i. 149 Organic Chemistry. Catalysis and the Formation of Petroleum. CAHL ENGLER anti E. SEVERIN (Zeitsch. angew. Chern. 1912 25 153-158).-Re- petition of Kunkler’s experiments on the distillation of crude oleic and stearic acids at atmospheric pressure (Chern. Zent~. 1910 i 2031) shows that decomposition begins a t 340° and 358’ respectively and that the formation of hydrocarbons is small and commences at about 400O. The suggestion of Kunkler and Schwedhelm (Abstr. 1909 i 281) that soaps may first be formed by the interaction of lime or alumina with fats and that these under theinfluence of heat may give rise first to ketones and eventually to the hydrocarbons of petroleum is untenable since ketones have not been found either in bitumens or petroleum and no indication of the existence of soaps in bitumen could be found by the authors.Various investigators have suggested that rock-forming materials by their action on organic remains may play some part in the formation of petroleum and some support to this view is afforded by the work of Sabatier Senderens and Mailhe on the catalytic decomposition of aliphatic acids and their esters by metallic oxides (compare Ipatieff Abstr. 1904 ii 644 645 ; 1911 i 937) and Grafe (Petroleum 1910 6 71) has pointed out that Lycopodium spores distilled with fuller’s earth afford a distillate similar in character to Scottish shale oil. The authors have therefore examined the distillates obtained from mixtures of oleic or stearic acid with diatomite fuller’s earth quartz sand and finely powdered quartz and find that these materials lower the temperature of decomposition and give rise to distillates richer in hydrocarbons than are obtained when the acids are distilled alone.Powdered quartz is the most efficient of the four followed by fuller’s earth which is better than either diatomite or sand (compare Hviid Petroleum 1910 6 429). The distillates full details of which are given in the original in general resemble those obtained by distillation of fatty acids under pressure (Abstr. 1888 928) but contain more undecomposed acid and less low-boiling hydrocarbons. The conclusion is drawn that in the conversion of organic remains into petroleum the influence of rock- forming materials as well as of time temperature and pressure must be taken into account. T. A.H. Presence of Cholesterol in Java Naphthas. CARL ENGLER and WILRELM STEINKOPF (J. Russ. Phys. Chem. Soc. 19 11,43 1820-1825). -The work of Koss (Abstr. 1911 i 761) which was carried out partly under the supervision of the authors and also its unauthorised publication are severely criticised. T. H. P. Valency of Carbon in So-called Unsaturated Compounds. ALEXEI E. TSCHITSCHIBABIN (J. Russ. Fhys. Chem. Xoc. 1911 43 1690-1735).-A discussion of the various explanations which have VOL. CII. 1. mi. 150 ABSTRACTS OF CHEMICAL PAPERS. been advanced of the unsaturated character of the carbon atom in different classes of organic compounds. T. H. P. PPy-Trimethylpea tane. LATHAM CLARKE and WEBSTER NEWTON JONES (J. Amer. Chem. Xoc. 1912 34 170-174).-1n continuation of a study of the octanes (Abstr.1911 i 354 and earlier abstracts) PPy-trimethylpentane has now been synthesised. By the action of magnesium ethyl bromide on pinacolin PPy-trimethylpentan-y-ol was produced and was converted into y-iodo-PPy-trimethylpentane by the action of iodine and amorphous phosphorus. On treating this carbinyl iodide with alcoholic potassium hydroxide /3/3-dimethyl-y-methylene- pentane was obtained and on passing this over finely divided nickel at 160° in a current of hydrogen PPy-trimethylpentane was produced. PPy-Trimethylpentalrz-y-ol CMe3*CMe(OH)*CH2Me b. p. 149-152'1 760 mm. is a colourless liquid with a camphor-like odour. The octyllene (PP-dirnethyll-y-methylenepentane) C:Me,*C( :CH,)*CH,Me b. p. 110~4-110~8°/760 mm. is a colourless mobile liquid with a faint musty odour.@Py-TrimethyZpentane CIMe,* CHMe* CH,Me b. p. 110~5-110~8°/760 mm. Di 0.7219 n$' 1.4164 is a colourless mobile liquid with a very faint odour. E. G. PG-Dimethylheptane. LATHAM CLARKE and SYDNEY A. BEGGS ( J . Amer. Chem. Xoc. 1912 34 60-62).-1n continuation of the work on the nonanes (following abstract) PG-dimethylheptane has been synthesised. When P-methyl-&pentanone (methyl isobutyl ketone) obtained by the hydrolysis of ethyl isopropylacetoacetate is treated with magnesium n-propyl iodide the nonylene (/3-methyZ-G-methyZeneheptane) CH,Me*CH2-C(:CH2)*CH2*C€€Me? b. p. 132-133' is obtained as a colourless liquid with an odour resembling that of petroleum. The position of the double bond was not established but there is little doubt that the formula assigned to the compound is correct.On passing a mixture of the nonylene and hydrogen over freshly reduced nickel /3G-de'methyt?heptane CH,Me*CH2*CHMe*CH2* CHMe b. p. 132*9-133'/752 mm. Di 0,7206 n z 1.4014 is produced as a colourless liquid witjh a petroleum-like odour. E. G. /kDimethylheptane. LATEIAM CLARKE and SYDNEY A. BEGGS ( J . Amer. Chem. Xoc. 1912 34 54-60).-1n a study of the octanes (Abstr. 1 91 I i 354 and earlier abstracts) certain relations have been discovered between the chemical constitution and physical properties. An investigation has been undertaken in order to ascer- tain whether similar relations occur in the nonane series and an account is now given of the synthesis and properties of fiedimethyl- heptane which has been obtained previously in an impure state by Welt (Abstr.1896 i 332). ,&Methyl-€- hexanone obtained by the hydrolysis of ethyl isobutylacetoacetate was converted into pcdimethyl-E-heptanol by means of magnesium The synthesis was effected in the following manner.i. 151 ORGANIC CHEMISTRY. ethyl bromide. The iodide of this alcohol was prepared and when boiled with alcoholic potassium hydroxide yielded ,!%methyl-r-methylene- heptane which was then reduced to PE-dimethylheptane. Pr- Dinaethyl-r-~LeptunoZ CH2Me*CMe(OH)*CH,*CH2*CHMe2 b. p. 172-1'74° is a colourless liquid with an odour of musty apples The non $en% ( p-me t h y I- E-nae t h y Zenehe pt m e ) CH2Me-C(:CH,)*CH2*CHz*CHMe b. p. 139-140° is n colourless liquid with a sweet petroleum-like odoiir.PE-Dimethylheptane CH~Me.CHRle.CH,*CH,*(=HMe b. p. 135.6-1 35.9"/760 mm. Dii 0.7 190 92 1 *4O20 obtained by passing a mixture of the nonylene and hydrogen over freshly reduced nickel at 160-1 SOo is a colourless liquid with a petroleum-like odour. E. G. Conjugated mi-Nitro-compounds. ARTHUR HANTZSCH and KURT VOIGT (Bey. 1912 45 85-117).-A number of nitro-compounds chiefly aliphatic substances containing NO attached to carbon have been examined spectrometricnlly to determine how the absorption spectrum is affected when the real nitro-group is changed to an mi- nitro-group. The chief result of the investigation has been the discovery of a new type of nitro-compound which is called a conjugated mi-nitro-compound. The nitro-group may be present in a substance in three forms each of which has its characteristic absorption curve.Aliphatic real nitro- compounds show very feeble selective absorption the curves exhibiting a very flat band or a kink beginning at oscillation frequency 3413. It is inmaterial whether the nitro-group is the only negative substituent in the molecule or whether another (NO NOH CO CO,EI CO,Et CO*NH CN Ph) is present provided that the intmduction of the latter does not produce a constitutive change in the nitro-group. A simple aci-nitro-group >C:XO*OH causes weak general absorption; such groups are present only in the salts of the nitropnraffins CHR:NO*OM. When however an aci-nitro- group is present together with another negative group X (one of those mentioned above) then without exception the substance exhibits very strong selective absorption the curve exhibiting a very deep band for thicknesses corresponding with 10 to 100 mm.of N/lO,OOO solution. Since the introduction of a negative group into a real nitro-compound has little optical influence whilst n simple aci-nitro-group alone causes general absorption it follows that the strong selective absorption exhibited by a substance containing both an nci-nitro- and another negative group must be conditioned by the influence of these two groups on one another. This influence i s represented by a peculiarly constituted six-membered ring . pro- duced by the union by a supplementary valency of a metallic or hydrogen atom or of an alkyl group with a negative atom of the __ negative (unsaturated) group X R*CqN0.-X- O;>(Na,H,Me). For examples X is a nitro-group in aci-dinitro-compounds (salts of di- and tri-nitromethane) an R*CO group in a-aci-nitroketones (the nitro- barbituric acids ; ethyl uci-nitrornalonate) and a cyano-group in a-cyano- 2i. 152 ABSTRACTS OF CHEMICAL PAPERS. aci- ni t ro- compounds ( f ulmi n uric esters ; aci-ni t rocyanop he u y lrnet hane). A n aci-nitro-group in this state is called a conjugated mi-nitro-group. I t s presence explains why the introduction of a third negative group into the molecule exerts so slight a n optical influence ; the third group can only have a feeble auxochromic effect. aci-Nitrophenylmethane and its salts contain a conjugated aci-nitro-group ; consequently the benzene nucleus by means of a supplementary valency (in the ortho- or para-position) can form part of the six-membered complex. Certain conjugated aci-nitro-compounds (fulminuric acid and the nitrobarbituric acids) are so stable that they cannot be converted even by concentrated sulphuric acid into real nitro-compounds.Further- more substances containing a simple aci-nitro-group together with another unsaturated group are incapable of existence ; therefore when a real nitro-compound containing another unsaturated group is trans- formed into an aci-nitro-compound a conjugated mi-nitro-group is always produced. The chromoisomerism of certain conjugated aci-nitro-compounds for example the yellow and the colourless salts of the nitrobarbituric acids cannot be explained by regarding the yellow salt as containing a conjugated aci-nitro-group and the colourleas salt as containing a simple mi-nitro-group because the latter group cannot exist in such compounds.Both salts contain the conjugated aci-nitro-group. The colour of the yellow salt is due to a shifting of the absorption band towards the red end of the spectrum. Chromoisomerism in such cases therefore is merely valency isomerism and is represented thus -E*O-M -C*NO:O * and -Q:"--- -C:NO*d When the ionisation of a substance containing a conjugated aci- nitro-group is unaccompanied by secondary changes the ions are optically identical with the undissociated acid and therefore contain the peculiar Pix-membered ring. This result leads to Werner's theory that the formation of ions is in the first step a case of hydrate formation.For the particular examples under discussion the ionisa- tion is represented by the scheme --X.. R * c < ~ ~ . ~ > H + R*c<G.:>H-- -OH 2 -+ I n conclusion attention is drawn to the extensive optical and chemical analogies between negatively substituted nitro-compounds on the one hand and negatively substituted ketones (ethyl acetoacetat,e) on the other. c. s. Aliphatic Nitro-compounds. XII. Constitution of aci- Nitro-compounds. WILHELM STEINKOPF and BORIS J URGENS (J. p r . Chem. 1911 [ii] 84 686-713. Compare Abstr. 1911 i 530).-The formation of hydroxamic chlorides by the action of hydrogen chloride on aliphatic nitro-compounds is referred by the authors to the decom- position of the mi-nitro-compound into the corresponding aldebyde and nitroxyl which then combine t o form a nitroso-alcohol (I); the latter compound reacts with hydrogen chloride yielding a ehloronitroso-ORGANIC CHEMISTRY.i. 153 couipound (Il) which then undergoes transformation into the hydrox- aniic chloride (III) RS shown in the following scheme R*CH:NO*OH -+ R*CHO+ :NOH -+ (I) R*CH(NO)*OH -+ (11) R*CHCl*NO -+ (111) R*CCl:N*OH. This view is supported (1) by the observations of Nef (Abstr. 1895 i 3) and also of Hantzsch and Veit (Abstr. 1899 i 401) who find that mi-nitro-derivatives of hydrocarbons readily decompose into aldehyde nitrous oxide and water; (2) by the formation of hydr- oxamic acids by the direct combination of aldehydes and nitroxyl (Angeli) and (3) by the production of blue o r green colorations due to the formation of chloronitroso-compounds R*CHCl*NO when salts of the nitro-derivatives of aliphatic hydrocarbons are acidified in aqueous or ethereal solution.Attempts have been made to isolate these coloured compounds in the case of nitromethane nitropropane and nitro- ethane but only with the last-mentioned compound were the attempts successful. When a suspension of the sodium salt of aci-nitroethane in a large volume of ether is treated with an excess of hydrogen chloride and the resulting solution after removal of the sodium chloride rapidly evaporated chloronitrosoettiane (Piloty and Steinbock Rbstr. 1902 i 735) was obtained. If a small volume of ether is used and excess of hydrogen chloride avoided the product consists of ethyl- nitrolic acid. The formation of the latter compound is due to the action of nitrous acid produced by the decomposition of the intermediately formed nitroso-alcohol NO*CMeH*OH on unchanged nitroethane.Salts of nitro-compounds such as nitroacetic acid and nitroaceto- nitrile which contain strongly negative groups do not give blue or green colorations when treated with acids and the conclusion is there- fore diawn that in these cases decomposition of the mi-nitro-compound into aldehyde and nitroxyl does not take place. This view is supported by the behaviour of w-nitroacetophenone which on treatment with hydrogen chloride in ethereal solution yields w-chloro-w-oximinoacetophenone !Thiele and Haeckel Abstr. 