological Action of Nickel Carbon Oxide. By M. HAS- RioT and c. KICHET (C‘ompt. rend. HOG. Bid., 1891, 185--186).-This compound is extremely poisonous. The blood shows the spectrum of carbonic oxide haemoglobin. (Compare McKendrick and Snod- grass, Abstr., 1891, 1130.) Physiological Action of Nickel Carbon Oxide. By P. LANGLO~S (C‘ornpt. rend. Soc. Riol., 1891, 212--213).-T*he oxygen of VOL. LXII. 2 G W. I). H.3 6 6 ARSTRXCTS OF CHEIIICAL PAPERS. oxyhmmoglobin is displaced by this substance, but it is regarded as unsettled whether the compound formed is carbonic oxide haemo- globin, or harnoglobin united t o the nickel compound. W. D. H. Physiological Action of Trimethylamine. By COMREM ALE and BRUNELLE (Compt. rend.SOC. Uiol., 1891, 175--178).-Inhalation of the vapour of trimethylamine produces an increased secretion of saliva. The same effect follows its administration by the mouth, or under the skin, The alkalinity of the saliva is greater than normal. Occasionally vomiting is produced, also increase of the nasal mucus aiid of tears. There is always slight albuniinuria. After sub- cutaneoiis administration, there is local inflammation a t the point of injrctioni leaving a wound which takes a long time to heal. A dose of 3 centigrams per kilo. of body weight causes a lowering of body temperature. W. I). H. Physiological Action of Dinitrobenzene. By A. HURER (Virchods Archiv, 126, 240-270) .-The main effects of dinitro- benzene, as tested on both cold- and warm-blooded animals, are changes i n the blood, paralysis, and intense dyspnoea.The blood becomes of a dark chocolate coloiir ; the red corpuscles are largely deprived of their pigment, which in frogs partly collects round the nucleus. Spectroscopic investigation showed an absorption band in the red, reminding one of the similar band of acid h ~ m n t i n , and of methaemo- globin, b u t not identical with either. It is spoken of as the dinitro- benzene band, and it is considered that this compound acts in a specific manner on the blood pigment. After large doses, the urine was found to be brown in colour, and to contain a strongly reducing substance, and sometimes diriitrobenzene was itself present. The body temperature is lowered. The illness which workers in roburite factories suffer from appears to be caused by dinitrobenzene fumes.W. D H. Relation between the Chemical Constitution and Physio- logical Action of Compounds of the Aromatic Series. By G. ODDO (Guzzetta, 21, ii, 237-258).- BENZENE NUCLEUS.-I. 5atobenzene.-This componnd, prepared by the author’s method (Abstr., 1891, 696), has a very energetic antipyretic and analgesic action on mammals, both in the normal and febrile conditions. I t s snt,ipyretic action is probably more powerful than that of any other known substance, the temperature i n mammals falling almost to the point of collapse wit>h complete anmthesia; these effects last for 24 or more hours, paralysis and death often supervening. The action is accompanied by a rise in the pulse rate, and does not commence until some hours after admi- nistration, probably owing to its insolubility; the acidity of the stomach also affects the rapidity and extent of the action.It is probably eliminated from tho body by the skin and luugs. Frogs, on the other hand, exhibit convulsive movements and depressed pulse. It thus appears that azoimide does not retain its physiological pro- perties (Ber., 1890, 1023 ; Abstr., 1891, 56 and 524) when in com- bination with organic radicles.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 367 11. Benzamide acts as a gentle antipyretic; its action is rapidly It probably passes from the system developed. and soon ceases. t1,roiigh the skin and lungs. NAPHTHALENE NUCLEUS -Ethyl a-naphthylaroacetoacetate, C ,,H,*N,*CHAc*CO OEt (Ahstr., 1891, 1.381), gave neqatfive results in experiments on dogs and frogs.a- Acetonuphthalide, which resembles some well-known antipyretics of t h e benzene groiip in constitution, likewise gave rise to no noteworthy symptoms. This behaviour is attributed by the author to the physioiogical inactivity of the naphthalene nucleus. The phenrtuthrene nucleus appears to be similarly inactive, a sub- cutaneous injection of 0.04 gram only feebly affecting a frog. In conclusion, the aiithor ascribes the antipyretic properties of benzene compounds to the presence of the benzene nucleus, and regards the absence of tbese properties from naphthalene compouuds as indicative of the absence of a preformed benzene nucleus from these substances and hence as con6rmatory of Barn berger’s centric formuh.S. B. A. A.362 ABSTRACTS OF UHEhIICAL PAPERS.P h y s i o l o g i c a l C b e m i s t r y .Digestive Ferments in Crustacean Eggs. By J. E. Amr,ousand I!. HEIM (Compt. Tend. Xoc. Biol., 1891, 273--275).-Variouscrustacean eggs were found to contain an amylolytic, an inverting, anda tryptic ferment. Their amount and activity probably varies withthe degree of maturity of the eggs. These are regarded as enzymes,not as orgnnised ferments.Formation of Sugar in the Organism when Oxygen isdeficient. By A. DBSTKE (Compt rend. SOC. R i d , 1891, 681 -684).-The recent experiments of Amki (Abstr., 1891,1125-1392) and byZillessen (ibid., 1126) are merely confirmatory of some of fi more corn-W. D. HPHTSTOLOGICAL GHEXISTRT. 3 6.3plete nature made by the author some years ago (GZyc6mie asphyzique,1879) ; these are not dluded to b y the authors j u s t mentioned.Gases of Peptone Blood.By RLACHSTE IN (A&. f. Anat. U. P h y ~ i d . ,Ph?ysioZ. Ahth., 1891, 3!kh-401) .-In dogs, Labousse (Abstr., 1889,5:31) has shown tbat injection of “ peptone ” lessens t h e amount ofcarbonic anhydride in the blood, whilst the oxygen reniains normal,or rather over the normal. It is now shown t h a t in the rabbit, a nanimal whose blood is not rendered incoagulable by peptone, the samechange in the blood gases occurs. Moreovei., t h e amount of carbonicanhydride in the lymph is not lessened, and so t h e diminution is notexplicable on the ground of lessened metiibolism.The Specific Gravity of the Blood of Europeans living inthe Tropics.By M. GLOGNER (Virchow’s Archiv, 126, 109-1 13).-The specific gravity of the blood was estimated by Hammerschlag’smethod. A drop of blood is placed in a mixture of benzene andchloroform, and then benzene or alcohol, as the case may be, is addediintil the drop of blood swims. The mixture is filtered throughl i ~ e n , and its specific gravity, taken with the hydrometer, gives thatof the blood.The persons, 20 in number, on whom the observations were madewere Europeans who had lived for varying periods in the East IndiaLlands (six months to 29 years), and were suffering from varyingdegrees of “ tropical anEmia.” The average number of corpuscles wasfound to be normal ; but the sp. gr was 1.0% instead of the normal1.062.The anpmia thus appears to be due to loss i n the constit,uents(probably prote’ids) dissolved in the blood plasma.By C. EIJKMBN (Virchow’s Archiv, 1 2 6 , 113-124) .--This iiivestigation resembles that in the preceding abstract,hnt is rather more extensive. The specific gravity of blood was esti-mated by Schmaltz’ capillary pycnometer (Arch. KZin. Med., 1890) ;the corpusciilar richness by counting ; t h e percentage of hemoglobinby Flcischl’s haemometer. Observations were made both on Malaysand Europeans, t h e latter being classified according t o their length ofresidence in the tropics. The blood on t h e average. gave throughoutpractically the same number of corpuscles, and the same percentageof hemoglobin. The average specific gravity was 1,057, length ofstay in the Indies making no difference.Schmaltz gives t h e normalspecific gravity as 1.059 ; so there is a slight fall, but nothirig like sogreat as in the more familiar forms of anemia.By V. HARLEY (J.PPhysioZ., l2,391--408).-In view of Schenk’s statement ( A bstr., 1891,350, 504) that a considerable amount of sugar is lost when it is esti-mated in albuminous mixtures such as serum, a number of investiga-tions were made on this subject. A known amouiit of dextrose wasmixed with defibrinated calf’s blood, the prote’ids removed by aceticacid, heat, and filtration, and the sugar estimated in the filtrate andwashings ; t h e loss varied from 0 to 4.8 per cent. The reason of theW. D. H.W. D. H.W.D. H.Tropical Anemia.W. D. H.Disappearance of Sugar from the Blood364 ABSTRACTS OF CHEMICAL PAPERS.variation appears to be the behaviour of the prote‘id on heat coagulation ;if the coagulum formed is dense and firm, the loss of sugar is great. Ifthe proteid separates in loose, flocculent curds, the precipitate is morereadily washed, and the loss of sugar reduced to a minimum.Similar results followed experiments made with blood drawndirectly from an artery in a living animal, and also when othermet,hods of precipitating the proteids (potassio-mercuric iodide,mercuric chloride) were employed ; and the general conclusion isdrawn that the loss of sugar is due to mechanical retention by, notchemical combination with, the coagulated prote’id. In addition tothis, however, the element of time has to be taken into account; thelonger the blood, if fresh, and sugar solutions are mixed, the greateris the loss of the sugar ; this is not due to bacteria.The glycolvsisis of a progressive character. W. D. H.Glycolytic Power of Blood and Artificial Production ofDiabetes. By R. LBPINE and BARRAL (Compt. ?-end., 113, 729-730).-Moderate bleeding of a dog at first (after a short time) increasesthe glycolytic power of the blood, but repeated bleeding reduces it,.Ligature of Wirsung’s canal causes a great increase of the glycolyticpower of the blood. Giiitzner found that under the same conditionsthere was an increase in the saccharifying power of the urine, and theauthors find that this is true also of the blood.Section of the nervesof the pancreas is followed by a great increase in the glycolytic andsaccharifying power of the blood. Electrification of the lower endof the pancreatic nerves produces diabetes after a short time.C. H. B.Influence of Muscular Work on the Elimination of Creatinine.By J. MOITESSIER (Compt. rend. Soc. Rid., 1891, 573--574).-Aftermuscular work (walking), no increase in the amount of weatinine inthe urine was observed. The experiments were made on t.he author’sown person. W. D. H.Xanthocreatinine in the Urine. By G. COLOSANTJ ( Gazzetta,21, ii, 188--192).-The urine of the lion is very rich in urea, which,when extracted by Hoppe- Seyler’s method, crystallises in thin, snow-white scales, not i n needles as does that obtained from the urine ofthe dog.The alcoholic mother liquor from the crystallisation andwashing of the urea when concentrated is of a sjrupy consistency,and bas an aromatic odour; i t contains, besides much creatinine,xanthocreatinine, which may be separated as ’ a yellow, crystallinepowder.Monari (Abstr., 1886, 613) has shown that if large quantities ofcreatine, or creatinine, are introduced into the circulation, either byintravascular injection o r as the result of excessive muscular effort.,t,he bases are partly eliminated as xanthocreatinine. As bhe rich meat,diet of the lion introduces into the system large quantities of crea-tine, the author supposes that part of the base is secreted a s xautho-creatinine. w. J.PPHYSIOLOGIC A L OHE3IISTRY. 365IS Alcohol Eliminatsd by ths Milk? By F. R L i N G E m x N( V~TC~LOW’R Archie, 126, 72--80).--Hy administering fairly large dosesof alcoholic liquors to nursing women, none was ever f o u n d in themilk. I n animals in which proportionally larger doses were given,minute traces were occasionally found.Action of Pilocarpine on the Excretion of Milk. By. C.CORNEVIN (Compt. rend. SOC. Riol., 1891, 6%-630).-Pilocarpine IS adrug which increases the amount of many secretions, such as sweatand saliva. By experiments on cows, it was, however, found that itdoes not increase the amount of milk secreted. Analysis of the milkshowed a slight increase in the amount of lactose. There is no gig-cosuria. W. D. H.W. D. H.Excretion of Uric Acid and Urea.By W. P, HERRINGHAM andH. 0. DAVIES (J. Physiol., 12, 475--477).-Haig states that the pro-portion of uric acid to urea varies inversely with the daily totalacidity of the urine. Haig estimated uric acid by Haycraft’s method.In the present research, uric acid was estimated by Ludwig’s modifica-tion of Salkowski’s process, and urea by the hypobromite method.Two experiments were made, one of 16 days on a mixed diet, onc ofeight days on a vegetable diet. The proportion of uric acid to ureavaried, but bore no fixed relation to the total acidity of the urine.Excretion of Uric Acid, Urea, and Ammonia. By W. P.HERRINGHAM and E. W. GROVES ( J . Physiol., 12, 478-484.)-A seriesof experiments similar to the preceding, but performed more carefully,the composition of tbe diet being noted.The results obtained showedthat the excretion of uric acid does not vary inversely with the dailyacidity of the urine, aad that uric acid may be passed to the amountof .‘,t,h of the urea without bad effects. On three occasions sodinrnsalicylate was given; these coincided with large excretions of uricacid. This may, however, have been due to the salicyluric acid inthe urine ; or i t may have been accidental, as on other days, when nodrug was given, the excretion was as large,W. D. H.W. D. H.Heat Production in Nerves during Excitation. By G. N.STEWAW (J. Yhysiol., 12, 409--425).-1n the nerves of rabbits anddogs there is not even a rise of temperature of the general nervesheath of H$aat,h of a degree during excitation. On theoreticalgrounds, the statement of Rolleston CAbstr., 1890, 536), that a frog’snerve gives off heat when i t dies, is considered to be erroneous.W. D.H.Physiological Action of Nickel Carbon Oxide. By M. HAS-RioT and c. KICHET (C‘ompt. rend. HOG. Bid., 1891, 185--186).-Thiscompound is extremely poisonous. The blood shows the spectrumof carbonic oxide haemoglobin. (Compare McKendrick and Snod-grass, Abstr., 1891, 1130.)Physiological Action of Nickel Carbon Oxide. By P.LANGLO~S (C‘ornpt. rend. Soc. Riol., 1891, 212--213).-T*he oxygen ofVOL. LXII. 2 GW. I). H3 6 6 ARSTRXCTS OF CHEIIICAL PAPERS.oxyhmmoglobin is displaced by this substance, but it is regarded asunsettled whether the compound formed is carbonic oxide haemo-globin, or harnoglobin united t o the nickel compound.W.D. H.Physiological Action of Trimethylamine. By COMREM ALE andBRUNELLE (Compt. rend. SOC. Uiol., 1891, 175--178).-Inhalation ofthe vapour of trimethylamine produces an increased secretion ofsaliva. The same effect follows its administration by the mouth, orunder the skin, The alkalinity of the saliva is greater than normal.Occasionally vomiting is produced, also increase of the nasal mucusaiid of tears. There is always slight albuniinuria. After sub-cutaneoiis administration, there is local inflammation a t the point ofinjrctioni leaving a wound which takes a long time to heal. A doseof 3 centigrams per kilo. of body weight causes a lowering of bodytemperature.W. I). H.Physiological Action of Dinitrobenzene. By A. HURER(Virchods Archiv, 126, 240-270) .-The main effects of dinitro-benzene, as tested on both cold- and warm-blooded animals, are changesi n the blood, paralysis, and intense dyspnoea. The blood becomes ofa dark chocolate coloiir ; the red corpuscles are largely deprived oftheir pigment, which in frogs partly collects round the nucleus.Spectroscopic investigation showed an absorption band in the red,reminding one of the similar band of acid h ~ m n t i n , and of methaemo-globin, b u t not identical with either. It is spoken of as the dinitro-benzene band, and it is considered that this compound acts in aspecific manner on the blood pigment. After large doses, the urinewas found to be brown in colour, and to contain a strongly reducingsubstance, and sometimes diriitrobenzene was itself present.Thebody temperature is lowered. The illness which workers in roburitefactories suffer from appears to be caused by dinitrobenzene fumes.W. D H.Relation between the Chemical Constitution and Physio-logical Action of Compounds of the Aromatic Series. By G.ODDO (Guzzetta, 21, ii, 237-258).-BENZENE NUCLEUS.-I. 5atobenzene.-This componnd, preparedby the author’s method (Abstr., 1891, 696), has a very energeticantipyretic and analgesic action on mammals, both in the normaland febrile conditions. I t s snt,ipyretic action is probably morepowerful than that of any other known substance, the temperaturei n mammals falling almost to the point of collapse wit>h completeanmthesia; these effects last for 24 or more hours, paralysis anddeath often supervening. The action is accompanied by a rise inthe pulse rate, and does not commence until some hours after admi-nistration, probably owing to its insolubility; the acidity of thestomach also affects the rapidity and extent of the action. It isprobably eliminated from tho body by the skin and luugs. Frogs,on the other hand, exhibit convulsive movements and depressed pulse.It thus appears that azoimide does not retain its physiological pro-perties (Ber., 1890, 1023 ; Abstr., 1891, 56 and 524) when in com-bination with organic radiclesVEGETABLE PHYSIOLOGY AND AGRICULTURE. 36711. Benzamide acts as a gentle antipyretic; its action is rapidlyIt probably passes from the system developed. and soon ceases.t1,roiigh the skin and lungs.NAPHTHALENE NUCLEUS -Ethyl a-naphthylaroacetoacetate,C ,,H,*N,*CHAc*CO OEt(Ahstr., 1891, 1.381), gave neqatfive results in experiments on dogsand frogs. a- Acetonuphthalide, which resembles some well-knownantipyretics of t h e benzene groiip in constitution, likewise gave riseto no noteworthy symptoms. This behaviour is attributed by theauthor to the physioiogical inactivity of the naphthalene nucleus.The phenrtuthrene nucleus appears to be similarly inactive, a sub-cutaneous injection of 0.04 gram only feebly affecting a frog. Inconclusion, the aiithor ascribes the antipyretic properties of benzenecompounds to the presence of the benzene nucleus, and regards theabsence of tbese properties from naphthalene compouuds as indicativeof the absence of a preformed benzene nucleus from these substancesand hence as con6rmatory of Barn berger’s centric formuh.S. B. A. A

ISSN:0368-1769    

DOI:10.1039/CA8926200362

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 367 Chemistry of Vegetable Physiology and Agriculture. Nitrification of Organic Nitrogen. By T. LEONE and 0. &lAGhTANrNr ( Gazaetta, 21, ii, 206--908).-The authors have inst,itu ted experiments to determine whether organic nitrogen is completely con- verted into nitric acid by the nitrifying organism. A quantity of gelatin solution containing 0.04-0.07 gram of nitrogen was dissolved i n 2-3 litres of water, and kept at 32" for 45 days, after which time neither ammonia nor nitrons acid was present in the Bolution, so that the action may be considered to have ended. On determining the nitric acid, a deficit of 17.4-19.0 per cent. on the amount of nitrogen originally present was observed. This nitrogen must either have been evolved in the free state or remaiued in the solution as organic matter not convertible by the organism.The Sources of the Nitrogen of our Leguminous Crops. By Sir J. B. LAWES and J. H. C*It,BERT (Jour. By. Agri. Xoc. [3], 2, 657-720),- Both the scientific interest and practical value of legn- minous crops depend largely on the amqnnt of nitrogen they contain and on the sources of this nitrogen ; also on the great difference in these respects between them and the agricultural plants of other orders. Gmin and root crops and potatoes cannot be successfully grown without the application of nitrogenous manure, whilst the direct effect of such manure is to increase riot so much the nitrogen- ous as the non-nitrogenous constituents of the plants-the carbo- hydrates. This is well illustrated by the results of field exppriments made at Rothamsted; the results show that when nitrogenous W.J. P. 2 c 2368 ABSTRACTS OF CHEMICAL PAPERS. manures are applied in conjunction with minerals, there is an enorm- ons increase in the carbon assimilation and carbohydrates formed a s compared with the amounts assimilated under the influence of minerals only. On the other hand, leguminous crops, grown without nitrogenous manure, contain a higher percentage of nitrogen than non-leguminous crops, and yield also a much greater amount of nitrogen over a given area of land ; nitrogenous manures have little o r no effect when given to them, and the carbon assimilation is not materially increased. Roussingault's experiments, and the earlier experiments made at Rothamsted (this Journal, 1863, loo), showed that, under conditiolis of sterilisation and enclosure, there was no gaiu from free nitrogen in the growth of either Gyaminem, Legurninosa?, o r other plants.The results obtained by Hellripgel and others, and especially those ob- tained a t Rothamsted in 1888 (Abstr., 1890, 814), are next discussed. They show that, under non-sterilised conditions-in fact, with suit- able microbe infection of the soil-there was nodule formation on the roots and considerable fixation of free nitrogen. These results have received confirmation f rorn still more recent Rothamsled experi- ments, and also from t4he direct experiments of Schloesing, jun., and Tlaurent (Abstr., 1891, 553), who determined the loss of nitrogen which took place i n the confined air in which their plants were grown.In lg89, and since, quantitative experiments have been made with peas, beans, vetches, lupins, white clover, red clover, sanfoin, and lucerne ; that is to say, with four annuals and four plants of longer life. The results, as far a s they are available, show that without soil-extract seeding, and with no nodules, there was no gain of nitrogen ; whilst with soil extract, and with nodule formation, there was a considerable gain of nitrogen, in fact, very many times as much nitrogen in the products of growth as in the seeds sown. The difficulky at first exprrienced by Hellrieqel in obtaining good results with lupins, and a t Rothamsted with yellow and blue lupins in 1888, seems to be due to the infecting soil which was used being unsuitable.Nobbe's experiments (Abstr., 1891, 1533) indicate that there are a variety of leguminous nodule-organisms, which have very iliff erent effects with the diffkrent plants (compare also Beyerinck, Abstr., 1891, 7539). This would also be consistent with the observa- tions made a t Rothanisted with various plants, showing that the external appearance and distribution of the nodules were very clifierent in the case of peas, vetches, lupins, and other plants. A series of experiments was commenced at Rothamsted in 1890, with a view to the mor3 detailed examioat'ion of the roots of the plnilts than was possible in the case of the strictly quantitative series. The plants were grown in pits, so arranged that some of the plants of each description could be taken up and their roots examined at three (or four) successive periods of growth.Each plant was grown in sand supplied with minerals and soil extract, and in a ruixture of soil and mnd. Generally speaking, in sand, the area of infection was limited, but the nodules were of great size ; in soil with much greater distribution of the infccting organisms, there was a far greater number of nodules, which were, however, smaller than those grown in sand. The results of determinations of dry matter and nitrogen inVEGETARLE PHYSIOLOGY ASD AQRICZLTURE. 