1903 i 160) without the intermediate formation of a coloured nitroso- compound. aci-Phenylnitromethane which contains the feebly negative phenyl group occupies an intermediate position ; with ethereal hydrogen chloride it develops the blue coloration very slowly instead of instantly as in the case of the nitro-derivatives of aliphatic hydro- carbons and this coloration gradually disappears owing to the formation of benzhydroxamic acid.These differences in the behaviour of nitro-compounds are best explained on the assumption that the mi-nitro-derivative has the constitution CRH-N*O€I proposed by Hantzsch and not the \/ 0 Michael-Nef formula CHR:NO*OH now generally accepted. The stability of the carbazoxy-ring depends on the nature of the sub- stituents. When R=H or alkyl the ring is unstable and readily suffers complete rupture as indicated in the following scheme R-CH-/-N*OH 0 \)< -+ R*CHO + :N*OH.i.154 ABSTRACTS OF CHEMICAL PAPERS. On the other hand when R is a strongly negative group the stability of the ring is greatly increased so t h a t rupture occurs only at one point either between C and 0 with the formation of a nitro- compound as shown in (I) below or between N and 0 with the formation of a hydroxamic acid as indicated in (11) t- R*CH-NOOH \)< -3 R*CH2-N<<E or R*CH,*N< 0 I 0 (I.) o The evidence furnished by Nef in favour of the formula R*CH:NO*OH for mi-nitro-compounds is subjected to a critical examination and the conclusion is drawn that Hantzsch's formula affords a simpler and less forced explanation of the behaviour of these compounds. Numerous examples of the reactions of nitro-corn pounds and of a large number of other classes of compounds containing the carbazoxy-ring are cited in support of the authors' view.Speciflc Gravity Table of Alcohol-Water Mixtures at 17.5". WILHELM FRESENIUS and LEO GRUNHUT (Zeitsch. unal. Chem. 1912 51 123-124).-A useful table giving DiP5 for a number of mixtures of alcohol and water together with the corresponding alcohol % by weight and by volume and also alcohol in grams per Action of Potassium Hydroxide on Secondary Alcohols ; Diagnosis of Primary and Secondary Alcohols of High Molecular Weight. MARCEL GUERBET (Compt. rend. 1912 154 222-225. Compare this vol. i 67).-W hen secondary alcohols are heated at 230' with potassium hydroxide some oxidation occurs with production of potassium salts of acids but the greater part of the alcohol forms condensation products ; thus isopropyl alcohol yields formic and acetic acid together with P-methylpentan-8-01 and /3G-dimethylheptan-(-ol.The corresponding higher homologues are obtained from sec.-butyl alcohol and octyl alcohol. The ease with which the reaction is carried out renders it suitable for distinguishing w. 0. w. Specific Gravity and Hygroscopic Power of Glycerol. ANTON KAILAN (Zeitsclh. anal. Cliem. 1912 51 81-lOl).- Anhydrous glycerol has DY 1.26413. The density between 14' and 2OOLcan be calculated by the expression D:= 1.26413 + (15 - b) 0.000632 and a table is given of densities from 14.3' to 20.6'. Boiling points under various pressures bebween 9 and 32 mm. are also recorded. Glycerol rapidly absorbs moisture from the air and a number of determinations of the hygroscopic power of anhydrous and hydrated samples are given.It appears that a mixture containing 80% of glycerol is in equilibrium with air containing an average amount of moisture. The author also noticed that alcohol containing but little water absorbs in the same circumstances water four times more rapidly F. B. 100 C.C. L. DE K. between secondary and primary alcohols. than does a similar glycerol. L. DE K.ORGANIC CHEMISTRY. i. 155 Preparation of Epichlorohydrin from Dichlorohydrin and Alkalis. FARBENFABRIKEN VORM. FRIEDR. BAYER & Go. (D.R.-P. 239077).-'rVhen dichlorohydrin (129 parts) in 200 parts of water is slowly treated with 133 parts of 30% sodium hydroxide solution it yields 85 parts of epichlorohydrin; the sodium hydroxide may be replaced by its equivalent of potassium or ammonium hydroxide but the above concentrations must be carefully maintained.Tautomerism of the Dialkyl Phosphites. THADDEUS MILOBENDZKI (Bey. 1912 45 298-303).-Previous investigations (Abstr. 1807 i 391 ; 1908 ii 488; 1903 i 733; 1907 i 8 1899 i 659) bave indicated that dialkyl hydrogen phosphite in the free condition has the constitution (I) O:PH(OR),. From the behnviour of the esters in aqueous solution the author shows that they also exist in the tautomeric form (11) OH*P(OR),. Silver salts of the composition Ag*PO(OR) are precipitated from aqueous solutions of diisopropyl hydrogen phosphite (b. p. 74-75O/ 9 mrn.) and diethyl hydrogen phosphite (b. p. 66-67'/9 mm.) by the successive addition of silver nitrate and aqueous alkalis (ammonia sodium hydroxide and barium hydroxide); the addition of the reagents in the reverse order produces no precipitate.According to the author the silver salts OAg*P(OR) are readily soluble in water and the non-formation of a precipitate when the alkali is added before the silver nitrate is due to the transformation of the keto-ester (I) into the enolic form (11). The silver salts Ag*PO(OR) dissolve in excess of alkali owing to change into the tautomeric form induced by the hydroxyl ions; on acidifying the alkaline solutions the original salt is precipitated. Dialkyl hydrogen phosphites show the phenomenon of gradual neutralisation. The percentage of the ester (I) present in aquoous solutions has been determined by adding the equivalent amount of aqueous ammonia followed immediately by the addition of silver nitrate ; the amount of silver salt Ag*PO(OR) precipitated cor- responds with that of the ester of the formula (I) originally present ; with diethyl hydrogen phosphate the amount is 35%.That the enolic modifications of the esters are capable of existing in aqueous solution has also been shown by neutralising with aqueous barium hydroxide and then adding the equivalent amount of sulphuric acid; the solutions thus obtained do not show the phenomenon of gradrial neutralisation nor yield insoluble silver salts. Triethy 1 phosphite is hydrolysed by excess of aqueous sodium hydroxide to sodium diethyl hydrogen phosphite ; dialkyl hydrogen phosphites are not hydrolysed by alkalis.Experiments are also described showing that sodium diethyl phosphite prepared from sodium and diethyl hydrogen phosphite in ethereal solution exists in aqueous solution in the form NaO*P(OEt),. F. M. G. M. F. B. Constitution of Glycerophosphoric Acid Prepared by Eeteriflcation of Phosphoric Acid or Sodium Dihydrogen Phosphate. PAUL CARRE (Compt. rend. 1912 154 220-222,* Compare Abstr. 1904 i 133 215).-Sodium glycerophosphate * and Bdl. SOC. chirn. 1912 11 169-172.i. 156 ABSTHAC’l’S OF CHEMICAL PAPERS. prepared by Poulenc’s method was converted into glycerophosphoric acid by the process previously described. The product is identical in every respect with the acid formed in the direct esteritication of phosphoric acid by glycerol.The same acid is obtained when glycerol bromohydrin (3 mols.) is heated with silver phosphate and the resulting unstable ester OP[O*CH,*CH(OH)*CH,*OH] submitted t o hydrolysis. Poulenc’s compound must therefore be a salt of a-glycerophosphoric acid and not of the P-acid as stated by Paolini (Abstr. 1911 ii 774). The author has been unable to obtain Paolini’s Preparation of Glycol and Gly colhydrin Esters of Phosphoric Acid Glycerides ADOLF GHUN and FRITZ KADE (D.K.-P. 240075). -Cornpounds of general formula X*C,H,*O*PO(OH)*O*C,H,(O.CO. k)2 where R is an alkyl group and X halogen or hydroxyl can be rcadily prepared by the action of phosphoric oxide on distearin and etliylcne- glycol or halogenhydrins. brucine salt crystallising with 7H20. w. 0. w. The following products are described the compound C2H,C1*O*PO(OH)*0*C,H,(O-CO*C1,H35)2 w.p. 65-66’ ; the compound OH* C2H,*O* PO( OH)*O* C,H,( 0 *CO* C17H,,) 2 from ap-distearinphosphoric acid ester ethylenechlorohyclrin and glycol. The trirnetltyllamine salt C2H,C1*O*PO(O*NHlMes;.0.C,H,(O*CO*C17H35)~ m. p. 69”; and by the interaction of another molecule of trimethyl- amine the salt N Me,C1 C,H,*O*PO( O*N H Me3)*O*C,H,(0 *Corn C17Hs&. The Agglutination of Lecithins and Lecithin-protein Mixtures by Acids. J. FEINSCHMIDT (Biochem. Zeitsch. 1 9 12 38 244-251).-Aqueous susi ensions of lecithins of various origins have agglutination optima a t definite hydrogen ion concentrations which are identical with the isoelectric point. This varies in the different preparations between lo- and lo-* that is in somewhat strongly acid solutions.Neutral salts increase the turbidity of the solutions but make the actual agglutination point less sharp When lecithin and protein are mixed a new complex is formed in which the agglutination point shifts towards the less acid side; in this case the precipitation PAUL SABATIER and ALPHONSE MAILHE (Cornpt. rend. 1912 154 49-52. Compare Abstr. 191 1 i 258-416).-The catalytic decomposition of alkyl formates below 400’ is somewhat complicated and follows a different course from that of esters of higher acids. I n general two principal reactions occur represented by the equations (1) 2H*CO,R = H0CH.O + CO + R,O followed by the dehydration of the aldehyde with production of an unsaturated hydrocarbon ; (2) H*CO,R = CO + R*OH followed by dehydration or dehydrogenation of the alcohol.The water set free may effect hydrolysis the resulting formic acid then decomposing in the manner already described. F. M. G. M. is more energetic and coarser. s. B. s. Catalytic Decomposition of Formic Esters.ORGANIC CHEMIS'I'liY. i. 157 'i'ho nature of the catalyst considerably influences the course of reaction; thus in the case of methyl formate and titariiurn oxide reaction (1) predominates whilst with zinc oxide reaction (2) occurs almost exclusively. Both reactions take place with thorium dioxide. Finely divided platinum nickel and copper readily effect catalysis principally in accordance with equation (2). w. 0. w. C a t a l y t i c Formation of Saturated Aliphatic Esters from Formic EYters.PAUL SABATIER and ALPHONSE MAILHE (Compt. rend. 1912 154 175-177. Compare preceding abstract).-When ttm vapour of methyl formate and isobutyric acid in equimolecular proportions is pasmd over tit'anium oxide at 250' carbon monoxide is liberated and the condensed liquid contains 20% of methyl isobutyrate together with methyl alcohol and some isobutaldehyde. The esterification is explained by the decomposition of the methyl formate in the manner previously described whilst the aldehyde arises from reduction of the acid by formic acid. Thorium oxide acts in the same may but requires a higher temperature ; thus at 300-330° isovaleric acid and methyl formate give 40% of methyl isovalerate by volume and 16% of iso- valeraldehy de. Under these conditions the amount of ketone formed is inconsiderable but at 370° the condensed liquid contains 50% of ester 10% of isovalerone 15% of isovaleraldehyde and also methyl alcohol.Similar results have been obtained with higher acids and other alkyl formates. The direct reduction of acids by means of formic acid will be described in a further communication. w. 0. w. Optically Active Dialkylacetic Acids. EMIL FISCHER JULZUS HOLZAPFEL and HANS VON GWINNER (Bey. 1912 45 247-257. Compare Fischer and Platau Abstr. 1909 i ,62t)).-~-isoButylhexoic acid has been resolved into optically active components by crystal- lisation of the brucine salt. The difference between the butyl and isobuty 1 radicles is apparently enough t o cause pronounced optical asymmetry. a-isoButylvaleric acid has also been resolved but definite results were not obtained with a-isopropylvaleric acid.Ethyl butylisobutylmalonate prepared by the interaction of n-butyl bromide on ethyl isobutylmaloriate and sodium has b. p. 137-140'1 10 mm. When hydrolysed by means of todium hydroxide butgl isobutylnzulonic acid is obtained in colourless crystals m. p. 136-138'. The neutral solution of the ammonium salt gives a colourless precipitate with silver nitrate and crystalline precipitates of the corresponding salts with barium and calcium chlorides. On heating a t 1 60° butylisobutylucetic [a-isobutylhexoic] acid is obtaiced as a colour- less oil b. p. 145-145.5' (corr.)/lO mu. The brucine salt forms small microscopic prisms. The first separations were hydrolysed by heating with sulphuric acid.The optically active d-a-isobutyl- hexoic acid had [a] +5*73'. Ethyl propylisobwtylmulonate was obtained as a n oil b. p. 126'1 9.5 mm.i. 158 ABSTRACTS OF CHEMICAL PAPERS. Propylisobutylmalonic acid crystallises in stunted prisms or plates m. p. 147-149" (corr. decomp.). Propylisobutylacetic [a-isobutylvccleric] acid is a colourless oil D20 0.8928 b. p. 122' (corr.)/8*5 mm. ; it forms a colourless silver salt crystallising from ammonia in microscopic slender needles. The calcium salt also consists of microscopic slender needles. The bmcine salt forms microscopic small prisms and yields d-a-isobutylvaleric acid as a colourless oil m. p. 100°/0.5 mm. D22 0.8576 CUE] + gaso. The monoamide of propylisopropylmalonic acid CO,H*CPraPrp* CO*NH obtained by heating cganoisopropylvaleric acid with concentrated sulphuric acid crystallises in colourless bunches of intergrown prisms m.p. 137' (corr. decomp.). When heated over the flame in a distillation flask a-iso~rop~lvaZ~~ccm~de is obtained a t about 250'. It crystallises in slender colourless needles m. p. 131-1 33' (corr.). By the action of sulphuric acid and sodium nitrite at SO" propyl- isopropylacetic [a-isopropylvaleric] acid is obtained b. p. 11 6" (wrr.)/ 12 mm. 112-113°/9 mm. D17 0,9076. A partial resolution was obtained by means of the quinidine salt the acid formed having [a]? + 0.7'7'. E. F. A. Coniposition of Linseed Oil and the Distribution of Oxygen in Dried Layere of the Oil. 11. E. I. ORLOFF (J. Buss. Phys. Chem. SOC. 1911 43 1509-1524. Compare Abstr. 1910 i SlO).