3G9 the nodules of the plants taken up at, different periods indicate that in the case of the annual, whcn the seed is formed and the plant more or less exhausted, both the actual amount of nitrogen in the nodnles and its percentage in the dry substance are greatly reduced; but that with the plant of longer life, although the earlier-formed nodules become exhausted, others are constantly produced, thus pro- viding for future growth.And the results of these experiments, taken together with those of the quantitative series, show further an intimate connection between the gain of nitrogen by the LeguminosGe and the development of the nodules on their roots.. As to the manner in which nitrogen is fixed, it has been suggested that, under the conditions of the symbiosis, the plant is enabled to fix the free nitrogen of the atmosphere by its leaves ; but there is little or nothing i n the evidence we have which leads to this conclusion. It is also suggested that the bacteria of the nodules become distribnted in the soil and there fix nitrogen, which is subsequently taken by the plants from the soil.In the Rothamsted experiments, however, no gain of niti-ogen was observed in the soils. Berthelot found that soils both free from higher vegetation, and soils in which leguminous plants were growing, gained in nitrogen ; and Schloesing, ~ u n . , and Laurent also found fixation to take place in soils under the influence of lower plants-lichens and algE. Nevertheless, neither experience in practical agriculture, nor the nitrogen statistics of soils and crops, indicate any material fixation of free nitrogen under the agency of microbes within the soil, independently of leguminous growtk There is, however, evidencc that, in soils and subsoils containing combined nitrogen, lower organisms may serve the higher by bring- ing the organic nitrogen into an available form.As examples may be mentioned the fungus of fairy rings, the fungus mantle obsrrred by Frank on the roots of certain trees, and especially the nitrifying organisms. To return to the question of fixation, the most probable explanation seems to be that free nitrogen is fixed in the course of the development of the organisms within the nodules, and that the resulting nitrogenous compounds are absorbed and utilised by the plant. It may be mentioned that Loew (Abstr., 18’30, 10.52), viewing the question in the light of his own results with plalinuni in presence of alkali, suggested the possibility that the vegetable cell, with its active protoplasm, if in an alkaline condition, may fix free nitrogen with formation of ammonium nitrite.It was frequently found a t Rothamsted that the contents of the nodules, when apparently in an active condition, showed a weak alkaline reaction. Although much of the nitrogen o€ leguminous crops is sometimes obtained under the cmditions described, from the free nitrogen of the air, a good deal is taken up from the subsoil, chiefly as nitric acid derived from the organic matter present in the soil. A difficulty in the way of the assumption that much of the greater assimilation of the Leguminosae than by other plants is due to nitrification of the subsoil is the fact that the direct application of nitrates has but little effect on the growth of such plants.The two cases are, however, differen+ nitrates, when applied, percolate more or less alone through the soil, whilst nitrates formed as a result of action on the organic nitrogefi37 0 ABSTRACTS OF CHEMIOAL PAPERS. will probably be associated with other constituents liberated at the acime time. With regard to the more practical aspects of the subject, reference is made to the experiments of Schultz, of Lupitz, who has, for some years, grown leguminous crops overlarge areas of poor sandy soil. using kainite and phosphatic manures ; he finds the lands thereby muclt benefited for subsequent cereal and other crops. The system is extending in other parts of Germany, and in this country Mr. Mason, of Eynsham Hall, Oxon,is making extensive experinients on the subject. “ The experimental results which have been brought forward clearly established that there is great gain of nitrogen under some conditions.It has also been clearly shown that due infection of the soil and of the plant is an essential to success. The evidence at the Rame time points to the conclusion that the soil may be duly infected for the growth of one description or some descriptions of plant, but not for some other descriptions. The field experiments on leguminous crops at Rothamsted have further shown, so to speak, that land which is quite exhausted, so far as the growth of one leguminous crop is concerned,may still grow very luxuriant crops of another description of the same family, but of different habits of growth, and especially of different character and range of roots.This result, though undonbtedly more or less due to other causes also, is, nevertheless, in some cases doubtless dependent on the existence, the distribution, and the condition, of the appropriate microbes for the due infection of the different descriptions of plant. In fact, i t is pretty certain that success in any system involving a more extended growth of leguminous crops in our rota- tions will not be obtained without, having recourse to a considerable variation in the description of leguminous plant grown. Other essential conditions of success will generally be the liberal application of potash and phosphatic msnures, and sometimes chalking or liming, for the leguminous crop. Then, the questions would arise-how long the legumirions crop should occupy the land ; to what extent it shoulii be consumed on the land, or the manure from its consumption be re- turned ; or, under what conditioiis the whole, o r part, of it should bc ploughed i n ? Lastly, it is probable that more benefit would accrue to the lighter and poorer than to the heavier o r richer Foils by any such extended growth of leguminous crop.” Assimilation of Free Nitrogen by Plants in its Dependence on Species, on Nutrition, and on Soil.By B. FRANK (Lnndtc. Jahrb., 21, 1-44) .-1. Dependence o n Species. (a.) Cryptogums.- Earlier investigators ascribed to the non-chlorophyllous crypt ogams the power of assimilating free nitrogen (Jodin, Compt. rend., 55, 612 ; Hallier, Gdhrungsercheinungw, Leipzig, 1867), whilst more recently this has been denied (Nageli, Xitzungsber.kgZ. bail.. A kad., 1879). The author’s experiments w i t h a form of penicillium, with pure cultivations of the fungus of leguminous root-nodules, and with chlorophyllous ctlgi-52, show that, when grown in non-nitr ogenous mediib and in air free from combined nitrogen, they will develop, although only slowly, and take up elementar-y nitrogen. ( b . ) Phanw-oguns.- The experiments with phaneiogams were, like thoFe preriously de- N. H. M.VEGETABLE PHYSIOLOQP AND AQRICULTURE. 371 Seeds. grum 0.007 0*012 scribed (Ahstr , 1891, 353). made in glass pots or in glass dishes and expnsed to air. The first experiments were made with bnckwhertt and spurrey in sandy soi I (12 kilos.) ; a fallow experiment with heavy loam was also made.The following results were obtairied (compare results with oats and rape in loam and with yeilow lupins in sandy soil, loc. cit.) :- Sand. Produce. 1 Soil. Gain. grnms gram 1 grams grams 1-15 u.082 @*14)* (1.065) 1'15 0.111 1'21 0.159 -------_I--- TABLE I. Kind and number of plant. ___I-- 1. Buckwheat (18) .. 2. Corn spurrey . . . . Dry produce. -- grams 10.354 16.755 Nitrogen. At conclusion. I At cornmencement. -.- I- * Assuming the percentage given (1 '0178) to be a mieprint for 0 -0178. The gain in the soil was greatest in the case of yellow lupins ( b c . c k ) , and is there much too great to be due to the small amount of roots left in. In no case was there any material loss in the soil, show- ing that the nitrogen of the plants was derived from the air. 2.InJEuence of Nutrition.--In order to ascertain the effect of different nitrogenous manures on the amount of nitrogen fixed, ex- periments were made with yellow lupins which were grown in ignited sand supplied with minerals : some pots had no nitrogen, others had 0.12 gram of nitrogen, either as calcium nitrate, as ammonium sulph- ate, or as urea. I n each case there were two sets of experiments, one microbe-seeded and the other not. There mere four pots (one plant in ew.ch) for each experiment. I n most cases, there were no nodules formed in those pots which were iiot intentionally infected, and them were generally nodules on the roots of the plants to which soil was added for seeding. The total produce, &c., was determined in each experiment (the plants of the several pots of one set being takei. together).As there were some failures, the average amount of pro- duce f o r the successful pots arid the amount of nitrogen in it and in the seed sown is given in Table 11, p. 372. The actual gain, if any. cannot be ascertained, as, with the exception of the experiments with nitrates, the final amount of nitrogen in the sand was not determined. The results show t.hat yellow lupins mid peas, without the help of soil, develop orgallisms when snpplied with nitrogenous manure, b u t there is better development when the plants are infected and are nob supplied with conibined nitrogen than when the plants are not infected but are supplied with combined nitrogen. In the case of yellow lupins growing in symbiosis with soil organisms, the application of nitrogenous mainires (at least, as nitrqte, ammonia, and we.) seemq to act injuriously.Peas grow best under the simultaneous action of the symbiosis and nitrate,372 ABSTRACTS OF CHEMIOAL PAPERS. Dry pro- d uce (grams). TABLE 11. At commence- ment. Seed Nitrate, (gram). (gram). &C. Nitrogen. l l Produce (gram). As Tn pro- nitrate duce. N in seed (gram). - - 1. Yellow Lupin,c. . I I I '7 *859 4.890 { 7.088 5 *598 { 10 *071 1. Seeded ........... 2. Seeded calcium 3. Not seeded}nitrate 4. Seeded 1a:tlmon - 0-12 0'12 0*12 0.12 5 . Not seededrsulph. 6. Seeded 7. Not seeded}urea * * 0.039 0.057 0.052 0.0'71 0.048 8. Seeded ........... 9. Seeded lcalcium 10. Not seeded( nitrate 31. Seeded ammon 12. Not seeded} sulph. ' 0 -009 0 -009 0 -009 0.009 0 so09 0 -009 0 *009 2.264 6 '480 { 4.330 4.971 { 5 -468 - 0'12 0 -12 0'12 0.12 0'12 0 '12 At commencement.At conclusion. Soil. Seed. Total. Soil. Produce. Total. - - ~ - ~ - - 0'30 - 0-30 0.40 0 30 0.014 0.314 0.39 0.27 0'003 0'273 0.37 Pens. 2 . Oats.. .... 3. Rape ..... At conclusion. 1 I 8.26 2 -13 I I 0-112 0.094 0 -078 0 *051 0 -049 0 -092 0.111 - 0 -002 0 -007 12 '3 10.3 8 '6 5 . 5 5 *4 10.1 12.3 0 -009 0.009 0 -009 0.009 0 a 9 - 0*0015 0 '0010 4 . 2 13 '4 5 * 5 7 ' 5 5.1 3. I;/fiuence of Soil.-With regard to non-leguminous plants, a great difference in development was observed when oats and rape were grown in loamy soil (with 0.118 pcr cent. of nitrogen) and in sandy soil (containing 0.0035 per cent. of nitrogen). The results with loam have already been given (Zoc.cit.). Tho results given in Table I11 were obtained with the sandy soil. TABLE 111. Dry produce (grams). Nitrogen (grams).VEGETABLE PHYSIOLOGY AND AGRICULTURE. 3 i 3 The next experiments were made with yellow lupins and with peas grown in humous soil and in peaty soil, and the results are compared with those previously obtained with the same plants grown in sandy soil (toc. cit.). With regard to lupins, the plants grown in sterilised, yich soil (No. 2, i n Table IV) were entirely free from nodules, and lupins can, therefore, in a good soil, assimilate free nitrogen with- out the help of the symbiosis ; the power of assimilating free nitrogen is less in good soils than in poor, light soils, but in the poor soils this action is almost entirely due to the co-operation of the fuugus.Peas can also do without the symbiosis in good soil-the plants grown in sterilised soil (No. 5 ) were quite free from nodules-and take up free nitrogen from the air which is collected in the crop itself and in the crop-residue in the soil. But the symbiosis is of use even in humous soil, and increases the nitrogen assimilation. Peas did not grow very well in the peaty soil ; although there were nodules on the roots of plants grown in both the infected and the non-infected pots, the growth in the pot which was infected (with lupin soil) was much the greater. The next experiments were with red clover in sand (with minerals) in humous soil, and in peaty soil. The numerical results, together with those obtained with lupins and peas, are given in Table IV In the case of the sterilised red clover plants, several of t'he better plants grown in sand and many of those grown in soil had nodules when taken up.The results indicate that red clover, grown in sand, can only develop and take up free nitrogen when in symbiosis with the nodule fungus ; otherwise, practically no nitrogen will be assimi- lated. I n humous soil, red clover assimilates free nitrogen very readily, and eiiriches the soil in which it grows ; the symbiosis plays an im- portant part in the assimilation. At the same time. in spite of the symbiosis and oE the presence of the necessary minerals, the growth of red clover is, in sand, far less than in a good soil. In fact, in good soil, completely or nearly sterilised, the growth is greater than i n suitably infected sand.The experiments with pea.ty soil showed a much greater development with clover than with peas. S'anzmary.-A11 plants assimilat'e free nitrogen, but some of them require nitrogenous manures. There is only one plant (yellow lupin) which assimilates more nitrogen when grown in nitrogen-free soil than in presence of combined nitrogen. Peas, and probably most Legurninosw, yield large amounts of nitrogen only when supplied with combined nitrogen (especially nitrates), but the amount required is less than is generally supposed. Lupins should only be grown in poor soils; peas, red clover, and probably many othsr Legunainosce give better results when grown in good soils ; the more these plants are strengthened by the application of combined nitrogen, the more free nitrogeti they will be able to assimilate. Non-leguminous plants can only be made to recover from the state of hunger when grown in nitrogen-free soil by the application of combined nitrogen ; when they have thus gained strength, they assimilate free nitrogen.Legn- minous plants, on the other hand, recover from this period of nitrogen hunger, not only when they are supplied with combined nitrogen, (p. 374).374 ABSTRACTS OF CHEMICAL PAPERS. TABLE IV. 'Oil' grams. Dry 1 produce, Produce. At commencement. 1." 23.326 ' 8.6080 2.f- 26.636 8.6080 Y.$ 31.868 8'6080 -grams. I I I 0.0364 8.6640 9.6640 0.2816 9.9450 0.0364 8.6640 7-8560 0.3475 8'2035 0.0364 8-6640 8.7040 0-4565 9.1605 Nitrogen. 4.3901 4 '3901 4 -3901 At conclusion.0.0282 4.4183 5.1122 0.7'467 0 '0282 4 *4183 5 -3693 0 *3705 0 -0325 4 -4226 4 -8307 0 *64.39 5 -8589 5 -7398 5 '4746 Total. Gain. I 1 *440R 1,3215 1 -0520 Yeas in Humous Soil (4.08 kilos.). 4." 37 -983 5.t 27 'Otil 6.: 36.682 1 -3810 0 -4965 - 0 '4605 1 -8684 1 0 *7078 I 1.9762 1 1 -0457 0 -9543 0 -0637 1 -0'230 0 *0955 Zed Clover ila Humous Soil (11 kilos.). * Not sterilised. f Sterilised. Sterilised and seeded with hnmous soil. but also when they are infected with the leguminous nodule fungus. N. 11, M. Nitrogen Question. By H. IMMENDORFF (Landw. Jahrb., 21, 2&1--33U).--With regard to losses of nitrogen, there is no reason to suppose that when nitrogen compounds free from nitrites and nitratcs decompose without access of oxygen, free nitrogen will be libe~at~ed.This view is supported by the experimental results of Kellner (Zeit. physiol. Chem., 12, 95), Tacke (Lundu). Jalirb., 16, 917), and Ehren- b r g (Abstr., 1887, 172 and 746), and more recently of Schloesing (Abstr., 1890, 28%). The case is, however, different when nitrites and nitrates are present in the decomposing matter ; reduction takes place, free nitrogen is liberated, and all the intermediate oxy-VEGETABLE PHYSIOLOGY AND AGRICULTURE. 375 compounds will be formed (Tacke, Zoc. cit.). In Tacke’s experiments, the reduction was diminished, but not altogether prevented, by the presence of air, and it is possible that with still better Fentilation the reduction might have been stopped altogether. Losses of nitrogen during the process of nitrification was observed by Dehkrain (Abstr., 1887, 993), atid Tacke (Landw.Jahrb., 18,439), whilst in Ehrenberg’s experiments (Zoc. cit.), in which, however, ventilation was deficient, no evolution of free nitrogen was detected, and Schloesing’s results (Abstr., 1889, 638 and 1239) indicated that a loss of free nitrogen is not necessarily a consequence of nitrification. The power of fixing nitrogen, which Berthelot ascribes to some especially poor soils, was in no case confirmed by Schloesing (Abstr., 1888, 1330) ; not even after two years exposure of a soil to air. On the other hand, Berthelot’s results are support,ed by those of Gautier and Drouin, Dehkrain, Pechard and Tacke (Zoc. cit.1. Inasmuch as no constituent of soils is known to have the power of fixing nitrogen, the fixation, if admitted at all, is ascribed to bacteria ; and it seems not unlikely that the soil bacteria which fix nitrogen are identical with those which, as has been shown by the indirect experiments of Hellriegel and others, and the direct experiments of Schloesing and Lament, hare the same power when living in symbiosis with legu- minous plants.It may be mentioned, however, that in Btrthelot’s experiments, sterilised soils and soils infected with the contents of leguminous nodules, showed no material difference with regard to the amount of nitrogen they fixed. In the first series of the author’s experiments, mixtures of blood meal, garden soil, and chalk, and of bone meal, soil, and chalk respec- tively were kept for some months, a t a temperature of 28-30” in glass tubes, from which all the air had been expelled and replaced by oxyhydrogen mixture (prepared by electrolysis).The different parts of the apparatus, of which a sketch is given, were fused together, so as to avoid the use of joints or corks; and it was so arranged that samples of the gas could be obtained as often as desired for analysis, without interrupting the experiment. I n the first weeks, no appre- ciable amount of nitrogen was evolved, but subsequently there was tlr loss in Experiment 1 (with 14 856 grams of substance, containing 0.5151 gram of nitrogen) of 20 miligrams of nitrogen. I n Experi- ment 2 (with 14.5969 grams of soil, &c., containing 0.2208 gram of nitrogen) the loss of nitrogen was 11 milligrams. No nitrous oxide was given off.In the other series of experiments, layers of soil or other substances were put in alternate layers with pieces of glrlss rod in upright cylinders, so constructed that air free from combined nitrogen could be passed throngh from below, and any ammonia which might be given off absorbed by acid, and the quantity determined at the end of the experiment. The foilowing table shows the nature and amounts of the sub- stances experimented on, the total initial and final nitrogen; the nitrogen as nitric acid, and tbe nitrogen a8 ammonia, found at the end of the experiments. The experiments 1-6 extended over nearly a year, whilst the 0thel.S la3te.l f r o 4 16 to 22 weeks.3713 ABSTRACTS OF CHEMICAL PAPERS. grams 1 -1078 1.1144 3-1252 3*0c330 3.0852 1.1044 1.Arable eoil (100 grams). , 2. ?, 3 , * I 3. Arable soil (100 gram) st erilised ............. 4. Liipin soil (100 grams) . I 5. >, 9 7 ' 0. Lupin soil (100 grams) sterilised.. ........... -- gram 0 *0311 0 *OL96 0 0 0 0 -- 7. Arable soil (100 grams) and ammonium sulphatf containing 0 -115 gram 8. Arable soil (100 grams) with bone meal (5 grams) 9. Lupin soil (100 grams) with bone meal (5 grams: 10. Bone meal (9.4775 grams), chalk (2 grams) 11. Sonerneal(9.9'702 grama: 12. Blood meal (10.4941 grams), chalk (2 grams) 13. Horn meal and super phosphate" (equal parts 14. Horn meal and superphos phatet (21 -002 grams) . 15. Horn meal and super phosphate-gypsum 16. Bone meal (10.804' grams), and gypsum (1: prams) .............. 17. Bone meal (12.103' grams), and kainite (1 grAms) ..............18. Bone meal (10.G83' grams), and chalk (1( grams) .............. of nitrogen.. ......... ---- 21 -034 grams) ....... (22 -9694 grams) ...... 3 *l876 3 -2973 3 - 2822 i t com- mence- ment. 0 *0362 0 *lo92 0 *0454 Total. 0.4851 1'4284 0 -3620 0 -4180 granis 0 *1198 0'1214 0 -1209 0 -1061 0.1045 0 -1042 0 0 -- 0 *0132 0 *0033 0 -2363 0 -3169 0 '2890 0 '4484 0 '4717 1 '4074 0 -41 90 0*4284 0.4676 0'4317 0 -3660 0 *4250 0 -4154 0 * 4500 0.4987 0 -44a2 0 *0049 0 0 0 Nitrogen. At conclusion. As nitrate. I As ammonia. 0 *059( trace 0 -097C 0 *281t 0.307: 1 -0781 0 *1071 0 -199' [-.::: 0.243 0 -274 I n receiver. gram 0 *0008 0 -COO6 0'0033 0.0006 0 ,0006 0 -0056 -- trace trace 0 *0678 0 -1500 0 *0671 0.8149 0 0 '0020 0 -1018 0 '1170 0.0555 Gain or loss.gram - 0 * 01 20 - 0 .OOiO + 0*0033 - 0 '0231 - 0 '0193 + 0 -0002 - 0 -0487 - 0 -0196 - 0 -0069 + 0 ~0171 -+ 0.0133 f 0 -0210 - 0 -0040 - 0 *0070 + 0 -0036 - 0 -0216 - 0 '03 10 0 '2578 , -0 %087 I * Containing 33.7 per cent. of soluble phosphoric acid. + Containing 8.6 per cent. of soluble phosphoric acid.VEGET IRLE PHYSIOLOQT AND AORTaULTURE. 817 With regard to loss of free nitrogen, the results show that i t may take place during decomposition in presence of plenty of oxygen, both when nitrification takes place and when ammonia is formed. Gain of nitrogen took place (Experiments 10, 11, 12) in substances containing plenty of nitrogen, and coincidently with large production of ammonia. As other experiments indicate that under these con- ditions loss of free nitrogen takes place, this was probably also the case in these three experiments, and the gain must therefore bare been still greater than the numbers iidicate.The last six experi- ments are of further interest as showing the retentive power, or want of such a power, for ammonia of various substances. The super- phosphate retained the whole of the ammonia ; the superphosphate- gypsum, and gypsum kept back some, but allowed very much to escape. Kainite, on account of its greater solubility, acts more strongly in fixing ammonia than either superphosphate-gypsum or gypsum. Calcium carbonate assists the volatlilisation of ammonia. When phosphoric acid was used, there was no loss of free nitrogen, whilst, when other substances, especially kainite, were employed, the loss of free nitrogen was considerable.The author is, however, not prepared to say that the non-evolution of nitrogen was due to the presence of phosphoric acid (compare v. Krause, Abstr., 1890, 1340). I n the course of the first series of experiments, it was noticed that when the tube containing soil was filled with electrolytic gas, the gas disappeared entirely in a few days. I n order to ascertain whether this was due to the physical and chemical properties of the soil, or to micro-organisms, the following experiments were made :--25 grams of moderately moist arable soil was piit into the apparatus (similar to that used in the first set of experiments already described), wilich was exhausted and filled with the oxyhydrogen mixture. I n the first f o u r weeks there was only a slight absorption, but a good deal of carbonic anhydride was evolved ; afterwards the absorption was more rapid, and in abont five weeks almost the whole of the gas was absorbed, and nearly a vacuum produced. A similar experiment in which a few drops of chloroform were introduced into the apparatus showed that under these conditions only a trace of carbonic anhydride was given off, a n d that no absorption of the oxyhydrogen mixture took place, Two more experiments were made in which blood meal (5 grams) was mixed with the soil ; similar results were obtained.The absorp- tion of oxygen and hydrogen is therefore probably due to mic1.o- organisms in the soil. The author considers this power of unitilig oxygen and hydrogen to be more remarkable than the power of fixing nitrogen, and refers to the processes studied by Winogradsky, in which bacteria oxidise ferrous oxide to ferric oxide, hydrogen sulphide to sulphur, and finally to sulphuric acid, &c.Experiments were also made to see if pure cultivations of bacteria from pea and bean nodules have the power of assimilating free nitro- gen, but they alvays failed to develop well in nutritive solutions free from nitrogen. The following conclusions are drawn from the above results:- (1.) Loss of nitrogon can take place in decomposing nitrogenous3 i 8 ABSTRACTS OF CHEMICAL PAPERS. matter, independently of nitrification ; whilst it does not t t k e place when air is excluded. (2.) It is not established whether free nitro- gen is eliminsqted during the nitrification of ammonia with sufficient ventilation.(3.) Free nitrogen is fixed not only in poor soils, but i n materials rich in nitrogen. (4.) Superphosphates are excelleri t preservatives for farmyard manure, even when air has access. Super- phosphate-gypsum is of less value, whilst gypsum and kainite are far less effective still. (5.) Arable soil, aft#er undergoing a process of decomposition, has the power of uniting oxygen with hydrogen, the nniou being probably accomplished by bacteria. (6.) No kind of bacteria has as yet, with certainty, been isolated which has the power of fixing free nitrogen; although i t is established that the Legurninom, with the help of certain known bacteria, are in a position to employ free nitrogen to their advantage.Sketches are given of the apparatus employed, which was similar to that used by Tacke. After the above investigation mas completed, the author found that the absorption of oxygen and hydrogen by soils had been discovered bg de Saussure, in 1834. Licbig (Anmlen, 153, 142) considered the process to be a purely chemical one. Fixation of Free Nitrogen by Plants. By T. SCHLOESING, Jun., and E. LACRENT (Compt. rend., 113, 776--778).