- The author criticises Fokin's work (Abstr.1907 i 820) the results of his own experiments being in agreement with Genthe's theory (Zeitsch. angew. Chem. 1906 19 2087) except that he finds that when a layer of the oil 100-108 sq. em. in area weighs 0.1-0*15 gram 15-16% of oxygen is taken up although setting occurs when oniy 12% has been absorbed. Experiments in which a cobalt dryer was employed give for the rates at which oxygen is fixed results corresponding with the formula B + x where A re- dx/dt=k(A - z ) ( B + x ) or k = ____ presents the total amount of oxygen absorbed expressed as reduction of pressure x the atmospheric pressure and B a constant. After the oil has combined with 12% of its weight of oxygen a solid phase is formed and the further velocity of the absorbing process is expressed by dx/dt = k ( A -fx)(S +fx) where 3' the correction coefficient is less than unity and corresponds with the product of combination of the solid phase k f being a constant magnitude.In parallel with this chemical process proceeds a physical one of diffusion of the oxygen into the oil the amounts of oxygen in successive layers starting from the surface being in the proportions of n n2 n3 n' . . . np where n is less than 1 (0.5 0.6 etc.). The quantity of oxygen combined is related to the factor n according to the expression S/Q=n/(l -n) where Q is the quantity of combined oxygen corresponding with the iodine number and S is the amount of oxygen fouud i n each separate case. Assuming complete distribution A 1 t ( A +B)' 'adz* 7)ORGANIC CHEMISTRY.i. 159 of the oxygen by diffusion the value of n must be taken as two-thirds. T. H. P. Molecular Rearrangements in the Camphor Series. IX. Lauronolic Acid and Campholactone. WILLrAnr A. NOYRS and CHARLES E. BURKE (J. Amer. Chem. Soc. 1912 34 174-1S3).- Tiemarin (Abstr. 1901 i 6) found that lauronolic acid prepared from bromocamphoric anhydride has a rotatory power which differs con- siderably from t,hat of the acid obtained by the distillation of camphanic acid and suggested that the acid produced by the latter method con- sisted of a mixture of optical isomerides. This has now been proved to be the case. Lauronolic acid prepared from active bromocamphoric anhydride by Aschan's method (Abstr. 1895 i 154) has been obtained in the form of rosettes of long needles; it has m.p. 6*5-S0 b. p. 230-235' under the ordinary pressure vapour pressure 99-100 mm. at 184" D',"5 1.0109 Dt5 1.0133 D;') 1.0249 [a] + 1 8 7 - 7 O 12 1.47556 and the dissociation constnnt I. 1.36 x The calcium salt crystallises with 3II,O instead of only 2H,O as stated by Bredt (Abstr. 1911 i 417) and when heated with soda-lime yields laurolene. When hydrogen iodide is passed into a solution of lauronolic acid in light petroleum the hgdriodide is obtained in the form of yellow plates and is very unstable. On reducing this compound with zinc dust and alcohol dihydrolauronolic acid C,H,,*CO,H is produced which has DY'5 0.9008 [a]$'5 +1.74' vapour pressure 100 mm. at 178" and 749 mm. a t 215' and [n] 1.45786; the amide has m.p. By decomposing inactive bromocamphoric anhydride prepared from synthetical camphor inactive lauronolic and camphanic acids were obtained. Inactive lauronolic acid has m. p. 5-S.5" vapour pressure 100 rurn. a t 192" DY 1.0318 and [nID 1.47655; its calcium s a l t crystallises with 1 H,O. Campholactone preparcd in various ways from lauronolic acids of widely different rotatory powers has m. p. 50" and [a] - 21.7" and when warmed with barium hydroxide solution is converted into tho corresponding hydroxy-acid m. p. 143" and [a] + 16.0". 50-51". E. G. Molecular Rearrangements in the Camphor Series. VIII. Ganiphonolic Acid and Camphonololactone. WILLIAM A. NOYES E. E. GORSLINE and R. S. POTTER (J. Amer. Chem. Xoc. 1912 34 62-67).-Four hydroxy-acids and three lactones have been described which retain the tertiary carboxyl group of camphoric acid.The structural formulz assigned to these compounds have not been well established and the present work was therefore undertaken with the object of obtaining further evidence as t o their constitution. Camphononic acid prepared by a modification of Lapworth and Lenton's method (Trans. 1901 79 1287) has I ~ I . p. 289-2330" [a]:'' in benzene (2.4 grams in 100 c.c.) + 17-8°,L[a]2 in alcohol ( 3 grams in 100 c.c.) - 3.9". On reducing this acid with sodium and ainyli. 160 ABS'l'HACTY OF CHEMICAL PAPERY. alcohol cmyl camyhonolccte is obtained as a yellow viwons oil of b. p. 222-223O/40 mm. ; the calcium copper and silver salts were prepared. It is shown that the lactone obtained by Noyes and Taveau (Abstr.1906 i 397) by decomposing the nitroso-derivative CH2*CMe*Co of aminolauronic anhydride with sodium hydroxide is I $Me 1 identical with cis-camphonololactone (annexed formula) prepared by Bredt (Abstr. 1909 i 498) by the cHz*CH-o electrolytic reduction of camphononic acid. cis- cHz'CMe*Co,H I - 22*3O. The coriesponding hydroxy-acid cis- camphonolic acid (annexed formula) has m. p. UR,.&W(OH) 202-203' when rapidly heated [a] in alcohol (10 grams in 100 c.c.) +29*2O and on oxidation with chromic acid is converted into camphononic acid. Camphonololsctone has m. p. 165-167' a] in alcohol (5 grams in 100 c.c.) - 20.2' and [a (10 grams in 100 c.c.) E. G. The Melting Point of Oxalic Acid. EYVIND EODTKER (Chem. Zeil. 1912 36 105).-Purc crystallised oxalic acid does not appear to have a definite melting poiut ; a small crystal placed in a capillary tube had m.p. 99*5-101-5° whilst a layer in the capillary tube 1 mrn. in height had m. p. 100-102.5° when the temperature was raised very slowly and maintained a t 100' for about one minute. w. P. s. Conversion of Maleic into Funiaric Acid. SEBASTIAN M. TANATAR (J. Buss. Yhys. Chem. Soc. 1 If 11 43 1742-1 746).-It was discovered by Skraup (Abstr. 1891 1338) that the interaction of hydrogen sulphide and sulphur dioxide in aqueous solution in presence of maleic acid is accompanied by transformation of the latter acid into fumaric acid ; this ef€ect he termed Since the reaction liquid after filtration from the sulphur formed contains nothing capable of bringing about this transformation the author has investigated the action of sulphur on maleic acid.Milk of sulphur is without effect and the same is apparently the case with the sulphur separated by the action of hydrogen sulphide on ferric chloride in presence of maleic acid. With sodium thiosulphate and a mineral acid however which normally give precipitation of sulphur maleic acid prevents such precipitation and is simultaneously con- verted into fumaric acid ; a similar transforrustion is produced also without separation of sulphur by addition of the thiosulphate to a solution of maleic acid alone That these solutions contain no dissolved sulphur is shown by extraction with carbon disulphide and the con- clusion is drawn that it is the reaction of the thiosulphuric and maleic acids with formation of an unknown product that induces the isomeric change.This same change is brought about by treatment of maleic acid with ammonia or potassium polysulphide (liver of sulphur) although in the latter case i t may be due to the presence of thiosulphate. resonance." T. H. P.ORGAN1 C C €1 EM I WRY. i. 161 Relation between the Configuration and Rotation of t h e Lactones in t h e S u g a r and Saccharinic Acid Groups. EENEST ANDERSON (J. Amn2er. CImnz. SOC. 1912 34 51-54).-Hudson (Abstr. 1310 i 220) has pointed out that dextrorotatory sugw lactones have the ring on one side of the st'ructure whilst Izvorotatory lactones have it on the other. It is now shown that this relation is true not only for the lactones to which Hudson referred but for nearly all monobasic and some dibasic acid lactones in the sugitr and saccharinic acid groups.The configurations and specific rotations of eighteen such lactones are tabulated. The relation affords a new method for determining the I configuration of the lactones formed by certain dibasic acids. E. G. E thy1 Orthotrithioforrnate. BROE HOLMBERG (Bey. 19 12 45 364-365).--In reply to Houben and Schultze (this vol. i 5) it is claimed that the product obtained by the ant,hor (Abstr. 1907 i 474) was pure. D. F. T. Action of Potassium Hydroxide on Tetrolacetal. PAUL L. VIGUIER (Compt. Tend. 1912 154 2 17-220. Co-mpare Abstr. 1909 i 691 ; this vol. i 7).-When tetrolacetal (diethoxybutinene) is dropped on potassium hydroxide a t 1SO-200° a liquid distils and on fractionation yields a compound C,H,O b.p. 29-33"/16 mm. D19.5 0.826 mL9.B 1.462. CHiC*CH:CH*OEt since it forms an explosive silver derivative C,H70Ag and is hydrolysed by acids forming an unstable substance having the properties of the uldehyde CHiC*CH,.CHO. The latter changes spontaneously into tiiacetyl benzene acetoace taldehyde probably being produced first. Hydroxylamine yields 1-methylisooxazole. On treat- i n g the aldehyde with sernicarbazide hydrochloride a semicarbctxone C,H,ON,Cl is obtained ; this yields the corresponding aldehyde This probably has the constitution C,H,OCl on hydrolysis. w. 0. w. Tartardialdehyde. ALFRED WOHL and BRUNO MYLO (Bey. 1912 45 322-349).-From the result of their endeavours the authors conclude that the synthesis of tartnrdialdehyde by the symmetrical linking together of two molecules each containing two carbon atoms presents excessive difficulties and they have finally attained success by other means.The action on acetyl chloride of copper hydride gives ethyl acetate and ethylidene diacetate whilst the action of copper on the additive product of dibromoacetaldehyde and acetyl bromide yields bromovinyl acetate. Dibromoacetaldehyde also reacts slowly with magnesium methoxide the product *being a /3/3S(or SSp-)-trib~omo-y- keto-n-but32 alcohol b. p. 77-79°/14--16 mm. Glyoxal sodium bisulphite in acetic anhydride solution reacts with hydrogen chloride producing unstable s-tlichloroglycol diacetate b. p. 110-115°/14 mm. (compare Prud'homme Zeit. Chenz. 1870 380).i.162 ABSTRACTS OP CHEMICAL PAPERS. Ethyl diethoxyacetnte in ethereal solution with potassium gives as chief product a n un d istilla ble syrupy substance P-ii ydrox y -y-ket o- succimdialdehyde dietluJaceta1 CH(OEt),*CO*CH(Ol3)*CH(OEt) ; the substance was not obtainable in a pure state and the action of sodium gave still less satisfactory results. The action of sodium on the piperidide of diethoxyacetic acid (Wohl and Lange A bstr. 19OS i 943) yields monoethoxyacetopiperidide b. p. 72-74°/0-0S-0.1 1 mm. Diethoxyacetoh ydrazide obtained from the e thy1 ester mi t h h y tl razine in alcoholic solution forms capillary crystals m. p. 43-45' and has b. p. 110'/0.05 mm. ; it reacts with mercuric oxide or metaboric acid eliminating nitrogen and forming bis-diethoxyacetohydrcczide CH(OEt),*CO*NH*NH*CO*CH(OEt) which crystallises in needles m.p. 67-70'; the mercury copper and lead compounds are described. Iodine removes mercury from the mercnry compound with the formation of azo-a-ketodi-P-ethoxyetlmne CH(OEt),*CO*N :N*CO*CH(OEt) a viscous colourless oil b. p. 131-134'/0*07-0~08 mm. which on warming decomposes giving ethyl orthoformate instead of the desired tetraethoxydiacetyl CH(OEt),*CO-CO*CH( OEt),. Success was attained by starting with di-magnesium acetylene dibromide (from acetylene and magnesium ethyl bromide) which on treatment with ethyl orthoformate gives acetylenedialdehyde diethyl- acetal CH(OEt),.CiC*CH(OEt) D1H.5 0-956 (compare Jotsitch Chem. Zeit. 1907 31 979) ; by reduction with hydrogen in the presence of colloidal palladium this passes into mnleinuldekyde diethylucetul b.p. 112-112*5°/1 1 mm. DZ3 0.926 which is oxidisable by potassium permanganate (compare Wohl Abstr. 1898 i 556) into tartur- &aldehyde diethylacetal a viscous oil b. p. 157-160'/11 mm. Tho hydrolysis of this acetal is most satisfactorily accomplished by N/lO- sulphuric acid in the cold when a sweet solution of tartardiuldehpda is obtained ; this solution on slow evaporation deposits microscopic rieedles which having a bitter taste and being sparingly soluble in water probably represent a polymeric form ; they re-dissolve slowly in warm water giving a sweet solution which from i t s cryoscopic behaviour contains the substance in a unimoleculm condition ; this solution on evaporation gives a sweet amorphous residue.The diphenylhydraxone of tartardialdehyde forms yellow crystals m. p. 197.5" (corr. decomp.); no osazone was obtainable; the cli-semicurbaxone has m. p. 227.5' (corr. decomp.) ; the dioxime 153.5" (corr. decomp.). Oxidation of the tartardialdehyde by bromine water gives meso- tartaric acid ; for this reason the above ethylenic aldehyde is supposed to be t h a t corresponding with maleic acid. Dihydroxyacetone as an Intermediate Product of Alcoholic Fermentation. ARTHUR SLATOR (Bey. 1912 45 43-46).-1t is sometimes assumed t h a t dihydroxyacetone is an intermediate product of the alcoholic fermentation of dextrose (compare Buchner and Meisenheimer Abstr. 1910 ii 73'7). If this is the cilse dihydroxy- acetoue must be fermented by the yeast at least as quickly as D.F. 7'.ORGANIC CHEMISTRY. i. 163 dextrose. Experiments are quoted to show that during twenty minutes no dibydroxyacetone is fermented although a n equal weight of dextrose is entirely fermented by the same yeast during this time. The conclusion is drawn that dihydroxyacetone is not directly fermented and that it is therefore not an intermediate product of alcoholic fermentation. E. F. A. The Physico-chemical Bases of the Seliwanoff Lzevulose Reaction. HARRY XOENIGSFELD (Biochenz. Zeitsch. 19 12 38 310-320).