-An extension of the work on the Legutninom (Abstr., 1891, 353) t o other classes of plants. Two experimental methods were employed, the first con- sisting in measuring the decrease in volume of the nitrogen of the atmosphere in which the plants were confined, the other in estimnt- ing the increase of the total nitrogeii in the soil, seeds, and crop during the experiment. The results yielded by the two methods agree well.A s the conditions under which nitrogen might be absorhed were un- known, it was necessary to employ natxtral soil, for which purpose a. poor sandy earth was enriched with calcareous earth, and with garden soils in which grass, trefoil, lupin, and beaus had been grown ; it was watered with nutritive mineral solutions also, and, after the seeds had been sown, with an aqueous extract of the mixture of garden soils. In the first set of experiments, which extended over 39 months, the results were obscured by the growth of mosses and algm on the surface of the soil, and although it was found that the nitrogen ab- sorbed was markedly greater in the case of the leguminous pIarits (peas) than in those of the others (Jerusalem artichokes, oats, and tobacco plants), yet it could not be ascertained to which vegetation the absorption was due.That nit,rogen was assimilated during the growth of the cryptogams was evident, since in one of the blank experiments in which no appreciable growth appeared on the surface of the soil, no sensible amount of absorption took place, whilst in other blank experiments in which the lower growths had developed freely, a, considerable amount of nitrogen was taken up. In a second set of experiments, which extended over three months, the lower growth was prevented by covering the soil with a layer of calcined quwtz Rand, and it was found that neither with soil alone, N. H. M.VEQEThRIiE PRPSTOLO(:Y AND AGRICULTURE.879 nor with growing plants of oats, mustard, cress, or asparagus, WRS there any sensible absorption, whilst with peas, a very considerable amount of nitrogen was found. I n the last case i t was remarked, too, that nodosities had formed on the 1-oots. Rerthelot (ibid., 778-779), in calling attention to the above note, points out the confirmation which the results bring to his own researches and views on this subject. Prote'ids of the Maize-kernel. By R. H. CHITTENDEN and T. B. OSBORNE (Amer. Chem. J., 13, 453-468 ; compare Abstr., 1891,1285). -The authors propose to investigate, first, the prote'ids which Rre soluble in salt solution, but insoluble in water ; secondly, those which are soluble both in water and in salt solution, and, thirdly, those which are insoluble in water and salt solutions, but soluble in alcohol. When fine freshly-ground maize-meal is extracted in the cold with 10 per cent.sodium chloride solution, it yields a yellow solution, from which the prote'ids may be precipitated either by removing t b salt by dialysis or by adding ammonium sulphate to saturation. The precipitate is purified by redissolving in sodium chloride solution and again dialping, and then separates in small spheroids, which adhere to the walls of the dialyser, and closely approximate to crystals in character. The ammonium mlphate precipitate is partially soluble in water, and may therefore be treated with that solvent before digesting with sodium chloride, the two solutions being mixed before dialysing. 5 per cent. ammonium chloride solution may be sub- stituted for the sodium chloride, the prote'ids being precipitated as before by ammonium sulphate.The products obtained in this way were of practically identical composition :-C, 51.65 ; H, 6.82 ; N, 17.69; and S, 0.93. The yield of pure product obtained by the first method was 0.2 per cent. When the sodium chloride solutions of the protei'ds are heated, they become turbid, and a t a somewhat higher temperature form a flaky coagulum ; if this is filtered off, the clear filtrate undergoes the same changes when raised to a still higher temperature, and so on, several distinct fract'ions being obtained ; even when the solution has been boiled for some time, the filtrate often yields a precipitate with acetic acid. The temperatures of coagulation are not, however, very constant, as theg are considerably altered by slight variations in the methods of extracting and purifying the prote'ids. From a consideration of these phenomena it appears that the prote'id matter either consists of several distinct globulins, or is itself a, simple globulin capable of being split up by the action of heat.It may, for instance, be a mixture of variable proportions of vitellin and an uncoagulable globulin. Phytomyosin cannot ba present in quantity since very little precipitate is thrown down when the sodium chloride solution of the proteid is saturated with that salt. An attempt was made t o fractionate the proteid matter based on tohe facts that it is not entirely redissolved by sodium chloride solu- tion, and that the goluble portion is only partially reprecipitated by the addition of a large quantity of wateP.The fractious soluble h JN. W, The present paper relates to the first class.380 ABSTRAOTS OF CHEMICAL PAPERS. sodium chloride were of practically the same composition as the original proteids, but the insoluble fraction contained appreciably less nitrogen (15.59 per cent.). The formation of the insoluble prote'id may be explained by supposing that the globulin is partially con- verted into an aidbuminate. Another attempt was based on the rarying solubility of the proteiid in sodium chloride solutions of different strengths ; but the fractions obtained were unaltered in composition. JN. W. Choline and Betaine in Cotton Seed Foods. By W. MAX- WELL (Amer. Chem.J., 13, 469-471)..-The bases were extracted from finely ground cotton-seed cake with 70 per cent. alcohol, and purified by means of the mercurochlorides. The hydrochlorides pre- pared from the latter were separated by means of absolute alcohol, in which the beta'ine salt is very sparingly soluble. The relative amounts of choline and beta'ine hydrochloride thus obtained were as 1 to 5.7. The relative amounts obtained from cattle food prepared from a sample of the same cotton seed was as 1 t o 4.7. JN. W. Occurrence of Gums which yield Xylose. By A. VOSWINKEL (Chem. Centr., 1891, ii, 655 ; from Phaym. Centralkalle, 32,505-50;). -The author found these gums in several fungi, CantharelZus cibnrius, Hydnum repandzm, Clamria Jlava, C. botrytis, Psuliota camyesty is, Boletus edulis, and B.grnnulatus. It was separated by extracting the ground fungus with soda; the extract was then precipitated with alcohol, and the precipitate washed with alcohol containing a little hydrochloric acid. The product gave the phloroglucinol and furfur- aldehyde reactions, and was converted iuto xylose by dilute sulphuric acid. J. W. L. The PoisonouEi Constituent of the Ethereal Fern Extract, By E. POUJ~SON (Chem. Centr., 1891, ii, 673 ; horn Arch. expt. Path. Pharrri., 29, 1--24).-l'he author's experiments show that tlre poisonous properties of fern extract are due to an amorphous sub- stance which is the trueJZzcic acid. The acid is readily converted into its lactone, by simply boiling its ethereal solution. The lactone is named filiciii, by the author.The filicic acid melts at 184.3" ; filicin melts at lf23". The pure acid may be obtained from filicin by dis- solving the latter in cold dilute soda, and filtering the solution into dilute hydrochloric acid. The white precipitate is then dried over sulphuric acid. Determinations of the molecular weights of the two compounds by Raoult's method gave for filicin 642 and 654, which, in coujunction wit'h the analysis, indicates the formula C35H400,2, whilst, for filicic acid, the numbers 663-699 were obtained, and this, in conjunction with the analysis, indicates the formula C35H&13. The author considers filicic acid to be suitable f o r therapeuticit1 purposes ; it is readily soluble in the alimentary canal, but difficult lg reduced and either kills parasitic organisms or expels them, witliout damaging the canal.It appears to be more readily absorbed if taken with oil than iE taken alone. J. W. L.ANALYTICAL CHEMISTRY. 381 Ammonia in the Atmosphere and Rain Water of the Tropics. By V. MARCAKO and A . MUWZ (Compt. rend., 113: 729--781).-The observations, which extend over several years, were made near Caracas, Venezuela, in 10" N. latitude, a t an altitude of 922 metres above sea-level. The temperature of this locality is constant, the rains very intermittent, and the storms violent and numerous. It has already been shown (Abstr., 1889. 923) that the nitric and nitrous nitrogen in the air of this region is ten times more abundant than in that of more temperate climates, and it is now found that the ammonia is distinctly less, a surface of acidified water 1 square metre in area absorbing in 24 hours an average of 0.012.32 gram of ammonia, a s against 0.02 and 0.024 in France.This unexpected result is probably due to the formation of solid ammonium nitrite and nitrate in the air, a theory borne out by the excessive amount of ammonia found in the rain water, 0.00155 gram per litre on an average, tts against 0.00032 gram in Alsace (Boussingault) and 040097 a t Rothamsted (Lilwes and Gilbert). (Compare, however, next abstract.) JN. W. Ammonia in Rain Water. By ALBERT-L~VY (Compt. rend,, 113, 804--805).-The author points out that the figures of Lawes aud Gilbert quoted by Marcano and Muntz (precei'iiig abstract) varied considerably from year to year, and that, in 1856 for example, they found 0.00143 gram of ammonia per litre, an amount quite compar- able with those obtained by the authors criticised.H e also quotes various other data to show that the amount of ammonia in the rain water of Venezuela is not excessive ; the mean amount, for instance, i n the rain water of Montsouiis, France, where he has estimated the ammonia in every downpour for upwards of 16 years, is as much iLs 0.0022 gram per litre. JN. W.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 367Chemistry of Vegetable Physiology and Agriculture.Nitrification of Organic Nitrogen. By T. LEONE and 0.&lAGhTANrNr ( Gazaetta, 21, ii, 206--908).-The authors have inst,itu tedexperiments to determine whether organic nitrogen is completely con-verted into nitric acid by the nitrifying organism.A quantity ofgelatin solution containing 0.04-0.07 gram of nitrogen was dissolvedi n 2-3 litres of water, and kept at 32" for 45 days, after which timeneither ammonia nor nitrons acid was present in the Bolution, so thatthe action may be considered to have ended. On determining the nitricacid, a deficit of 17.4-19.0 per cent. on the amount of nitrogenoriginally present was observed. This nitrogen must either havebeen evolved in the free state or remaiued in the solution as organicmatter not convertible by the organism.The Sources of the Nitrogen of our Leguminous Crops. BySir J. B. LAWES and J. H. C*It,BERT (Jour. By. Agri. Xoc. [3], 2,657-720),- Both the scientific interest and practical value of legn-minous crops depend largely on the amqnnt of nitrogen they containand on the sources of this nitrogen ; also on the great difference inthese respects between them and the agricultural plants of otherorders.Gmin and root crops and potatoes cannot be successfullygrown without the application of nitrogenous manure, whilst thedirect effect of such manure is to increase riot so much the nitrogen-ous as the non-nitrogenous constituents of the plants-the carbo-hydrates. This is well illustrated by the results of field expprimentsmade at Rothamsted; the results show that when nitrogenousW. J. P.2 c 368 ABSTRACTS OF CHEMICAL PAPERS.manures are applied in conjunction with minerals, there is an enorm-ons increase in the carbon assimilation and carbohydrates formed a scompared with the amounts assimilated under the influence of mineralsonly.On the other hand, leguminous crops, grown without nitrogenousmanure, contain a higher percentage of nitrogen than non-leguminouscrops, and yield also a much greater amount of nitrogen over a givenarea of land ; nitrogenous manures have little o r no effect when givento them, and the carbon assimilation is not materially increased.Roussingault's experiments, and the earlier experiments made atRothamsted (this Journal, 1863, loo), showed that, under conditiolisof sterilisation and enclosure, there was no gaiu from free nitrogenin the growth of either Gyaminem, Legurninosa?, o r other plants. Theresults obtained by Hellripgel and others, and especially those ob-tained a t Rothamsted in 1888 (Abstr., 1890, 814), are next discussed.They show that, under non-sterilised conditions-in fact, with suit-able microbe infection of the soil-there was nodule formation on theroots and considerable fixation of free nitrogen.These results havereceived confirmation f rorn still more recent Rothamsled experi-ments, and also from t4he direct