-1t is shown that the Seliwanoff reaction for 13evulose is also yielded by dextrose when the latter is present in a concentration higher than 2”/ and also when the hydrochloric acid exceeds 12-12.5% i n strength. As the reaction appears to be due t o hydroxy- methylfurf uraldehycle formed from the laevulose and as under certain conditions lawulose can be formed from dextrose the author draws the conclusion that the latter sugar only gives a positive result in the Seliwanoff reaction when the conditions are such that it can b‘e con- verted in appreciable quantity into the former sugar.This hypotliesis is supported by the investigation of the action of acids and bases on dextrose which it is shown probably changes under certain conditions into fructose. Chemistry of the W o o d Dextrins. C. A. YLLNER (Zeitsch. nngew. Chern. 1912 25 103-107).-The dextrins obtained by Honig m d Schubert (Abstr. 1887 125) are mixtures of homologues from which the individual substances can be obtained only after repeated precipitation.The reducing power increases with the rotation of the dextrin; 1 gram of a dextrin with the rotation +25” corresponds with approximately 0.1 gram of cuprous oxide a rotation of +50° corresponding with about 0.2 gram of cuprous oxide. The velocity and extent of hydrolytic decomposition with acids w:is do termined. T. 8. P. Photolytic Decomposition of Smokelees Powders by Ultra- violet Light. Influence of Stabilisers. Damaged Powders. DANIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 191 2 154 201-203. Compare t h i s vol. ii 2 LO),-Exposure of nitroglycerol to the light from a quartz-mercury lamp results in decomposition with production of the following gases CO (24 vols.) CO (19.5 vols.) N (39 vols.) N,O (7 vols.) XO (9 vols.) with a considerable amount of nitrogen peroxide which however is not evolved from the gelatinised material treated with stabilisers.At a distance of 20 mm. from the lamp powders stabiliJed with amyl alcohol withstood decomposition better tshan those containing diphenylamine whereas at 50 mm. diphenylamine was the more effective stabiliser. Damaged Erench naval powders showed themselves less resistant to the rays S. B. S. than sound powders of the same compobition. w. 0. w. General Method for the Preparation of Aliphatic Amines by Catalytic Reduction of Alkyl Nitrites. GEOHGES GAUDION ( A mn. Chim. Phys. 191 2 [viii] 25 125-1 36).-The author has applied Sabatier and Senderens’ method (Abstr. 1905 i 333) of catalytici. 164 ABSTRACTS OF CHEMICAL PAPERS. reduction by means of finely divided nickel or copper in presence of hydrogen to a series of alkyl nitrites and finds that these are reduced giving t h e corresponding secondary amine with small amounts of the primary amine and very small quantities of the tertiary amine.Nickel generally acted at a lower temperature than copper ; thus in the case of isoamyl nitrite the former gave good results a t 220-230' and the latter at 350'. Several possible explanations of the reaction are discussed and it is considered that i t is best explained by assuming that the alkyl nitrites are first isomerised into the corresponding nitro-paraffins which are then reduced in the ordinary way. This explanation is the more probable in view of the fact that the reaction seems to take place in the same way as the catalytic reduction of the nitro-paraffins investigated by Sabatier and Senderens (Abstr.1902 i 701). T. A. H. Ammonium a n d Sulphonium Perchlorates. Relations between Solubility and Constitution KARL A. HOFMANN KURT HOBOLD and FRITZ Quoos (Annalen 1912 386 304-317. Compare Abstr. 1910 i 818; 1911 i 608).-Ammonium and sulphinium perchlorates are eminently suitable substances for the study of the relationship betwoen solubility and constitution because they do not form hydrates are nearly allied crystallographically and whilst not being hydrolysed in aqueous solution are electrolytically dissociated to the same order of magnitude ; several factors therefore which might possibly mask the relationship are eliminated from the field. The following perchlorates are described (the numbers in brackets denote the grams of water in the saturated solution at 15' containing one gram-molecule of the salt) NH,*CIO (635) ; NHMe,*ClO (800) ; NMe,*ClO (32,640) ; NMe,Et*ClO (1710) ; NMe,Pr.C1O4 doubly refracting rhombic plates or prisms m.p. 118' (1310) ; N31e3(C3H5)*C104 thin rectangular plates m. p. 90' (100) ; ClO,*NMe,*C,H almost rectangular plates m. p. 186' (5810) ; C10,*NMe3*C,H,I doubly refracting rhombic plates or prisms (10,300) ; NMe,Ph*C104 rhombic crystals m. p. 1 7 5 O (decornp.) (1315) ; CH2Z*NMe3*C104 rhombic or monoclinic plates m. p. 184' (decomp.) (9535) ; C10,*NMe3*CH2*CH(OH)=CH2*OH thin doubly refracting rhombic plates sinters at 86O (150) ; NEt,-ClO (6130) ; NMeEt3*C110 rhombic plates (915) ; NEt3Pr*C10 quadratic prisms m.p. 275" (3090) ; NMe,Et,*C10 (150) ; C2H,(NH,*C104) rhombic plates (200) ; U,H,(NMe,*ClO,) stout rhombic plates (28,700) ; C3H,(NMe3*C10,) doubly refracting leaflets (23,500) ; SMe,-ClO stout rhombic prisms or elongated plates m. p. above 267O (1280) ; SMe2Et*C10 elongated rhombic plates (840) ; SMe,Pr-ClO (1700) ; ClO,*SMe,*C,H (1650) ; C,H,(SMe,*ClO,) rhombic prisms m. p. 250' (2360) ; ClO,*SBIe,*CH CH elongated plates (1 368) ; C3H,(SMe,*C10,) (2480). The most striking result is the sparing solubility of the quaternary ammonium perchlorates in comparison with the great solubility of metbylmnmonium perchlorate ( 1 20) dimethylammonium perchlorate (70) diethylammonium perchlorate (1 15) and ethylnmmonium per- chlorate (70). Another striking fact is the enormous difference in theORGANIC CHEMISTRY.i. 165 solubilities of quaternary ammonium perchlorates containing like alkyl groups from those containing unlike alkyl groups ; for example NMe4-C104 (32,640) NMe,Et*ClO (1710). These two groups of per- chlorates also differ in their stability towards alkaline potassium permanganate those of the type NR,*C10 being stable whilst members of the other group are rapidly oxidised at the ordinary temperature. The molecular dilutions of glyceryltrimethylammonium perchlorate (150) and of choline perchlorate (70) show how enormously the solubility is increased by the introduction of hydroxyl groups ; when the hydroxyl groups are esterified however the solubility is very largely diminished as shown in the case of nitratocholine perchlorate (40,000). Deductions similar to the preceding can be drawn in the case of the sulphinium perchlorates.c. s. Decompoaition of Quaternary Ammonium Hydroxides. 11. JULIUS VON BRAUN (Annalen 19 12 386 273-303. Compare Abstr. 1911 i 610).-The decomposition by heat 01 diammonium hydroxides of the type OH*NMe,*[CH,],*NMe,*OH may result in the formation of di-olefines unsaturated tertiary amines or ditertiary diamines. Substances in which x is 3 5 7 and 10 have been examined. All four yield by decomposition unsaturated tertiary amines CH,:CH*[CH,],-,*NMe the amount of which increases as x increases ; thus hexamethyldecylenediammonium iodide I*NMe,*[CH,],,*NMe,I white leaflets m. p. 231° obtained from arc-di-iododecane (Abstr. 1910 i 25) and alcoholic trimethylamine at loo' is converted by the usual treatment into a syrupy mass of hexumethyldecylenediamrnolzium hydroxide by the distillation of which very little di-olefine (unex- amined) is formed the chief product being a mixture of 30% of dimethyldecenylamine CH,:CH*[CH,],*NMe b.p. 118-1 20°/17 mm. (platinichloride ; picrate m. p. 137" ; methiodide m. p. 137-140') and 50% of aK-tetrumethyldiaminodecune C,,H,,N b. p. 157-15So/ 17 mm. (platinichloride m. p. lS9" [decomp.]; pacrate rn. p. 139-140'). The distillation of trimethyldecenylammonium hydroxide gives a 75% yield of dimethyldecenylamine ; hence the latter can be obtained from hexa- methyldecylenediammonium hydroxide with comparative ease and in good yield. Bexameth y Zheptylenediammonium bromide Br*NMe,*[ CH&*NMe,*Br m.p. 245O prepared from ar)-dibromoheptane and alcoholic trimethyl- arnine a t looo forms a diammonium hydroxide the distillation of which yields about 15% of a heptadiene 28-29% of di~methylheptenyl- amine CH,:CH*[CH,],-NMe b. p. 166-1 69" or 60-65'/10 mm. (picrute m. p. 88' ; methiodide m. p. 120°) and 51% of ay-tetrarnethyl- diccminoheptane NMe,*[CH,],*NMe b. p. 225-230' (decomp.) or 101-102°/10 mm. (picrate m. p. 136"; dimethiodide m. p. 242'). Unlike the two preceding diammonium hydroxides hexnmethyl- amylenediammonium hydroxide prepared from the iodide (loc. cit.) begins to decompose during the evaporation of its aqueous solution. Its complete decomposition yields mainly trimethylamine water and piperylene very little tetramethyldiaminopentane b.p. 193-1 94' VOL. CII. i. ni 166 ABSTRACTS OF CHEMICAL PAPERS. (platinichlode m. p. 218' [decomp.]; picrate m. p. 149") and dimethyIpenterLylallnine (isolated as the naethioditle m. p. 200O) being produced. Similar results are obtained by the decomposition of hexa- methylbutylenediammonium hydroxide and hexamethylpropylene- diammonium hydroxide ; in the latter case the non-nitrogenous pro- duct is not allene but a mixture of viscous oxidation products from which an unsaturated substance C,HIoO (semicnrbaxone m. p. 192O) probably an isomeride CH3*CO*CH,*CMe:CH of meeityl oxide has been isolated. The experiments indicate that in the decomposition of diammonium hydroxides whilst the lower members of the series decompose simultaneously at both ends of the chain the higher members experience changes first a t one end of the chain only.For example OH*NMe,*[CH2],o*NMc~3*OH -+ Me*OH + OH*N11Ze,*[CH2],,-NMe2 and H,O + NMe + OH*NMe;[CH,],*CH:CH ; then OH*NMe,*[CH,],,*NMe -+ MeOH+NMe,*[CH,],,*NMe and H,O+NMe,+ CH,:CH*[CH,],*NMe whilst OH*NMe,*[CH,],*CH:CH -+ MeOH + NMe,*[CH,],*CH:CH and H20 + NMe + C,,H, It has been shown (Zoc. c d . ) that the presence of an ethylenic linking in an aliphatic group in a quaternary ammonium hydroxide facilitates the elimination of the group when the point of unsaturation is adjacent to the nitrogen atom. The decomposition of the hydroxides OH-NMe,*[CH,],*CH:CH shows that the loosening influence of the ethylenic linking weakens as its distance from the nitrogen atom increases ; trimethyldecenylammoni um hydroxide yields not more hydrocarbon than does the corresponding saturated quaternary ammonium hydroxide.c. s. The Asymmetric Cobalt Atom. V. ALFRED WERNER (Bey. 1912 45 121-1SO).-According t o the author's theory there are two possible salts of triethylenediaminecobalt which stand t o each other in the relation of object and mirror-image and are not super- posable. These may be represented thus Such compounds form the simplest possible case of molecular asymmetry being specially characterised by having all the co-ordination positions of the central atom occupied by structurally identical groups the asymmetry being caused by the special spatial arrangement of these groups. Such asymmetry the author denotes as molecuulas. asymmetry I1 (compare Abstr.1911 i 838) and he has been successful in resolving some of the salts into the optically active isomerides. Resolution by means of the camphorsulphonates a-bromo- camphorsulphonates etc. was unsuccessful since the salts woiild not crystallise. Triethylenediaminecobaltic tartrate w:ts obtained in theORGANIC CHEMISTRY. i. 167 crystalline condition however and proved to he a partial racemate which underwent slight resolution on fritctional crystallisation the extent of the resolution being ascertaiiied by taking advantage of the very strong rotation dispersion of these compounds. The lesser soluble crystals contained an excess of the Iavo-i~omeride the final mother liquors containing the excess of the dextro-isomeride ; the pure isomerides could then be isolated by making use of the fact that their bromides mere readily soluble in concentrated hydrobromic acid the rttcemic bromide being almost insoluble.'J'he yields of the active components were very poor by this wethod which was theii replaced by the following Co en3 c' I'i o does not form a partial racemate and by one recrystallisation can be separated into the sparingIy soluble d-ti iethylenediamiriecobaltic chloride-d- tartrate and the readily soluble Z-tIiethylenediaminecobaltic chloride- d-tartrate from which other salts can be obtained without difiiculty. The bromide tartrates behave similarly to the chloride tartrates. The specific rotations of the various salts are very large and the rotation dispersion is very marked as shown by the following table The chloride tartrate I 1 C f 4 6 [a],.[QI,. [MID. [q.. ............ { &45" { +552'50 &153'6" Chloride - 560 Bromide ............ { rkl65 + 195'5 ............ Nitrate {%I ( - 4 4 { 2;; - 187 1 +46 The active salts are very stable; their solutions cau be evaporated down with concentrated hydrochloric or hydrobromic acid without suffering any loss of activity. The active isomerides w e much more readily soluble than the racemates. The triethylenediaminecobaltic salts (Co en,)X are best prepared as follows 10 grams of cobalt chloride are dissolved in 150 grams of 10% ethylenediamine and oxidised by leading air through the solution. The brown solution so obtained is acidified with hydrochloric acid evaporated to crystallisation the crystals dissolved in water and ammonium nitrate added t o the solution whereby 1 6-dicliloro- diethylenediaminecobaltic nitrate is precipitated.After collecting this salt the filtrate is precipitated with sodium bromide giving pure triethylenediaminecobaltic bromide. C,H,O,) is obtained from the bromide by double decomposition with silver tartrate ; i t crystallises in spherical aggregates of light yellow needles. Tri- ethyZenedianiimcobuZtic chloride-turtrate Co en3 o is prepai ed by interaction of 1 molecule of the chloride with 1 molecule of silver tartrate the precipitate of silver chloride being extracted with boiling water until pure white in colour. The solutions thus obtained are concentrated and allowed to crystallise columnar and tabular crystals separating ; these are collected and the filtrate further concentrated.