experiments of Schloesing, jun., andTlaurent (Abstr., 1891, 553), who determined the loss of nitrogenwhich took place i n the confined air in which their plants were grown.In lg89, and since, quantitative experiments have been made withpeas, beans, vetches, lupins, white clover, red clover, sanfoin, andlucerne ; that is to say, with four annuals and four plants of longerlife. The results, as far a s they are available, show that withoutsoil-extract seeding, and with no nodules, there was no gain ofnitrogen ; whilst with soil extract, and with nodule formation, therewas a considerable gain of nitrogen, in fact, very many times as muchnitrogen in the products of growth as in the seeds sown.The difficulky at first exprrienced by Hellrieqel in obtaining goodresults with lupins, and a t Rothamsted with yellow and blue lupinsin 1888, seems to be due to the infecting soil which was used beingunsuitable. Nobbe's experiments (Abstr., 1891, 1533) indicate thatthere are a variety of leguminous nodule-organisms, which have veryiliff erent effects with the diffkrent plants (compare also Beyerinck,Abstr., 1891, 7539).This would also be consistent with the observa-tions made a t Rothanisted with various plants, showing that theexternal appearance and distribution of the nodules were veryclifierent in the case of peas, vetches, lupins, and other plants.A series of experiments was commenced at Rothamsted in 1890,with a view to the mor3 detailed examioat'ion of the roots of the plniltsthan was possible in the case of the strictly quantitative series.Theplants were grown in pits, so arranged that some of the plants of eachdescription could be taken up and their roots examined at three (orfour) successive periods of growth. Each plant was grown in sandsupplied with minerals and soil extract, and in a ruixture of soiland mnd. Generally speaking, in sand, the area of infection waslimited, but the nodules were of great size ; in soil with much greaterdistribution of the infccting organisms, there was a far greaternumber of nodules, which were, however, smaller than those grown insand.The results of determinations of dry matter and nitrogen iVEGETARLE PHYSIOLOGY ASD AQRICZLTURE. 3G9the nodules of the plants taken up at, different periods indicate thatin the case of the annual, whcn the seed is formed and the plantmore or less exhausted, both the actual amount of nitrogen in thenodnles and its percentage in the dry substance are greatly reduced;but that with the plant of longer life, although the earlier-formednodules become exhausted, others are constantly produced, thus pro-viding for future growth.And the results of these experiments,taken together with those of the quantitative series, show further anintimate connection between the gain of nitrogen by the LeguminosGeand the development of the nodules on their roots..As to the manner in which nitrogen is fixed, it has been suggestedthat, under the conditions of the symbiosis, the plant is enabled to fixthe free nitrogen of the atmosphere by its leaves ; but there is little ornothing i n the evidence we have which leads to this conclusion. It isalso suggested that the bacteria of the nodules become distribnted inthe soil and there fix nitrogen, which is subsequently taken by theplants from the soil. In the Rothamsted experiments, however, nogain of niti-ogen was observed in the soils.Berthelot found that soilsboth free from higher vegetation, and soils in which leguminousplants were growing, gained in nitrogen ; and Schloesing, ~ u n . , andLaurent also found fixation to take place in soils under the influenceof lower plants-lichens and algE. Nevertheless, neither experiencein practical agriculture, nor the nitrogen statistics of soils and crops,indicate any material fixation of free nitrogen under the agency ofmicrobes within the soil, independently of leguminous growtkThere is, however, evidencc that, in soils and subsoils containingcombined nitrogen, lower organisms may serve the higher by bring-ing the organic nitrogen into an available form. As examples maybe mentioned the fungus of fairy rings, the fungus mantle obsrrredby Frank on the roots of certain trees, and especially the nitrifyingorganisms.To return to the question of fixation, the most probableexplanation seems to be that free nitrogen is fixed in the course ofthe development of the organisms within the nodules, and that theresulting nitrogenous compounds are absorbed and utilised by theplant. It may be mentioned that Loew (Abstr., 18’30, 10.52), viewingthe question in the light of his own results with plalinuni in presenceof alkali, suggested the possibility that the vegetable cell, with itsactive protoplasm, if in an alkaline condition, may fix free nitrogenwith formation of ammonium nitrite. It was frequently found a tRothamsted that the contents of the nodules, when apparently in anactive condition, showed a weak alkaline reaction.Although much of the nitrogen o€ leguminous crops is sometimesobtained under the cmditions described, from the free nitrogen of theair, a good deal is taken up from the subsoil, chiefly as nitric acidderived from the organic matter present in the soil.A difficulty in theway of the assumption that much of the greater assimilation of theLeguminosae than by other plants is due to nitrification of the subsoilis the fact that the direct application of nitrates has but little effect onthe growth of such plants. The two cases are, however, differen+nitrates, when applied, percolate more or less alone through the soil,whilst nitrates formed as a result of action on the organic nitrogef37 0 ABSTRACTS OF CHEMIOAL PAPERS.will probably be associated with other constituents liberated at theacime time.With regard to the more practical aspects of the subject, referenceis made to the experiments of Schultz, of Lupitz, who has, for someyears, grown leguminous crops overlarge areas of poor sandy soil.using kainite and phosphatic manures ; he finds the lands thereby mucltbenefited for subsequent cereal and other crops.The system isextending in other parts of Germany, and in this country Mr. Mason,of Eynsham Hall, Oxon,is making extensive experinients on the subject.“ The experimental results which have been brought forward clearlyestablished that there is great gain of nitrogen under some conditions.It has also been clearly shown that due infection of the soil and ofthe plant is an essential to success.The evidence at the Rame timepoints to the conclusion that the soil may be duly infected for thegrowth of one description or some descriptions of plant, but not forsome other descriptions. The field experiments on leguminous cropsat Rothamsted have further shown, so to speak, that land which is quiteexhausted, so far as the growth of one leguminous crop is concerned,maystill grow very luxuriant crops of another description of the same family,but of different habits of growth, and especially of different characterand range of roots. This result, though undonbtedly more or lessdue to other causes also, is, nevertheless, in some cases doubtlessdependent on the existence, the distribution, and the condition, of theappropriate microbes for the due infection of the different descriptionsof plant.In fact, i t is pretty certain that success in any systeminvolving a more extended growth of leguminous crops in our rota-tions will not be obtained without, having recourse to a considerablevariation in the description of leguminous plant grown. Otheressential conditions of success will generally be the liberal applicationof potash and phosphatic msnures, and sometimes chalking or liming,for the leguminous crop. Then, the questions would arise-how longthe legumirions crop should occupy the land ; to what extent it shouliibe consumed on the land, or the manure from its consumption be re-turned ; or, under what conditioiis the whole, o r part, of it should bcploughed i n ? Lastly, it is probable that more benefit would accrueto the lighter and poorer than to the heavier o r richer Foils by anysuch extended growth of leguminous crop.”Assimilation of Free Nitrogen by Plants in its Dependenceon Species, on Nutrition, and on Soil.By B. FRANK (Lnndtc.Jahrb., 21, 1-44) .-1. Dependence o n Species. (a.) Cryptogums.-Earlier investigators ascribed to the non-chlorophyllous crypt ogamsthe power of assimilating free nitrogen (Jodin, Compt. rend., 55,612 ; Hallier, Gdhrungsercheinungw, Leipzig, 1867), whilst morerecently this has been denied (Nageli, Xitzungsber. kgZ. bail.. A kad.,1879). The author’s experiments w i t h a form of penicillium, withpure cultivations of the fungus of leguminous root-nodules, and withchlorophyllous ctlgi-52, show that, when grown in non-nitr ogenous mediiband in air free from combined nitrogen, they will develop, althoughonly slowly, and take up elementar-y nitrogen. ( b .) Phanw-oguns.-The experiments with phaneiogams were, like thoFe preriously de-N. H. MVEGETABLE PHYSIOLOQP AND AQRICULTURE. 371Seeds.grum0.0070*012scribed (Ahstr , 1891, 353). made in glass pots or in glass dishes andexpnsed to air. The first experiments were made with bnckwhertt andspurrey in sandy soi I (12 kilos.) ; a fallow experiment with heavy loamwas also made. The following results were obtairied (compare resultswith oats and rape in loam and with yeilow lupins in sandy soil, loc.cit.) :-Sand.Produce. 1 Soil. Gain.grnms gram 1 grams grams1-15 u.082 @*14)* (1.065)1'15 0.111 1'21 0.159-------_I---TABLE I.Kind and numberof plant.___I--1. Buckwheat (18) ..2. Corn spurrey . . . .Dryproduce.--grams10.35416.755Nitrogen.At conclusion. I At cornmencement.-.- I-* Assuming the percentage given (1 '0178) to be a mieprint for 0 -0178.The gain in the soil was greatest in the case of yellow lupins ( b c .c k ) , and is there much too great to be due to the small amount ofroots left in. In no case was there any material loss in the soil, show-ing that the nitrogen of the plants was derived from the air.2. InJEuence of Nutrition.--In order to ascertain the effect ofdifferent nitrogenous manures on the amount of nitrogen fixed, ex-periments were made with yellow lupins which were grown in ignitedsand supplied with minerals : some pots had no nitrogen, others had0.12 gram of nitrogen, either as calcium nitrate, as ammonium sulph-ate, or as urea.I n each case there were two sets of experiments, onemicrobe-seeded and the other not. There mere four pots (one plantin ew.ch) for each experiment. I n most cases, there were no nodulesformed in those pots which were iiot intentionally infected, and themwere generally nodules on the roots of the plants to which soil wasadded for seeding. The total produce, &c., was determined in eachexperiment (the plants of the several pots of one set being takei.together). As there were some failures, the average amount of pro-duce f o r the successful pots arid the amount of nitrogen in it and inthe seed sown is given in Table 11, p.372. The actual gain, if any.cannot be ascertained, as, with the exception of the experiments withnitrates, the final amount of nitrogen in the sand was not determined.The results show t.hat yellow lupins mid peas, without the help ofsoil, develop orgallisms when snpplied with nitrogenous manure, b u tthere is better development when the plants are infected and are nobsupplied with conibined nitrogen than when the plants are not infectedbut are supplied with combined nitrogen. In the case of yellowlupins growing in symbiosis with soil organisms, the application ofnitrogenous mainires (at least, as nitrqte, ammonia, and we.) seemqto act injuriously.Peas grow best under the simultaneous action ofthe symbiosis and nitrate372 ABSTRACTS OF CHEMIOAL PAPERS.Drypro-d uce(grams).TABLE 11.At commence-ment.Seed Nitrate,(gram). (gram).&C.Nitrogen. l lProduce(gram).As Tn pro-nitrate duce. N in seed(gram). - - 1.Yellow Lupin,c..I I I'7 *8594.890 { 7.0885 *598 { 10 *0711. Seeded ...........2. Seeded calcium3. Not seeded}nitrate4. Seeded 1a:tlmon-0-120'120*120.125 . Not seededrsulph.6. Seeded7. Not seeded}urea * *0.0390.0570.0520.0'710.0488. Seeded ...........9. Seeded lcalcium10. Not seeded( nitrate31. Seeded ammon12. Not seeded} sulph. '0 -0090 -0090 -0090.0090 so090 -0090 *0092.2646 '480 { 4.3304.971 { 5 -468-0'120 -120'120.120'120 '12At commencement.At conclusion.Soil. Seed. Total. Soil. Produce. Total.- - ~ - ~ - -0'30 - 0-30 0.400 30 0.014 0.314 0.390.27 0'003 0'273 0.37Pens.2 . Oats.. ....3. Rape .....At conclusion.1 I8.262 -13I I0-1120.0940 -0780 *0510 -0490 -0920.111-0 -0020 -00712 '310.38 '65 . 