~~iethylenediami~aeco~c6l~ic tccrtrccte (Co I 1 9 r a 12 2i. I68 ABSTRACTS OF CHEMICAL PAPERS. A second crop of crystals often separates and then the concentrated solution sets t o a jelly-like mass. The crystals consist of d-triethylene- diumineco6aZtic chloride-tartrute [co en3]::~4~6,5H20 and are purified by one recrystalhation from water ; they have [a] + IOi" [MI +517.6' [.Ic + 3 5 O [MIc + 179.4O. The gel consists of tile corresponding Zaevo-salt mixed with srriall quail tities of the d-isomeride. d-T?wiethylenediuminecoba~t~c bromide-tartrate Co en3 C4H ,5 H,O is obtained similarly and forms R felted mass of light yellow silky needles which in contact with the solution slowly change to much darker stout plate-shaped crystals ; they have [a] + 9 8 O [MI + 555' [ale + 38" Lr\l] + 2 11 *7'.The corresponding laevo- isomeride forms a gel. d-~riethylenediu~,zinecobaItir bromide [Co en3]Br3,2H,0 is prepared from either the bromide-tartrate or the chloride-tartrate by trituration with warm concentrated hydrobromic acid. The soliition after filtering deposits large hexagonal plates which are probably an acid bromide ; on recrystallisation from water large columnar crystals of the bromide are obtained. The I-bromide [Co eo3]BrR,2H20 is similarly prepared from the gel of I-bromide-tartrate or 1-chloride- tartrate the sparingly soluble racemic bromide remaining undissolved. The d- and 1-chlorides [Co en,]CI3,H2O are obtained from the bromides by reaction with silver chloride; they crystallise in small golden- yellow needle-shaped crystals The d- and 1-nitrates [Co enJ(N03)3 are prepared from the bromide by treatment with the theoretical quantity of silver nitrate ; they form pyratuidal crystals 'which are readily soluble in water. L I l B r 4 6 T.S. P. Preparation of Hexamethylenetetramine Borocitrates. ATHENSTAEDT and REDEKEH (D.R.-P. 238962).-Alkali and magnesium borocitrates have been previously described. The hexametiiylene- tetrsmine derivatives have now been obtained by thoroughly mixing the required proportions of the ingredients in either concentrated aqueous or alcoholic solution. They form colourless crystalline powders and are readily soluble in water or alcohol. liex:ccmetl~ylenetetra~~~?~~ borocitrutes having the following composition a r e mentioned C,H,O7,3WBO,,2C,Hl2N decomp.182O ; CGH,0,,3HB0,,3C t-i 13N4 192' ; ~ C G H s 0 7 2 H B 0 2 3 C H 2 ~ ~ 185' ; 2C,El8O7,4HBO,,3U,H1,N 180" ; 2C,H,07,6 I€B0,,3C,H,,N4 178'. F. M. G . M. Compounds of Chromic Hydroxide with Amino-acids Derived frod Proteins. LOUIS HUGOUNENQ and ALBERT MOREL (Compt. rend. 1912 154 119-120).-Chromic hydroxide (1 mol.) dissolved in a boiling aqueous solution of glycine (6 mols.) gives a purple-red solution which deposits red crystals containing four mole- cules of the amino-acid and two hydroxyl groups to two atomsORGANIC CHEMISTRY. i. 169 of chromium. The excess of chromic hydroxide is removed by lixiviittion or treatment with acid. The filtrate from the red crystals 0 1 1 slow evaporation deposits brilliant vermilion acicular prisms of a compound containing six molecules of the amino-acid t o two atoms of chromium Both compounds are soluble in acids and are slowly decomposed byalkalis. They do not show the ordinary reactions of chromium salts but resemble more closely the chromoxalates.w. 0. w. Action of Amino-acids on Sugars ; Formation of Substances Resembling Melanins. LOUIS U. MAILLARD (Compt. s*end. 191 2 154 66-68. Compare this vol. i 13).-Continuing his experiments on the action of natural polyhydric alcohols on amino-acids the author finds that when glycine is heated on the water-bath with four times its weight of dextrose and the same amount of water i t rapidly loses carbon dioxide and forms dark brown cyclic condensation products the molecules of which contain a t least two dextrose residues to one nitrogen atom.They are said to be identical with the melanin pig- ments obtained in the hydrolysis of proteins. If this is so the comparatively low yield of amino-acids in such hydrolyses receives an explanation. The reaction is instantaneous between glycine and xylose or arabinose rapid in the case of galactose and mannose slow with lactose and maltose whilst several hours elapse before it occurs in the case of sucrose. Of the common amino-acids alanine is the most act iv w. 0. w. The Action of Moist S u l p h u r on Cholic Acid and Taurine. J. A. A. AUZIES (Rev. gen. chim. pure up$ 1911 14 278-280). -A study of the composition of the gall and bile of cattle and pigs from which the author corroborates the results of Langheld (AbLtr.19OS ii 211). Cholic acid OH*NMe,*CH,*CO,H is prepared by mixing calcium chloroacetate (1.92 parts) with trimethylnmine (1.18 parts) and heatiug the chloride of ccdciurn trimethylctmmoniumacetate so obtained with milk of lime at 120-150". Acetaldehyde is heated at 140' with chlorosulphonic acid CH,*CHO + SO,HCl= HCI + SO,€€*CH,*CHO ttie product converted into its calcium salt (CRO*CH,*SO,~,Ca which by treatment with ammonium hydroxide yields the aldehyde amiiiotii;t [NH,*CH(OII)*CH2-S0,]2Ca this loses water (2 mols.) on heating and 1s converted into the imine (NH :CH*CH,*SO,),Ca which after reduction to the corresponding amine and elimination of calcium with sulphuric acid furnishes the required taurine. Preparation of Brom oacylisocarbamide Ethers.FARBEN- FABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 240353).-When iso- carbamide ethers of the general formula NH,-C(0R):NH (R = alkyl or alkylaryl) are treated with bromodiethylacotyl halides they yield bromo-a-ethylbutyrylisocarbamide ethers which are of therapeutic value. Bromo-c~-etl~ylbutyrylisocarbamide mzethyl eLher colourless crystals m. p. 7 2 O was obtained by boiling brorno-a-ethyl butyryl bromide with Tnurine is prepared on an industrial scale as follows F. M. G.M.i. 170 ABSTRACTS OF CHEMICAL PAPERS methyl iiocarbamide hydrochloride (Abstr. 1900 i 340) in aqueous solution cooling and rendering alkaline when the product separated. F. M. G. M. Specific Rotatory Power of Glutamine. Ammonium Glutamate. ERNST SCHULZE and GEORQ TRIER (Bey.1912 45 257-262).-Supposed pure preparations of glutamine obtained from different plant preparations by precipitation with mercuric nitrate and continued crystallisation shorn [a] varying from + 5.4" to 8.9". By purification of the copper salt these preparations all yield glutamine of constant rotatory power [.ID + 6" to 7". The higher values are due to the presence of traces of glutamic acid which acting as an acid increases the rotatory power of glutamine. Glutamic acid forms a monobasic amm,onium salt [aID - 3*6O which begins t o lose ammonia when kept over concentrated sulphuric acid and readily loses ammonia when evaporated iu aqueous solution. Since glutamine when boiled in aqueous solution is to some extent hydrolysed to the ammonium salt the presence of glutamic acid is explained.E. F. A. Action of Ammonia on Ammonium Thiocyanate. WALTER P. BRADLEY and W. B. ALEXANDER (J. Amel.. Chem. Soc. 1912 34 15-24).-Comparatively few substances become deliquescent on exposure to dry ammonia and of these autmooium thiocyanate appears to possess the property in the highest degree the deliquesoence continuing up to a temperature of 88". The absorptive power f the salt was determined a t various temperatures between 0" and 100". At O" the product corltained 43.10% of ammonia; a t 25O 31.16%; at 50° 19.40%; a t 7 5 O 6-17% whilst a t 100' none was absorbed. F.-p. determinations were made of solutions of ammonium thiocyanate 111 ammonia the concentrations ranging from 0% to 100% of the latter. On plotting the results it is shown that there are certainly three and probably five compounds formed. The former are NH,CNS,NH LU.p. - 16" (metaytable) ; NH4CNS,3NH m. p. - 38' ; and NH,CN S 8N H m. p. about -87". The ot8her two compounds are N,H4CNS,6NH m. p. -76" and NH4CNS,7NH8 m. p. -84'. Indications were also obtained of the possible existence of the compound 2NH4CNS,13NH I I I . p. about -SO". - 9 6 O . E. G. The lowest eutectic point was in the vicinity of The Composition of Prussian Blue. P. WORINGER (Chem. Zeit. 1912 36 73).-Evidence for regarding Prussian blue as a ferro- cyanide hns been given by Hofrnann Heine and Hochtlen (Abstr. 1905 i 38). On the other hand when a ferric salt is precipitated with an excess of potassium ferrocyanide the filtrate contains considerable yunnti ties of potassium ferricyanide formed by the reactions FeCI + K,Fe(CN) = FeCl + K3Fe(UN) + KCl = KEeFe(CN) + 3KC1 and in the filtrate 3KFeFe(CN) = Fe,[Fe(CN),] + K,Fe(CN&.If aiximonium carbonate solution is added to a boiling suspension ofORGANIC CHEMISTRY i. 171 Prussian blue ammonium ferricyanide as well as ferrocyanide is found in the tiltrate and the iron remains as Pe,O,. This is considered to prove that Prussian blue is a ferricyanide. C. H. D. Organic Boro-Nitrogen Compounds ARDEN RICHARD JOHNSON (J. Physical. CJLetn. 19 12 16 1-28).-A series of compounds of boron tribromide with amines and nitriles was prepared in which boron as well as nitrogen is supposed to function as quinquevalent. Various additive compounds of boron trichloride tribromide and t,ri-iodide with ammonia are known in which the proportion of ammonia varies from 1.5 to 15 molecules per molecule of boron compound.Boron tribromide reacts with amines and nitriles with liberation of heat and additive compounds of the type (X)N:BBr are apparently formed in most cases. The nitriles and tertiary amines except trimethylamine give fairly stable crystalline products. Compounds of this type were also isolated from the primary isoamylamine and aniline. The compounds of the aliphatic secondary amines im- mediately lose hydrogen bromide amorphous products of the type R,N*BBr2 resulting. Similarly the product from ethylamine has the constitution NHEt- BBr With methylamine the reaction apparently goes a stage further and the product isolated has the formula B(NHMe),Br.Piperidine and diphenylamine give compounds of the type (YNH),,BBr3. The compounds were prepared by passing the dry gaseous amines into a carbon tetrachloride solution of boron tribromide or by adding the bromide Eolution from a burette to the anhydrous amine or nitrile dissolved in carbon tetrachloride. I n aome cases an oily insoluble product containing excess of amine was first formed and afterwards converted into a solid product by further addition of bromide. The substances (NHNe)2:BBr NBEt*B13r2,. NH,(C,H,,):BBr NH2Ph:BBr NMe,*BBr and NPr2*BBr2 are white amorphous solids sparingly soluble in carbon tetrachloride. The monoisoamylamine compound which may be handled in the air turns yellow in sunlight but does not dissociate very rapidly below 40'.When heated up quickly it appears to melt and decompose simultaneously. It burns furiously colouring the flame intensely green. Tbe isoamyl compound N(C,H,,),:BBr may be crystallised from carbon tetrachloride. It dissolves in water giving diisoamylamine hydrobromide and boric acid. The substance SC,H,,N BBr is formed from piperidine in a violent reaction which must be moderated by careful cooling. It has been obtained as a pale yellow precipitate which readily loses hydrogen bromide when exposed over sodium hydroxide in a desiccator being converted into the szcbstance (31,H,oN-BBr,(C,H,1N),. The latter is a stable solid giving greenish-yellow fluorescing solutions in organic solvents. The substance 3NHPh2,BBr is a white precipitate comparatively stable in air.. Trimethylamine reacts with boron tribromide with development of heat. White fumes were givea of€ and no solid compound could bei. 172 ABSTRACTS OF CHEMICAL PAPERS. isolated. The substance NEt,:BBr crystallises from carbon tetra- chloride in long slender prisms. The substance NMe,Ph:BBr forms a camphor-like crystalline hygroscopic mass. When exposed in a desiccator over sodium hydroxide the elements of methyl bromide are removed and the substance NMePhOBBr? remains. The latter is very rapidly decomposed by hot alkali with precipitation of boron nitride BK. The pyridine compound C,H,N:BBr is a snow-white amorphous mass fairly stable in the air but tending to dissociate with rising temperature; a t 120' i t turns brown and sinters.When placed in a desiccator over sodium hydroxide the elements of hydrogen bromide are removed and the substance C,H,N-BBr remains as a stable powder. It is suggested that boron is probably combined with the carbon as well as the nitrogen of the pyridine nucleus in this compound. The white substance C,H7N BBr formed from quinoliiie IS more stable than the pyridine compound and scarcely fumes in the air. The substances CNMeIBBr CNEt:BBr and CNPh:BBr are obtained from their carbon tetrachloride solutions as white crystals The methyl compound dissociates very rapidly a t 30° and the ethyl compound is slightly more stable. The substance CH2Ph*CN:BBr3 which is difficult to purify by crystallisation was obtained as a slightly yellow crystalline mass. Most of the above boron tribromide compounds decompose or sublime without melting.Some of the nitrile compounds may be heated to nearly 200' before decomposing. Of the amine products those of pyridine and quinoline are the most stable. The products of decomposition by heat probably contain boron nitride in most cases. The substances described are violently decomposed by water absolute alcohol acetaldehyde and acetic acid the products containing boric acid accompanied by hydrogen bromide ethyl bromide bromoacetaldehyde and acetyl bromide respectively. Acetone the esters and ether have a less violent action and crystalline products containing boron and carbon have been obtained. Hydrocarbons usually exert no solvent action on boron bromide compounds but with prolonged contact in sunlight the hydrocarbon assumes a red to brown tint.A slow decom- position also occurs in contact with chloroform and bromoform. Carbon tetrachloride and tetrabromide in which the substances are but slightly soluble have no chemical action on them. It melts with some decomposition. R. J. C. Preparation of Me thylcyclopentape. S. S. NAMETKIN (J. IZUSS. Phys. (?hem. Xoc. l911,43,1611-1613).-The preparation of methyl- cyclopentane by the action of fuming hydriodic acid a t 100-105° on cycZopentanylcarbinoI (compare Zelinsky Absbr. 1908 i 727) and reduction of the iodide thus obtained by means of zinc dust in aqueous alcoholic solution gives a product containing cyclohexane. Hence when heated with hydriodic acid the cyclopen tanylcarbinol undergoes partial isomerisation into a six-carbon atom ring compound.Similar cases of the ready isomerisatioh of substituted cyclic carbinols have been observed by Demjsnoff (Abstr. 1910 i 838) and by Kijner (Abstr. 1905 i 772; 1908 i 530 864; 1911 i 42). T. H. P.OKGANIC CHEMISTRY. i. 173 Polymerisation of Diethylene Hydrocarbons. Polymerisation of as-Dimethylallene. IV. SERGIUS V. LEBEDEFF (J. Nuss. Phys. Chem. Soc. 1911 43 1735-1739).-For a n unsymmetrical di- substituted allene six dimerides are possible three of each of the F-QZC types F-7:' and Two of the compounds of the former c-c:c C=C-C of these types have been obtained (Abstr. 1911 i 774) failure to isolate the third being due probably to its high velocity of polymeriss- tion. The author's results indicate that the velocity of polymerisation of hydrocarbons with conjugated systems of double linkings :C:C*C:C increases with diminution of the loading of the extreme carbon atoms and with increase of that of the intermediate ones.Hence of the three dimerides of as-dirnethylallene of the first type 1 2-diiso- propenylcyclobutane should be the most stable 1 1 2 2-tetramethyl- 3 4-dimethylenec~clobu tane should occupy an intermediate position in this respect (Zoc. cit.) and the third 3 3-dimethyl-Tmethylene- 1 -isopropenylcycZobutane sbould readily polymerise. By the choice of suitable conditions the remaining dimeride (the second) has now been obtained. . . 1 1 2 2-Tetramethyl-3 4-dimethyZenecyclobutane has b. p. 140-141°/760 mm. 66-67'755 mm. DSo 0.7927 r$ 1.46063 ~i 1.45701 n:? 1,46988 nz 1.47807 and yields tetramethylsuccinic acid when treated with ozone. The physical properties of these three dimerides some of whicb were given wrongly in the previous paper are as follows Optical exalta- B.p. DIO. tion. 1 2-Dis~~pro~cr1ylc~cZobutsne ............ ... ...... ... ... 179-181" 0'8422 2'34 1 l-Dimethyl-2-metliylene-3-isopropcnylcycZobutane 149-150 0.7982 2.09 1 1 2 2-Tetrainethyl-3 4-dimethylenecyclobutane 140-141 0 7927 1-81 As regards the non-formation of dimerides of the second of the two types given above it is pointed out that the relations of unsaturated compounds to reactions of combination indicate clearly that the tensions of the affinities in the molecule are distributed unequally. For the complex :C:C:C they are directed the most strongly towards the middle carbon atom so that combination of the two molecules takes place first a t this place there being possible the two annexed 2 3 1 arrangements.CH,:C:CMe CH,=C:CAle With the former of these arrange- ments further saturation of the free CH,:b:CMe CMe,:C:CH affinities gives the two dimerides 1 1 2 2-tetramethyl-3 4-dimethylenecycZobutane whilst with the latter owing t o its symmetrical character only one dimeride namely 1 1 -dimethyl-2-methylene-3 -isopropenylcycZobutane is obtained. This scheme hence excludes the possibility of formation of dimerides of the second type. T. H. P. and 1 2 3 3 1 2 - diisopropenylcyclobutane andi. 174 ABSTRACTS OF CHEMICAL PAPERS. Chemical Action of Light. XXII. Autoxidations. I. GIACOMO TJ.CIAMICIAN and PAUL SILBER (Bey. 1912,45 38-43 ; Atti R. Accccd. Liizcei 191 1 [v] 20 ii 673-677).-Aromatic hydrocarbons on prolonged exposure to the action of light in presence of water in an atmosphere of oxygen in sealed vessels are partly oxidised to the corresponding carboxylic acids ; small quantities of the corresponding aldehydes and of formic acid are also formed. Thus toluene yields benzoic acid and benzaldehyde ; p-xylene gives p-toluic acid m. p. 181" and a little terephthalic acid as well as traces of the aldehyde ; m-xylene forms m-toluic acid m. p. 11 lo and isophthalic acid ; o-xylene forms 0-toluic acid m. p. 107-108". p-Cymene yields some aldehyde p-cuminic acid m. p. 119" p-propenylbenzoic acid m. p. 165" and a-hydroxy-p-cuminic acid m.p. 156". I n the dark the hydrocarbons are unchanged. p- and 0- Nitrotoluene also phenanthrene are practically unaltered after prolonged exposure to light. E. F. A. [Orientation in the Benzene Nucleus.] JULIUS OBERMILLER (h'er. 1912 45 165-167. Cornpare Abstr. 1911 i 960).-The author upholds his claim of priority over Holleman (this vol. i 20) and maintains that there is no essential difference between their views concerning substitution in the benzene nucleus. F. B. Benzene Hexachlorides and their Decomposition into Trichlorobenzenes. T. VAN DER LINDEN (Bey. 19 12,45 23 1-247). -a- and P-Benzene hexachlorides prepared by the action of chlorine on benzene in snnlight form a eutectic solidifying at 155.5". This p i n t was mistaken for the melting point by Matthew (Trans.1891 59 166). I n addition to the a- and p-isomerides two new benzene hexachlorides are formed in the reaction all four compounds are stereoisomerides. The y-isomczride crystallises in needles and lozenge- shaped forms m. p. 112- 1 13" ; the 6-isomeride forms slender lustrous twin platelets m. p. 129-132". 0n:decomposition of a- benzene hexachloride with alkali a mixture of 1 2 4- 1 2 3- and 1 3 5-trichlorobenzenes is obtained. The temperature at which decomposition is effected has no influence on the relative proportions of these or is this proportion altered on replacing potassium hydroxide by sodium hydroxide or substituting methyl alcohol for ethyl alcohol. The proportion is however altered by the use of pyridine or quinoline more of the 1 2 4- and less of the 1 2 3- isomeride being obtained the amount of the 1 3 5-trichlorobenzene remaining constant. @-Benzene hexachloride when decomposed by potassium hydroxide in ethyl alcohol yields the same three trichlorobenzenes as the a-isomeride but in different proportions which are very similar to those obtained on decomposing the a-isomeride with pyridine.Pyridine however has hardly any action on the /I-compound. y-Benzene hexachloride yields the three trichlorobenzenes in slightly different proportions than either of the a- or P-isomerides. It was not found possible to eliminate the chlorine in stages neitherORGAKIC CHEMISTRY. i. 175 could hydrogen chloride be split off by means of aluminirim or ferric chlorides. The fact that a considerable proportion of 1 2 3-trichlorobenzene is formed indicates that the elimination of hydrogen chloride is not entirely between two neighbouring carbon atoms.E. F. A. Preparation of 7-Chloropropylbenzene and its Homologues. EMANUEL MERCK ( D. R. -P. ~ 3 9 0 7 6 ) . - y - C h Z o r o ~ ~ r o ~ ~ Z ~ ~ ~ ~ e ~ e C:,H,.CH,*CH,*C H,Cl a colourless oil with penetrating odour b. p. 279-220" or llOo/21 mm. is obtained in 78% yield from y-chloropropylanilino by diazotisation and subsequent reduction with stannous chloride in alkaline solution. F. M. G. M. 2-Chloro-3 5-dinitrotoluene. WALTHER BORSCHE and ANNA FIEDLER (Bey. 191 1 45 270-273).-2-Chloro-3 5-dinitrotoluene is formed in only small quantity by nitrating o-chlorotoluene and does not constitute the main product of the reaction as stated by Nietzki and Rehe (Abstr.1893 i 15). It crystallises from alcohol in stout yellow rhombs m. p. 63-64'; Nietzki and Rehe give 45'. It is best prepared by heating 2-chloro-3-nitrotoluene or 2-chloro-5- nitrotoluene with a mixture of equal parts of sulphuric and fuming nitric acids for two hours on the water-bath. The above-mentioned mononitro-compounds are conveniently pre- pared by nitrating aceto-o-toluidide and hydrolysing the product with hydrochloric acid ; the resulting mixture of 3-nitro- and 5-nitro-0- toluidine is separated by steam distillation and the amino-group replaced by chlorine according to Ullmann's method. 4-Chloro-3 5-dinitrotoluene has m. p. 116-11'i0 and not 48' as given by Horiig (Abstr. 1887 1034). ' F. B. Conversion of the Bromonitrobenzenes into the Corre- sponding Dichlorobenzenes by Phosphorus Pentachloride.JULIUS SCHMIDT and HANS WAGNER (AnnuZen 1912,387 164-165)- When heated with phosphorus pentnchloride in a sealed tube at 180' for six hours 0- m- and p-bromonitrobenzenes are converted more or less smoothly into 0- rn- and p-dichlorcbenzenes. c. s. Action of Nitric Acid on cycZoPentane and Methylcyclopen- tane. S. 8. NAMETKIN (J. Buss. Phys. Chem. Xoc. 191 1 43 1603-1611. Compare Abstr. 1910 i 830).- Nitrocyclopentune C5H,*N02 obt,ained by the interaction of aluminium nitrate and cyclopentane iu a sealed tube is a colourless liquid b. p. 90-9lo/40mm. DY 1.0776 r, 1-4518 with the characteristic odour of secondary nitro-compounds. On oxidation with nitric acid it yields glutaric acid which is also formed when cyclopentane itself is oxidised.Nitration of methylcyclopentane by means of nitric acid yields 1 -nitro-1-methylcyclopentane and 2-nitro-1 -methylcycEopentane b. p. 98-99'/40 mm. Di2 1.0381 rng 1.4488 (compare Markownikoff Abstr. 1899 i 799). Thus in the secondary nitro-product of methylcyclopentane thei. 176 ABSTRACTS OF CHEMICAL PAPERS. nitro-group occupies the a-position whilst in that of methylcydo- liexane i t occupies the P-position. The above two nitro-compounds formed by the nitration of methylcydopentane are accompanied by succinic and a-methylglutaric acids; probable schemes are given for the formation of these two acids. T. H. P. The Preparation of ~-2-Dinitrotoluene its Honiologues and Derivatives. SOCIETE CHIMIQUE DES USINES DU R H ~ N E (L).R.-P.239'353).-w-2-Di,~itrotoZueize NO;C,II;CH,.NO or NO C6H4 C H NO (OH) m. p. 67' is readily prepared in 70% yield by heating o-nitrotolueno (2 parts) a t 1 10-220° during eight hours with the gradual addition of 70% nitric acid (1 part) o-nitrobenzaldehyde and o-nitrobeuzoic wid being simultaneously produced as by-products. The followiug compounds are desribed ~-4-dirnitrotoZuene m. p. 9 1" ; 4-Ch~OrO-o-2- di&trotoZue?z,e In. p. 112' ; 4-bro?no-w-2-tlinitrotoZuel..Le m. p. 113.5' ; Ci-chZoro-w-2-clinitrotolu~ne m. p. 82' ; whilst o-nitro-m-xylem yields a mixture of w-6-dinitro-m-xyZene m. p. 86*5" and o-4-clinitro-m-xyle?~e u1. p. 64". F. M. G.M. Preparation of Chloroalkylarylsulphonic Acids and of Chloroalkylarylcarboxylic Acids.BADISCHE ANILIN- & SODA- PABHIK (D.R.-P. 23931 l).-o-Chlorotoluene-p-suZphonic acid is readily prepared by slowly dropping water (18 parts) into w-chlorotoluene-p- sulphonyl chloride (225 parts) dissolved in 80 parts of hot alcohol. The sodium salt SO,Na*C,H,*CH,CI is sparingly soluble in water. w-Dichlorotoluene-m-suZph.0 rr y? chlo?*ide a crys tal line powder insoluble in water and prepared by the action of phosphorus pentachloride on benzaldehyde-?it-sulphonic acid is converted by the foregoing treatment into w-dichlorotoluenc-m-sulphonic acid ; the sodium salt is moderately soluble in water. w-ChZovo-p-toluoyl chEoride a colourless oil b. p. 150-155O (pre- pared by chlorinating a hot solution of p-toluoyl chloride) when dissolved and maintained a t 0-5" in 08% sulphuric acid until the evolution of hydrogen chloride ceases furnishes w-chloro-p-toluic acid m.p. 190-192" (decornp.) and insoluble in water. F. 1sI. G. M. Preparation of Aromatic Sulphonyl Ammonium Corn- Dounda. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 239i63).- When sodium o-chlorotoluene-p-sulphonate is he&ted with dimethyl- aniline at TO" it yields the compound C,H4<YH2>NMoPh a bO3 colourless powder. Ethyl w-2-dichZorotoluene-p-sulp7to~~ate a colourless oil prepared by hydrolysing the corresponding sulphonyl chloride with sodium ethoxide when similarly treated furnishes the compound S0,Et*CGH,Cl-CH2-NC1Me,Ph in colourless hygroscopic crystals readily soluble in water and alcohol. F. M. G. M.ORGANIC CHEMlS‘rHY. i.177 System of Noiiienclature for Bridged Rings.” VICTOR GRIGNARD (Bull. SOC. c h 2 . 1912 [iv] 11 184-129).-The author proposes to avoid the inconveniences of von Baeyer’s system of nomenclature for such structures by (1) selecting for the nucleus of the name t h a t of the fundamental ring which is immediately apparent traversed by one or more bridges; (2) numbering the atoms in the bridges after those of the fundamental ring so that the bridges appear t o be merely particular substituents attached a t two points arid identified in the name by their ‘ 6 characteristic.” This character- istic consists of the numbers of all the atoms which appear in the ‘‘ bridge,” and the highest number in it indicates the total number of carbon atoms in the structure. The number of constituent rings apart from the fundamental ring is always twice the number of bridges and is indicated by prefixes bicyclo tetracyclo etc.Where the bridge contains a n ethylenic linking these prefixes become bicycleno and tetracycleno respectively and the number of the atom at which the double linking begins is accented in the “character- istic.” The following examples of the application of the system may be given 1 I 1 T. A. H. Compounds of A n t i m o n y Trichloride and Tribromide with Polynuclear Benzene Hydrocarbons. KoRIs N. MENSCRUTKIN (J. 12uss. Phys. Chem. Soc. 191 1 43 1805-18~0).