55 *410.112.30 -0090.0090 -0090.0090 a 9-0*00150 '00104 . 213 '45 * 57 ' 55.13. I;/fiuence of Soil.-With regard to non-leguminous plants, a greatdifference in development was observed when oats and rape weregrown in loamy soil (with 0.118 pcr cent. of nitrogen) and in sandysoil (containing 0.0035 per cent. of nitrogen). The results with loamhave already been given (Zoc. cit.).Tho results given in Table I11were obtained with the sandy soil.TABLE 111.Dryproduce(grams).Nitrogen (grams)VEGETABLE PHYSIOLOGY AND AGRICULTURE. 3 i 3The next experiments were made with yellow lupins and with peasgrown in humous soil and in peaty soil, and the results are comparedwith those previously obtained with the same plants grown in sandysoil (toc. cit.). With regard to lupins, the plants grown in sterilised,yich soil (No. 2, i n Table IV) were entirely free from nodules, andlupins can, therefore, in a good soil, assimilate free nitrogen with-out the help of the symbiosis ; the power of assimilating free nitrogenis less in good soils than in poor, light soils, but in the poor soils thisaction is almost entirely due to the co-operation of the fuugus.Peas can also do without the symbiosis in good soil-the plantsgrown in sterilised soil (No.5 ) were quite free from nodules-and takeup free nitrogen from the air which is collected in the crop itself andin the crop-residue in the soil. But the symbiosis is of use even inhumous soil, and increases the nitrogen assimilation. Peas did notgrow very well in the peaty soil ; although there were nodules on theroots of plants grown in both the infected and the non-infected pots,the growth in the pot which was infected (with lupin soil) was muchthe greater.The next experiments were with red clover in sand (with minerals)in humous soil, and in peaty soil. The numerical results, togetherwith those obtained with lupins and peas, are given in Table IVIn the case of the sterilised red clover plants, several of t'he betterplants grown in sand and many of those grown in soil had noduleswhen taken up.The results indicate that red clover, grown in sand,can only develop and take up free nitrogen when in symbiosis withthe nodule fungus ; otherwise, practically no nitrogen will be assimi-lated. I n humous soil, red clover assimilates free nitrogen very readily,and eiiriches the soil in which it grows ; the symbiosis plays an im-portant part in the assimilation. At the same time. in spite of thesymbiosis and oE the presence of the necessary minerals, the growthof red clover is, in sand, far less than in a good soil. In fact, in goodsoil, completely or nearly sterilised, the growth is greater than i nsuitably infected sand.The experiments with pea.ty soil showed amuch greater development with clover than with peas.S'anzmary.-A11 plants assimilat'e free nitrogen, but some of themrequire nitrogenous manures. There is only one plant (yellow lupin)which assimilates more nitrogen when grown in nitrogen-free soilthan in presence of combined nitrogen. Peas, and probably mostLegurninosw, yield large amounts of nitrogen only when supplied withcombined nitrogen (especially nitrates), but the amount required isless than is generally supposed. Lupins should only be grown inpoor soils; peas, red clover, and probably many othsr Legunainoscegive better results when grown in good soils ; the more these plantsare strengthened by the application of combined nitrogen, the morefree nitrogeti they will be able to assimilate. Non-leguminous plantscan only be made to recover from the state of hunger when grown innitrogen-free soil by the application of combined nitrogen ; whenthey have thus gained strength, they assimilate free nitrogen.Legn-minous plants, on the other hand, recover from this period of nitrogenhunger, not only when they are supplied with combined nitrogen,(p. 374)374 ABSTRACTS OF CHEMICAL PAPERS.TABLE IV.'Oil'grams.Dry 1 produce,Produce.At commencement.1." 23.326 ' 8.60802.f- 26.636 8.6080Y.$ 31.868 8'6080-grams. I I I0.0364 8.6640 9.6640 0.2816 9.94500.0364 8.6640 7-8560 0.3475 8'20350.0364 8-6640 8.7040 0-4565 9.1605Nitrogen.4.39014 '39014 -3901At conclusion.0.0282 4.4183 5.1122 0.7'4670 '0282 4 *4183 5 -3693 0 *37050 -0325 4 -4226 4 -8307 0 *64.395 -85895 -73985 '4746Total.Gain. I1 *440R1,32151 -0520Yeas in Humous Soil (4.08 kilos.).4." 37 -9835.t 27 'Otil6.: 36.6821 -38100 -4965- 0 '46051 -8684 1 0 *7078 I 1.9762 1 1 -04570 -9543 0 -0637 1 -0'230 0 *0955Zed Clover ila Humous Soil (11 kilos.).* Not sterilised. f Sterilised. Sterilised and seeded with hnmous soil.but also when they are infected with the leguminous nodule fungus.N. 11, M.Nitrogen Question. By H. IMMENDORFF (Landw. Jahrb., 21,2&1--33U).--With regard to losses of nitrogen, there is no reason tosuppose that when nitrogen compounds free from nitrites and nitratcsdecompose without access of oxygen, free nitrogen will be libe~at~ed.This view is supported by the experimental results of Kellner (Zeit.physiol.Chem., 12, 95), Tacke (Lundu). Jalirb., 16, 917), and Ehren-b r g (Abstr., 1887, 172 and 746), and more recently of Schloesing(Abstr., 1890, 28%). The case is, however, different when nitritesand nitrates are present in the decomposing matter ; reduction takesplace, free nitrogen is liberated, and all the intermediate oxyVEGETABLE PHYSIOLOGY AND AGRICULTURE. 375compounds will be formed (Tacke, Zoc. cit.). In Tacke’s experiments,the reduction was diminished, but not altogether prevented, by thepresence of air, and it is possible that with still better Fentilationthe reduction might have been stopped altogether.Losses of nitrogenduring the process of nitrification was observed by Dehkrain (Abstr.,1887, 993), atid Tacke (Landw. Jahrb., 18,439), whilst in Ehrenberg’sexperiments (Zoc. cit.), in which, however, ventilation was deficient,no evolution of free nitrogen was detected, and Schloesing’s results(Abstr., 1889, 638 and 1239) indicated that a loss of free nitrogen isnot necessarily a consequence of nitrification.The power of fixing nitrogen, which Berthelot ascribes to someespecially poor soils, was in no case confirmed by Schloesing (Abstr.,1888, 1330) ; not even after two years exposure of a soil to air. Onthe other hand, Berthelot’s results are support,ed by those of Gautierand Drouin, Dehkrain, Pechard and Tacke (Zoc.cit.1. Inasmuch as noconstituent of soils is known to have the power of fixing nitrogen, thefixation, if admitted at all, is ascribed to bacteria ; and it seems notunlikely that the soil bacteria which fix nitrogen are identical withthose which, as has been shown by the indirect experiments ofHellriegel and others, and the direct experiments of Schloesing andLament, hare the same power when living in symbiosis with legu-minous plants. It may be mentioned, however, that in Btrthelot’sexperiments, sterilised soils and soils infected with the contentsof leguminous nodules, showed no material difference with regard tothe amount of nitrogen they fixed.In the first series of the author’s experiments, mixtures of bloodmeal, garden soil, and chalk, and of bone meal, soil, and chalk respec-tively were kept for some months, a t a temperature of 28-30” inglass tubes, from which all the air had been expelled and replaced byoxyhydrogen mixture (prepared by electrolysis).The different partsof the apparatus, of which a sketch is given, were fused together, soas to avoid the use of joints or corks; and it was so arranged thatsamples of the gas could be obtained as often as desired for analysis,without interrupting the experiment. I n the first weeks, no appre-ciable amount of nitrogen was evolved, but subsequently there was tlrloss in Experiment 1 (with 14 856 grams of substance, containing0.5151 gram of nitrogen) of 20 miligrams of nitrogen. I n Experi-ment 2 (with 14.5969 grams of soil, &c., containing 0.2208 gram ofnitrogen) the loss of nitrogen was 11 milligrams.No nitrous oxidewas given off.In the other series of experiments, layers of soil or other substanceswere put in alternate layers with pieces of glrlss rod in uprightcylinders, so constructed that air free from combined nitrogen couldbe passed throngh from below, and any ammonia which might begiven off absorbed by acid, and the quantity determined at the end ofthe experiment.The foilowing table shows the nature and amounts of the sub-stances experimented on, the total initial and final nitrogen; thenitrogen as nitric acid, and tbe nitrogen a8 ammonia, found at theend of the experiments. The experiments 1-6 extended over nearlya year, whilst the 0thel.S la3te.l f r o 4 16 to 22 weeks3713 ABSTRACTS OF CHEMICAL PAPERS.grams1 -10781.11443-12523*0c3303.08521.10441.Arable eoil (100 grams). ,2. ?, 3 , * I 3. Arable soil (100 gram)st erilised .............4. Liipin soil (100 grams) . I5. >, 9 7 '0. Lupin soil (100 grams)sterilised.. ...........--gram0 *03110 *OL960000 --7. Arable soil (100 grams)and ammonium sulphatfcontaining 0 -115 gram8. Arable soil (100 grams)with bone meal (5 grams)9. Lupin soil (100 grams)with bone meal (5 grams:10. Bone meal (9.4775grams), chalk (2 grams)11. Sonerneal(9.9'702 grama:12. Blood meal (10.4941grams), chalk (2 grams)13. Horn meal and superphosphate" (equal parts14. Horn meal and superphosphatet (21 -002 grams) .15.Horn meal and superphosphate-gypsum16. Bone meal (10.804'grams), and gypsum (1:prams) ..............17. Bone meal (12.103'grams), and kainite (1grAms) ..............18. Bone meal (10.G83'grams), and chalk (1(grams) ..............of nitrogen.. .........----21 -034 grams) .......(22 -9694 grams) ......3 *l8763 -29733 - 2822i t com-mence-ment.0 *03620 *lo920 *0454Total.0.48511'42840 -36200 -4180granis0 *11980'12140 -12090 -10610.10450 -104200 --0 *01320 *00330 -23630 -31690 '28900 '44840 '47171 '40740 -41 900*42840.46760'43170 -36600 *42500 -41540 * 45000.49870 -44a20 *0049000Nitrogen.At conclusion.Asnitrate.IAs ammonia.0 *059(trace0 -097C0 *281t0.307:1 -07810 *10710 -199'[-.:::0.2430 -274I nreceiver.gram0 *00080 -COO60'00330.00060 ,00060 -0056--tracetrace0 *06780 -15000 *06710.814900 '00200 -10180 '11700.0555Gain orloss.gram - 0 * 01 20 - 0 .OOiO+ 0*0033 - 0 '0231 - 0 '0193+ 0 -0002- 0 -0487- 0 -0196- 0 -0069+ 0 ~0171-+ 0.0133f 0 -0210- 0 -0040- 0 *0070+ 0 -0036- 0 -0216- 0 '03 100 '2578 , -0 %087I* Containing 33.7 per cent.of soluble phosphoric acid. + Containing 8.6 per cent. of soluble phosphoric acidVEGET IRLE PHYSIOLOQT AND AORTaULTURE. 817With regard to loss of free nitrogen, the results show that i t maytake place during decomposition in presence of plenty of oxygen,both when nitrification takes place and when ammonia is formed.Gain of nitrogen took place (Experiments 10, 11, 12) in substancescontaining plenty of nitrogen, and coincidently with large productionof ammonia.As other experiments indicate that under these con-ditions loss of free nitrogen takes place, this was probably also thecase in these three experiments, and the gain must therefore barebeen still greater than the numbers iidicate. The last six experi-ments are of further interest as showing the retentive power, or wantof such a power, for ammonia of various substances. The super-phosphate retained the whole of the ammonia ; the superphosphate-gypsum, and gypsum kept back some, but allowed very much toescape.Kainite, on account of its greater solubility, acts morestrongly in fixing ammonia than either superphosphate-gypsum orgypsum. Calcium carbonate assists the volatlilisation of ammonia.When phosphoric acid was used, there was no loss of free nitrogen,whilst, when other substances, especially kainite, were employed, theloss of free nitrogen was considerable. The author is, however, notprepared to say that the non-evolution of nitrogen was due to thepresence of phosphoric acid (compare v. Krause, Abstr., 1890,1340).I n the course of the first series of experiments, it was noticed thatwhen the tube containing soil was filled with electrolytic gas, the gasdisappeared entirely in a few days. I n order to ascertain whetherthis was due to the physical and chemical properties of the soil, orto micro-organisms, the following experiments were made :--25 gramsof moderately moist arable soil was piit into the apparatus (similarto that used in the first set of experiments already described), wilichwas exhausted and filled with the oxyhydrogen mixture.I n the firstf o u r weeks there was only a slight absorption, but a good deal ofcarbonic anhydride was evolved ; afterwards the absorption was morerapid, and in abont five weeks almost the whole of the gas wasabsorbed, and nearly a vacuum produced. A similar experiment inwhich a few drops of chloroform were introduced into the apparatusshowed that under these conditions only a trace of carbonic anhydridewas given off, a n d that no absorption of the oxyhydrogen mixture tookplace, Two more experiments were made in which blood meal (5 grams)was mixed with the soil ; similar results were obtained.The absorp-tion of oxygen and hydrogen is therefore probably due to mic1.o-organisms in the soil. The author considers this power of unitiligoxygen and hydrogen to be more remarkable than the power offixing nitrogen, and refers to the processes studied by Winogradsky,in which bacteria oxidise ferrous oxide to ferric oxide, hydrogensulphide to sulphur, and finally to sulphuric acid, &c.Experiments were also made to see if pure cultivations of bacteriafrom pea and bean nodules have the power of assimilating free nitro-gen, but they alvays failed to develop well in nutritive solutions freefrom nitrogen.The following conclusions are drawn from the above results:-(1.) Loss of nitrogon can take place in decomposing nitrogenou3 i 8 ABSTRACTS OF CHEMICAL PAPERS.matter, independently of nitrification ; whilst it does not t t k e placewhen air is excluded.