- 1 Iiphenyl and diphenylmethano form with antimony trihalitles mole- ciilitr compounds containing 2 mols. of antimony salt to 1 mol. of hydrocarbon 2SbC13,C,H,Ph m.p. 71” ; 2SbBr,,C6H,Ph 60.5’ ; 2Sbl,,O,H,Ph 161’ ; 2SbCl,,CH,Ph m. p. 100’ ; 2SbBr,,CH2Ph m. p. YO”. Xach concentration-temperature diagram exhibits two eut,ectic points as follows M. p. Hydro- System. carbon. SbCIs-C,H,Ph 70.5” S b Br,-CtjH ,Ph S b ‘2 I,- C H 1 ’11 7 0 -5 S1) 12 - C H ,l’h S I ) Br,-CH,I’h 26 70.5 2 6 1st eutectic point. +7 Tempera- ture. n. 50” 2’2 47 1-75 68 89.4 22-5 15’6 22.5 14.6 - 2nd eiitectic point. 7- Tempera- ture. 12.. 57” 0.18 60.5 0.52 67 82 0.18 160 0.2 0-6 M. p SbX,. 7 3” 94 166 73 94 With antimony trichloride and . tri-iodide diphenyl gives stable compounds which melt without decomposing whilst with antimony tribrornide it yields a compound with a melting point in the region of unstable equilibrium.i. 1'78 ABSTRACTS OF CHEMICAL PAPERS.Triphenylmethane forms no molecular cornpound with antimony tri- bromide but with the trichloride i t gives the compound SbCI,,CHPh melting a t 49.5' in the region of unstable equilibrium. The diagram consists of three branches the first eutectic point corresponding with SbC1,,0*93CHPh3 lying at 49O and the second with SbC13,0*37CHPh at 35'. The diminished capacity t o form compounds with antimony tri- halides otlserved in the case of triphenylmethane may be related t o the fact that this hydrocai-lion differs considerably in its chemical properties from diphenylmethane ; thus i t forms molecular com- pounds with benzene and other hydrocarbons and yields metallic derivatives etc. Colorations are often observed on fusing these polynuclear hydro- carbons with antimony trihalides (compare -Watson Smith Abstr.18'79 831). T. H. P. Halogen Derivatives of Fluorene and Bisdiphenylene- ethylene. JULIUS SCHMIDT and HANS WAGNER (Annalen 191 2 387 147-1 64).-The method of converting 9 9-dichlorofluorene into bisdiphenylene-ethylene by heating with copper powder in benzene (Abstr. 1910 i 550) has been applied t o other halogenated fluorene derivatives ; thus 9 9-dichZoro-2-bromoftzcorene F,H,Br >CCI In. p. ( 7 3 4 - 178") colourless needles obtained from 2-bromofluorenone and phos- phorus pentachloride at 160-lSOo is converted into 2 2'-dibromo- C;,H,Br >C:C<fE3Br m. p. 312O red crystals bisdiphenylene- ethy Zene or by sublimation yellowish-green needles. This substance is con- verted into 2 ; 2'-dibromobisdip12enyZ~ne-etlzccneJ C6H4- 6 4 ?6H3Br>CH*CH<<H $? H Br m.p. 272') colourless needles by heating its ethereal solution with platinum black for eight hours in R current of hydrogen aud reacts additively with chlorine in cliloroform and with bromine in carbon disulphide in sunlight to form respectively 9 Y'-dichEoro-2 2'-dibromo- xn. p. 268O colour- $! H Br bisdiphen yZene-ethane ?6H3Br>CC1 cCl< less crystals and 2 2' 9 9'-tetrabroinobasdzphenylene-ethne m. p. 258'; the latter in benzene reacts with silver acetate to form the c6H4- 6 4 c6H4- C 6 H 4 ?6H3Br m. p. 285'. diacetate 3->C(OAc)*C(OAc)<C 9 9-DicAZoro-2 'I-dibromoJuorene H Br >CCl m. p. 260") colour- c6H4 ?,".,".r C,K,Br less needles obtained from 2 7-dibiomofluorenone and phosphorus pentachloride a t 210-2'20° is converted by copper into 2 :2' :7 :7'-tetra- 364' red AromobisdiphenyZene-ethylem 76H3Br>C:C< C,H3Br' p.crystals from which the following substances have been prepared 9 B'-dichZoro-2 2' 7 :'i'-tetrubrornobisd~~}~e~a~lerLe-~t?~ane m. p. 298-299' H Br C6H,BrORGANIC CHEMISTRY. i. 179 colourless needles; 2 2' 7 5' 9 9'-hexccbromobisdip?henylene-ethane m. p. 310° colourless crystals ; 2 2' 7 7'-tetrab~omobisdiphe.lzylelze- ethane m. p. 284' colonrless leaflets. The disappearance of colour coincidently with that of the ethylenic linking is noteworthy. When heated in a sealed tube a t 180' for six hours fluorenone and phosphorus pentachloride yield 9 9'-dichZorobisdiphenyZene-etha.ne m. p. 235-236' 2 7 9 Y-tetraclAZoroJuorene m.p. 215' and a little 2 7-dichZoroJEuorenone (?) m. p. 187-189'. 2 7-Dichlorofluorenone m. p. lS5-1S6O (which appears to be identical with Goldschmiedt and Schranzhofer's P-dichlorofluorenone) is obtained best by heating 2 7-dinitrofluorenone with phosphorus pentnchlorids in a sealed tube a t 17O-1SO0 and boiling the resulting 2 7 8 9-tetrachlorofluorene with water ; it forms an oxime decomp. 243' phenylhydraxone decomp. 186-187' and semicurbaxone decomp. 345' and is converted by copper into 2 2' 7 7'-tetracl~Zorobisdiphenytene-ethylene a red substance m. p. above 380'. c. s. The Preparation and Reactions of Bis-a-hydrindone-(2 2-)- spiran. HERMANN LEUCHS and DAN RADULESCU (Ber. 1912 45 189-201).-Dibenzylmalonic acid the preparation of which is fully described is converted by means of phosphorus pentachloride in to dibenxylmaZony2 chloride b.p. 216-21So/17 mm. 232-235"/32 mm. m. p. 68-69'. When dissolved in ether and treated with ammonia and aniline respectively this yields the corresponding amide (m. p. 198-199") and anilide (m. p. 196-197'). Boiling alcohol converts i t into the ester. During distillation of the chloride under diminished pressure as also when it is heated at 250-270' for some time hydrogen chloride is evolved and small quantities of bis-a-hydrindone- ( 2 2-)spiran formed. The latter is best prepared by distilling the chlosids under diminished pressure in the presence of 2% of alumininni chloride. It has b. p. 255-257'/12 mm. (corr.) m. p. 174'. Phenyl- hydrazine converts i t into bis-a-hydrindone-( 2 2-)-spiranbispl~en?/I- hydrazone colourless prisms m.p. 200-201° (decomp.). When treated with hydroxylamine a substance C17€11302N is formed (m. p. 214-215") which possibly has the formula c G H < E ~ ~ > c < ~ ~ D c G H ~ * Under the action of sodium hydroxide bis-a-hydrindone-( 2 2-)-spiran readily yields the sodium salt of a strong monobasic acid which is stable towards excess of alkali. The free acid has m. p. 140-142' and when heated a t 220° evolves water vapour with the reforma- tion of spiran. The composition of the acid is probably expressed by the for mula C,H,<2$&'HC(C6H4. It can be resolved into optically active forms by crystallisation of the brucine salt from acetone. Attempts were made to prepare the methyl ester of the acid by the action of methyl iodide on the silver salt. When distilled under diminished pressure it decomposed with the regeneration of spiran.Bis-a-hydrindone-(2 2-)-spiran when treated with alcoholic ammonia The ester could not be obtained in the crystalline state.i. 180 ABSTRACTS OF CHEMICAL PAPERS. forms two compounds C17H,,0N m. p. 246-248' (decomp.) and CIpH,,O2N. The latter when rapidly heated melts a t 124-128O (decomp,) and is readily transformed into the former by heating it above its m. p. or by treating i t with concentrated hydrochloric acid. These substances are probably not the nitrile and amide described acid since * neithei evolves ammonia when potassium hydroxide. The following formulae are proposed for them c 6 H 4 < ~ ~ ~ > c < ~ ~ ~ > c 6 H 4 and of the above- treated with provisional I y Anhydrobig-a-hydrindonespiran obtained in small quantity by the distillation of dibenzylmalonyl chloride under ordinary pressure in the presence of 4% of aluminium chloride crystallises from glacial acetic acid in light red needles m.p. 256-257'. H. W. Reactivity of Side-chains in Nuclear Nitrated Hornologues of Benzene. WALTHER BORSCHE (Annulen 19 12 386 35 1-3~9.- One of the halogen atoms is readily substituted the other only with difficulty when 1 3-dichloro-4 6-dinitrobenzene is warmed in ether with an excess of ethyl sodioacetoacetate. On the other hand both methyl groups react readily when 4 6-dinitro-m-xylene and benzaldehyde (2 mols.) are heated at 190' with a little piperidine ; the main product is 4 6-dinitro-1 3-distyrylbenzene C,H,(NO,),(CH:UHPh) m.p. 186' yellow needles very little 4 6-dinitro-3-methylstilbene C,H,Me(NO,),*CH:CHPh m. p. 145* being formed. Trinitromesitylene dinitromesitylene trinitro-$-cumene and 2 4-dinitroethylbenzene do not react with benzaldehyde. 2 4 6-Trinitrotoluene yields trinitrostilbene (Ullmann and Gschwind Abstr. 1908 i 622). 2 4 6-Trinitro-m-xylene benzaldehyde and a little piperidine when heated in boiling amyl alcoholic solution yield 2 4 6-ts.initro- 1 3-cZistyylbenzene C22H1506NS m. p. 147-148' yellow needles. Corresponding substances C,,H1?O,N3 m. p. 155' and C2,Hl3OI0N5 m. p. 268' (decomp.) are obtained with anisaldehyde and p-nitro- benzaldehyde respectively.These condensations proceed most smoothly in the toluene series less readily in the xylene series and badly or not at all in the mesitylene series. The author is of opinion that in these nitrated methylbenzenes the distribution of the residual affinity of the benzene nucleus is such that when only one methyl group is present the influence of the residual affinity is concentrated on the carbon atom of this methyl group its hydrogen atoms therefore becoming more mobile; as however the symmetry of the whole molecule is increased by the introduction of two and three methyl groups the influence of the residual affinity is distributed between the methyl groups with the result that their hydrogen atoms become less and less mobile. In the case of tbe chloronitrobenzenes the elimination of the halogen atom is due according to the author not to any weakening of the union between it and the carbon atom but rather t o a striving of the molecule t o assume an ortho- or para- quiuonoid structure ; the reagent s then held additively the final product being obtained by the elimination of a halide ; thus :ORGANIC CHEMISTRY.i. 181 Ullmann and Gschwind (Zoc. c k ) have shown that the reactivity of the methyl groiip in 2 4-diuitrotoluene still persists when one of the nitro-groups is replaced by a carboxy lie sulphonic or cyanogen group. The author finds however that in 6-nitro-4-cyano-m-xylene only one methyl group reacts with benzaldehyde and a little piperidine at 190-20Oo giving a very poor yield of 6-nitro-4-cyano-3-methyZ- stilbene (?) NO,*C,H,Me(CN)*CH :CHPh M.p. 183-184O yellow needles. 2 4-Dicyanotoluene does not react with benzsldehyde. 4 6-Dinitro-1 3-distyrylbenzene forms a tetrabromide C,H,(NO,),(CHRr*C HPhEr) m. p. 207-20bO (decomp.) and by reduction with stannous chloride and acetic and hydrochloric acids yields 4 6-diamino- 1 3-distyryZbenzer~e m. p. 204O yellow crystals with green fluor- escence. The base forms fluorescent solutions yields a dibenxoyl derivative which is unchanged at 2 7 5 O and react3 with benz- aldehyde in boiling alcohol to form the dibenxylidene derivative C,H,(N:CHPh),(CH:CHPh) in. p. 238-239' deep yellow non- fluorescent needles. A methyl-alcoholic solution of the base is reduced by hydrogen in the presence of a little colloidal pitlladium yielding 4 6-diamino- 1 3-di-P-phenyZethy2benxen~ C,H,( NH,),(CH,*CH,Ph) (diacet9Z derivative m.p. 224'; dibenzoyl derivative m. p. 273'). 4-Cyano-m-xylene and nitric acid D 1.52 a t 0' yield a mixture of sparingly soluble (in alcohol) yellowish prisms m. p. 107-108° (probably 6-nitro-4-cyano-m-xytene) and easily soluble white needles m. p. 120-1 2 1' (probably 4-cyano-2-nitro-m-rylene). By diazotisa- tion and treatment with cuprous cyanide 4-cyano-o-toluidine yields Non-Existence of $-Diphenyleneketone [ $-Fluorone]. A New Red Hydrocarbon. RUDOLF PUMMERER (Ber. 1912 45 294-298).-The red modification of fluorone obtained by Kerp (Abstr. 1896 i 238 ; compare also Stobbe ibid. 1911 i 651) by the distillation of calcium diphenoxide is shown to be the ordinary yellow variety of fluorone contaminated with traces of the red substance first observed by Fittig and Ostermayer (this Journ.1873 892) and shown by them to be produced simultaneously in the This red impurity is insoluble in alcohol /\-fN and solvents of low b. p. but dissolves to a slight II I I extent in solutions of fluorone from which i t may be \/\/\/ removed by shaking in the cold with animal charcoal. I II It may be isolated by repeatedly triturating the /\/\/\ '' red fluorone" with cold alcohol and crystsllis- 'I 1-11 I ing the residue from benzene. It forms slender \/ \/ lancet-shaped crystals m. p. 306O yields strongly 2 4-dicyanotoZuene m. p. 144-145' white needles. c. s. distillation. VOL. CII. 1. 0i. 182 ABSTRACTS OF CHEMICAL PAPERS. yellow fluorescent solutions and has the composition C26H14.On account of its bright red colour the hydrocarbon is termed by the author rubicene. Its constitution has not yet been definitely established but argu- ments are advanced in favour of the formula given on the preceding page. With bromine in chloroform solution it forms a bromo-substitution product ; the picrate crystallises in very slender brownish-red prisms. Kerp's "red fluorone" contains in addition to rubicene a white substance which remains behind on dissolving the ketone in concen- trated sulphuric acid. F. B. Isomeric SchiFs Bases. BRONISLAW PAWLEWSKI (Chem. Zentr. 1912 i 2 9 ; from Chem. Polski 1911 11 121-122).-0f the five substances obtained by the author by condensing benzoin with benzylamine one m. p. 88-90' is the trans-modification of benxylidene- benxylamine CHPh:N*CH,Ph and is stereoisomeric therefore with the liquid benzylidenebenzylamine b.p. 200-202'/10-20 mm. The Homo-chromoiaomerism of the Phenylmethylpicr- amides. ARTHUR HANTZSCH (Bey. 1912 45 360-363)- Polemical ; a reply to Biilmann (Abstr. 1911 i 963). F R ~ D ~ R I C REVERDIN and ARMAND DE Luc (Bey. 1912 45 349-354).-A continuation of earlier work (Abstr. 