(2.) It is not established whether free nitro-gen is eliminsqted during the nitrification of ammonia with sufficientventilation. (3.) Free nitrogen is fixed not only in poor soils, buti n materials rich in nitrogen. (4.) Superphosphates are excelleri tpreservatives for farmyard manure, even when air has access. Super-phosphate-gypsum is of less value, whilst gypsum and kainite are farless effective still. (5.) Arable soil, aft#er undergoing a process ofdecomposition, has the power of uniting oxygen with hydrogen, thenniou being probably accomplished by bacteria.(6.) No kind ofbacteria has as yet, with certainty, been isolated which has thepower of fixing free nitrogen; although i t is established that theLegurninom, with the help of certain known bacteria, are in a positionto employ free nitrogen to their advantage.Sketches are given of the apparatus employed, which was similarto that used by Tacke.After the above investigation mas completed, the author found thatthe absorption of oxygen and hydrogen by soils had been discoveredbg de Saussure, in 1834. Licbig (Anmlen, 153, 142) considered theprocess to be a purely chemical one.Fixation of Free Nitrogen by Plants. By T. SCHLOESING, Jun.,and E. LACRENT (Compt.rend., 113, 776--778).-An extension ofthe work on the Legutninom (Abstr., 1891, 353) t o other classes ofplants. Two experimental methods were employed, the first con-sisting in measuring the decrease in volume of the nitrogen of theatmosphere in which the plants were confined, the other in estimnt-ing the increase of the total nitrogeii in the soil, seeds, and crop duringthe experiment. The results yielded by the two methods agree well.A s the conditions under which nitrogen might be absorhed were un-known, it was necessary to employ natxtral soil, for which purpose a.poor sandy earth was enriched with calcareous earth, and withgarden soils in which grass, trefoil, lupin, and beaus had been grown ;it was watered with nutritive mineral solutions also, and, after theseeds had been sown, with an aqueous extract of the mixture ofgarden soils.In the first set of experiments, which extended over 39 months,the results were obscured by the growth of mosses and algm on thesurface of the soil, and although it was found that the nitrogen ab-sorbed was markedly greater in the case of the leguminous pIarits(peas) than in those of the others (Jerusalem artichokes, oats, andtobacco plants), yet it could not be ascertained to which vegetationthe absorption was due.That nit,rogen was assimilated during thegrowth of the cryptogams was evident, since in one of the blankexperiments in which no appreciable growth appeared on the surfaceof the soil, no sensible amount of absorption took place, whilst inother blank experiments in which the lower growths had developedfreely, a, considerable amount of nitrogen was taken up.In a second set of experiments, which extended over three months,the lower growth was prevented by covering the soil with a layer ofcalcined quwtz Rand, and it was found that neither with soil alone,N.H. MVEQEThRIiE PRPSTOLO(:Y AND AGRICULTURE. 879nor with growing plants of oats, mustard, cress, or asparagus, WRSthere any sensible absorption, whilst with peas, a very considerableamount of nitrogen was found. I n the last case i t was remarked,too, that nodosities had formed on the 1-oots.Rerthelot (ibid., 778-779), in calling attention to the above note,points out the confirmation which the results bring to his ownresearches and views on this subject.Prote'ids of the Maize-kernel.By R. H. CHITTENDEN and T. B.OSBORNE (Amer. Chem. J., 13, 453-468 ; compare Abstr., 1891,1285).-The authors propose to investigate, first, the prote'ids which Rresoluble in salt solution, but insoluble in water ; secondly, those whichare soluble both in water and in salt solution, and, thirdly, thosewhich are insoluble in water and salt solutions, but soluble inalcohol.When fine freshly-ground maize-meal is extracted in the cold with10 per cent. sodium chloride solution, it yields a yellow solution,from which the prote'ids may be precipitated either by removing t bsalt by dialysis or by adding ammonium sulphate to saturation. Theprecipitate is purified by redissolving in sodium chloride solution andagain dialping, and then separates in small spheroids, which adhereto the walls of the dialyser, and closely approximate to crystals incharacter.The ammonium mlphate precipitate is partially solublein water, and may therefore be treated with that solvent beforedigesting with sodium chloride, the two solutions being mixed beforedialysing. 5 per cent. ammonium chloride solution may be sub-stituted for the sodium chloride, the prote'ids being precipitated asbefore by ammonium sulphate. The products obtained in this waywere of practically identical composition :-C, 51.65 ; H, 6.82 ;N, 17.69; and S, 0.93. The yield of pure product obtained by thefirst method was 0.2 per cent.When the sodium chloride solutions of the protei'ds are heated,they become turbid, and a t a somewhat higher temperature form aflaky coagulum ; if this is filtered off, the clear filtrate undergoes thesame changes when raised to a still higher temperature, and so on,several distinct fract'ions being obtained ; even when the solutionhas been boiled for some time, the filtrate often yields a precipitatewith acetic acid.The temperatures of coagulation are not, however,very constant, as theg are considerably altered by slight variationsin the methods of extracting and purifying the prote'ids. From aconsideration of these phenomena it appears that the prote'id mattereither consists of several distinct globulins, or is itself a, simpleglobulin capable of being split up by the action of heat.It may,for instance, be a mixture of variable proportions of vitellin and anuncoagulable globulin. Phytomyosin cannot ba present in quantitysince very little precipitate is thrown down when the sodium chloridesolution of the proteid is saturated with that salt.An attempt was made t o fractionate the proteid matter based ontohe facts that it is not entirely redissolved by sodium chloride solu-tion, and that the goluble portion is only partially reprecipitated by theaddition of a large quantity of wateP. The fractious soluble hJN. W,The present paper relates to the first class380 ABSTRAOTS OF CHEMICAL PAPERS.sodium chloride were of practically the same composition as theoriginal proteids, but the insoluble fraction contained appreciably lessnitrogen (15.59 per cent.).The formation of the insoluble prote'idmay be explained by supposing that the globulin is partially con-verted into an aidbuminate. Another attempt was based on therarying solubility of the proteiid in sodium chloride solutions ofdifferent strengths ; but the fractions obtained were unaltered incomposition. JN. W.Choline and Betaine in Cotton Seed Foods. By W. MAX-WELL (Amer. Chem. J., 13, 469-471)..-The bases were extractedfrom finely ground cotton-seed cake with 70 per cent. alcohol, andpurified by means of the mercurochlorides. The hydrochlorides pre-pared from the latter were separated by means of absolute alcohol, inwhich the beta'ine salt is very sparingly soluble. The relative amountsof choline and beta'ine hydrochloride thus obtained were as 1 to 5.7.The relative amounts obtained from cattle food prepared from a sampleof the same cotton seed was as 1 t o 4.7.JN. W.Occurrence of Gums which yield Xylose. By A. VOSWINKEL(Chem. Centr., 1891, ii, 655 ; from Phaym. Centralkalle, 32,505-50;).-The author found these gums in several fungi, CantharelZus cibnrius,Hydnum repandzm, Clamria Jlava, C. botrytis, Psuliota camyesty is,Boletus edulis, and B. grnnulatus. It was separated by extracting theground fungus with soda; the extract was then precipitated withalcohol, and the precipitate washed with alcohol containing a littlehydrochloric acid. The product gave the phloroglucinol and furfur-aldehyde reactions, and was converted iuto xylose by dilute sulphuricacid. J. W. L.The PoisonouEi Constituent of the Ethereal Fern Extract,By E. POUJ~SON (Chem. Centr., 1891, ii, 673 ; horn Arch. expt. Path.Pharrri., 29, 1--24).-l'he author's experiments show that tlrepoisonous properties of fern extract are due to an amorphous sub-stance which is the trueJZzcic acid. The acid is readily converted intoits lactone, by simply boiling its ethereal solution. The lactone isnamed filiciii, by the author. The filicic acid melts at 184.3" ; filicinmelts at lf23". The pure acid may be obtained from filicin by dis-solving the latter in cold dilute soda, and filtering the solution intodilute hydrochloric acid. The white precipitate is then dried oversulphuric acid. Determinations of the molecular weights of the twocompounds by Raoult's method gave for filicin 642 and 654, which,in coujunction wit'h the analysis, indicates the formula C35H400,2,whilst, for filicic acid, the numbers 663-699 were obtained, and this,in conjunction with the analysis, indicates the formula C35H&13.The author considers filicic acid to be suitable f o r therapeuticit1purposes ; it is readily soluble in the alimentary canal, but difficult lgreduced and either kills parasitic organisms or expels them, witlioutdamaging the canal. It appears to be more readily absorbed if takenwith oil than iE taken alone. J. W. LANALYTICAL CHEMISTRY. 381Ammonia in the Atmosphere and Rain Water of the Tropics.By V. MARCAKO and A . MUWZ (Compt. rend., 113: 729--781).-Theobservations, which extend over several years, were made nearCaracas, Venezuela, in 10" N. latitude, a t an altitude of 922 metresabove sea-level. The temperature of this locality is constant, therains very intermittent, and the storms violent and numerous. Ithas already been shown (Abstr., 1889. 923) that the nitric andnitrous nitrogen in the air of this region is ten times more abundantthan in that of more temperate climates, and it is now found that theammonia is distinctly less, a surface of acidified water 1 square metrein area absorbing in 24 hours an average of 0.012.32 gram of ammonia,a s against 0.02 and 0.024 in France. This unexpected result is probablydue to the formation of solid ammonium nitrite and nitrate in the air,a theory borne out by the excessive amount of ammonia found in therain water, 0.00155 gram per litre on an average, tts against 0.00032gram in Alsace (Boussingault) and 040097 a t Rothamsted (Lilwesand Gilbert). (Compare, however, next abstract.) JN. W.Ammonia in Rain Water. By ALBERT-L~VY (Compt. rend,, 113,804--805).-The author points out that the figures of Lawes audGilbert quoted by Marcano and Muntz (precei'iiig abstract) variedconsiderably from year to year, and that, in 1856 for example, theyfound 0.00143 gram of ammonia per litre, an amount quite compar-able with those obtained by the authors criticised. H e also quotesvarious other data to show that the amount of ammonia in the rainwater of Venezuela is not excessive ; the mean amount, for instance,i n the rain water of Montsouiis, France, where he has estimated theammonia in every downpour for upwards of 16 years, is as much iLs0.0022 gram per litre. JN. W

ISSN:0368-1769    

DOI:10.1039/CA8926200367

出版商:RSC    

年代:1892

数据来源: RSC