1909 i 377 913 ; 1910 i 470) in which a study has been made of the effect of the subetitution of the nitrobenzoyl group into the amino-group of p-anisidine on the behaviour of the base towards nitration. m-Nitro benxenesulphon yl-p-anisidide NO,*C,H,~SO,*NK~C,H,~O~~e obtained by the action of the acid chloride on the base forms white needles m. p.135'; the acetyl derivative forms needles m. p. 1 8 1-1 82'. o-Nitrotoluene-p-sulphonyl-p-anisidide obtained similarly forms needle crystals m. p. 81'; acetyl derivative m. p. 161'. The nitration of the above nitrobenzenesulphonyl-p-anisidide with nitric acid D 1.38 without cooling (max. temperature 36') gives as chief product an orange-yellow dinitro-derivative m. p. 1 70° which can be hydrolysed to the corresponding free base 2 5-dinitro-p-anisidine. I f the temperature is allowed to rise to 62" a mixture of the previous dinitro-compound with the isomeric 3 5-dinitro-compound m. p. 165-166' is obtained; this forms white needles and hydrolyses to 3 5-dinitro-4-aminoanisole. If the mixture during nitration is heated over a free flame there is obtained the nitrobenxemesulphonyl deriv- ative of 2 3 6-trinitro-4-aminoanisole which forms small prismatic crystals ni.p. 189-190'. When nitrated as an emulsion in acetic acid at 70' with nitric acid D 1.38 the main product is the above 3 5-dinitro-derivative. With nitric acid D 1.52 between 0' and 5' the product consists of a mixture of the 2 5-dinitro- and the 2 3 6-trinitro-derivatives; at higher temperatures decomposition occurs ; if the nitration with acid of this strength is perFormed at 5-10' in an emulsion in acetic acid described by Mason and Winder (Trans. 1894 SS 191). c. s. D. F. T. Nitration of the Acyl Derivatives of p-Anisidine.ORGANIC CHEMISTRY. i. 183 a mononitro-derivative is obtained (yellow needles m. p. 127O) which on hydrolyais gives 3-nitro-4-aminoanisole. With nitric acid D 1.38 the above-mentioned nitrotoluenesulphonyl- p-anisidide at 36' yields a mononitro-derivative (prismatic crystals m.p..13Y),the constitution of which is shown by its hydrolysis to 3-nitro- p-anisidine. At higher tern p erat ures the r~itrotolueneaulphonyl derivatives of 3 5-dinitro- and 2 3 6-trinitro-p-anisidine are obtained (m. p. 125-140' and 184-185O respectively); the former of these is also the product of nitrating a solution in acetic acid. With nitric acid D 1.52 at 5-10' the product contains the nitro- toluenesulphonyl derivatives of 2 3-dinitro-p-anisidine and 2 5- dinitro-p-anisidine (m. .p. of acyl derivatives 180' and 154' respectively); on nitrating in acetic acid in the cold the above- mentioned nitrotoluenesulphonyl derivatives of 3-nitro-p-anisidine and 2 5-dinitro-panisidine are obtained the latter preponderating.D. F. T. Decomposition of Mixed Phenyl Oxides in Presence of Nickel and Hydrogen. ALPHONSE MAILHE and M. MURAT (Bull. Soc. chim. 1912 [iv] 11 122-123).-1t is shown that all phenyl alkyl oxides when passed over heated nickel in a current of hydrogen are decomposed in accordance with the equations (1) C,H,*O*R + H = C,H,*OH + RH and (2) C,H,*O*K. + H2 = C,H + R*OH the alcohol and the paraffinic hydrocarbon formed being destroyed by the further action of the nickel. Anisole is most readily attacked and yields 52% of the possible weight of phenol whilst phenyl isoamyl oxide yields ouly 22%. Diphenyl oxide is attacked with great difficulty and gives only 6% of the possible weight of phenol.Veratrole at 205O yields 16% of the possible weight oE guaiacol and the latter on further treatment at 205' yields a mixture of phenol and catechol. T A. H. [Preparation of p- Aminophenyl Methyl Mercaptole.] AKTIEN- GESELLSCHAFT FUR ANILIN-FABRIKATION (D.R.-P. 239310).-p-Bmino- phanyl methyl mercaptole a colourless oil comparing favourably with phenacetin in therapeutical action is obtained by reducing p-nitro- phenyl methyl mercaptole (Blanksma Abstr. 1902 i 281); the salts are colourless and crystalline and the acatyl derivative forms colourless needles m. p. 127-128'. F. M. G. M. Preparation of 4-Chloro-a-naphthol. AKTIEN-GESELLSCHAFT FGR ANILIN-FABHIKATION (D.R.-P. 240038).-It is found that 4-chloro- a-naphthol can be prepared by treating a-naphthol arylsulphonyl ethers with chlorinating agents.a-Naphthyl p-toluenesulphonate colourless needles m. p. 83-84' prepared by the action of p-toluenesulphonyl chloride on sodium a-naphthoxide in alcoholic solution was dissolved in carbon tetrachloride and treated with chlorine when a satisfactory yield of 4-chloro-a-naphthol (m. p. 116') was obtained. F. M. G. M. 0 2i. 184 ABSTRACTS OF CHEMICAL PAPERS. The Red Coloration Produced in the Ferric Chloride Reaction with Catecbol in Alkaline Solution. I. RUDOLF FRIEDRICH WEINLAND and KARL BINDER (Bey. 1912 45 148-154). -The green coloration of an aqueous catechol solution produced by ferric chloride is changed to deep red on the addition of sodium potassium ammonium barium calcium and magnesium hydroxides.The red coloration is due to the formation of salts of an acid analogous to the ferricyanides or ferrioxttlates. The potassium salt K3[Fe”’(C6H40,),],2H20 is obtained as a lustrous crystalline brownish-black to dark brouze-red powder consisting of microscopic triangular priBms by the addition of ferric acetate to a solution of catechol in strong aqueous potassium hydroxide. It readily dissolves in water to deep red solutions which are decolorised by excess of acid with the liberation of catechol. When heated with sodium sulphide or potassium cyanide in aqueous solution the potassium salt is decomposed yielding ferrous sulphide and potassium ferro- cyanide respectively although in the presence of potassium hydroxide the aqueous solutions may be heated with the substances without undergoing change.The tendency to form salts of the above acid is so pronounced that freshly precipitated ferric hydroxide in the presence of aqueous alkalis or ammonia dissolves on the addition of catechol forming the corresponding alkali or ammonium salt. The ammonium salt ( NH4)3[Fe”’( C6H402)J,H20 prepared in a similar manner to the sodium salt is a brownish-black powder consisting of microscopic fliLt violet-red needles. Tho sodium salt Nas[ Fe’;’(C6H4OJ3] 1 OH,O forms microscopic red hexagonal columns capped with truncated pyramids. The lead salt is precipitated quantitatively on the addition of lead acetate to an aqueous solution of a n alkali salt. The morphine and strychnine salts are crystalline; the quinine and brucine salts are amorphous.Similar complex salts stable towards alkalis are obtained from catechol and aluminium cupric nickel cobalt and manganous salts and also from pyrogallol salicylic gallic or protocatechuic acids and ferric salts in alkaline solution. H,[ ~’”’’(CsH4@2)31 F. B. Derivatives of 4-Amino-orcinol (2-Amino-3 5-dihydroxy- toluene). FERDINAND HENHICH G. TAUBERT and H. BIRKNER (Ber. 1912 45 303-314. Compare Abstr. 1903 i 413).-2-Amino- orcinol has now been isolated in the free condition by the addition of sodium hydroxide t o a cold aqueous solution of the hydro- chloride in quantity just insufficient for complete decomposition. It crystallises from ethyl acetate in lustrous silvery-white leaflets decomposing a t 188-1 go’ with previous darkening at 160-180’.Its hydrochloride is oxidised by chromic acid in aqueous solution to 4-chloro-3-hydroxytolupuinone C O < ~ ~ ~ ~ ~ ~ ~ > C O which forms intensely yellow crystals m. p. 181-182’ volatile in ether vapour dissolves in alkalis yielding intensely red solutions and is reduced byORGANIC CHEMISTRY. i. 185 sulphur dioxide in aqueous solution to 4-chloro-2 3 5-trihydroxytoluene C,H70,CI colourless needles m. p. 137.5'. Acidification of the solutions of the quinone in aqueous ammonia or sodium carbonate results in formation of a substance having the same composition as the original quinone. This substance separates from benzene or chloro- form in yellow crystals darkening a t 220' dissolves in water less readily than the original quinone and is not volatile in ether vapour; but whether these differences are to be referred t o isomerism or polymerism has not yet been determined.That the auinone has the above constitution and not that of the isomeric been established by the synthesis of the latter compound from 2-amino-orcinol hydrochloride. This is converted by amyl nitrite in alcoholic solution into orcinoZ-2-diazoniunz chlo~ide a yellowish- white powder which forms with cuprous chloride a red crystal- line additive compound C,H2Me(OH),*N2CI,Cu2CI2. When heated under diminished pressure the additive compound melts a t SO-go' and decomposes a t a higher temperature into 2-chZoro-orcinol C,H,O,Cl m. p. 138-139O with previous sintering a t 115". The last-named compound reacts with amyl nitrite and potassium hydroxide in alcoholic solution to form the potassium sa.lt of 2-chloro- 6-nitroso-orcinol from which the free nitroso-compound is obtained by acidification with dilute sulphuric acid.2-ChZoro-6-nitroso-orcinol C7H,0,NCI exists in two modifications a stable yellow crystalline form melting a t 159-1 60' with previous darkening and a brown modification which passes into the yellow variety when heated. 2-ChZoro-6-amino-orcinoZ hydrochloride is obtained in slender white needles by reducing the preceding nitroso-compound with stannous chloride and hydrochloric acid. It is oxidised by chromic acid in aqueous solution to 6-chZo~o-3-hydrozytoZuene ruby-red crystals m. p. 165-166' (decomp.). F. B. Constitution of Diisoeugenol. ERNESTO PUXEDDU (Atti R. Accnd. Lincei 1912 [v] 21 i 42-46.Compare Abstr. 1909 i 225).-The paper deals with the action of light on isoeugenol and on its methyl ethyl and propyl ethers as well as the action of light on eugenol and its ethers. The author has also examined the action of nitrous acid on isoeugenol ethyl ether and on diisoeugenol diethyl ether. When a solution of 100 grams of isoeugenol in 200 C.C. of alcohol is treated with 25 C.C. of hydrochloric acid and exposed to light in a sealed tube crystals of diisoeugenol are quickly deposited and if the precipitate is collected after t w o days the yield amounts to 60%. If the filtered solution is again exposed to light a further quantity of the polymeride can be obtained. The mother liquors show a splendid blue fluorescence. Under the same conditions sulphuric acid also acts feebly as a polymerising agent.isoEugeno1 methyl ether isoeugenol ethyl ether and isoeugenol propyl ether yield the analogous polymerides when treated in the same way. isoEugenoZ propyl ether C,,HI,O,,i. 186 ABSTRACTS OF CHEMICAL PAPERS. prepared from isoeugenol with sodium propoxide and propyl iodide crystallises in long prismatic needles m. p. 54O. Diisoeugenol dipropyl ether (G,3H,,0,!2 forms prismatic needles m. p. 94". Eugenol and Its methyl and ethyl ethers under the same conditions are not acted on by light. When isoeugenol ethyl ether is treated with glacial acetic acid and potassium nitrite a substance C,,H,,O,N is obtained which crystallises in yellow tabular prisms m. p. 8 5 O . It is assigned the formula of the peroxide C,H,(OMe)(OEt)*F- -No0 CMe:N*(J' analogous t o that from isoeugenol methyl ether (compare Malagnini Abstr.1895 i 35). Diisoeugenol diethyl ether does not react with nitrous acid and therefore probably does not contain an unsaturated side-chain. R. V. 8. Action of Phorone on Catechol and Pyrogallol. MARIO GHTGLTENO ( A t t i R. Accad. Sci. Torino 1912 4'7 16-22).-Fabinyi and Szdki (compare Abstr. 1905 i 591 888) obtained products by heating acetone with catechol and with pyrogallol in a sealed tube at 145". I n the present paper i t is shown that the formulae ascribed t o these substances are incorrect. Under tbe conditions of experiment the acetone is condensed to phorone which reacts with the phenols giving substances of the following constitutions respectively and C(CH:CMe,),[C,H,( OH),],.This explains the existence of the tetrabromo- and dibromo-derivatives. I n confirmation of this view the authors have prepared the same substances using phorone instead of acetone. It is not necessary to heat the mixture a t 145'; the same products are obtained when phorone and the phenol are heated together in a sealed tube a t looo o r even in an open flask with condenser. I n t h e case of the product from pyrogallol the somewhat discordant analyses of Fabinpi and Szdki are explained by the fact that the substance contains 1 mol. H,O which i t loses completely only at 130-140° and which i t re-absorbs very readily on exposure to air. R. V. S. C(CH:CMe,)*[C,H,(OH),] Action of Formic Acid on Triarylcarbinols. ALFRED GUYOT and A. KOVACHE (Compt.rend. 1912,154 121-122).-Triarylcarbiools are readily reduced when treated with twenty times their weight of crystallisable formic acid giving the corresponding hydrocarbons with formation of water and evolution of carbon dioxide. The reaction may be made use of for accurately determining the number of hydroxyl groups in such carbinols by weighing the carbon dioxide evolved from less than a gram of the substance. Quantitative results were obtained with triphenylcarbinol phenyldi-p-tolylcarbinol o-benzoyltriphenyl- carbinol and 9 10-diphenylanthranol whilst 9-phenylanthrmol and 9 10-dihydroxy-3 10 10-triphenyldihydroanthraceoe gave less than the calculated amount of carbon dioxide although the yield of hydrocarbon was theoretical. w. 0. w.ORGANIC CHEMISTRY.i. 187 The Walden Inversion and Substitution Processes. EMIL FISCHER (Annalem 1912 386 374-386. Compare Abstr. 1911 i 418).-An amplification of the author’s view that the phenomena met with in the addition of halogens or halogen hydracids to stereoisomeric unsaturated compounds are probably of a similar type to the Walden inversion Reactions such as t h a t whereby both inactive dibromo- succinic acids result by the addition of bromine to maleic or to fumaric acid have been regarded by Werner and by van’t Hoff as exceptional and due to a specific action of the halogen. Examples are given however to show that similar results may be obtained by the addition of groups or atoms other than halogens. It is true that the oxidation of cinnamamide by potassium permanganate yields only one phenyl- gZyceYam,ide OH*CHPh*CH(OH)*CO*NH2 m.p. 161-162’ (corr.) (which yields the phenylglyceric acid having m. p. 1 41° by hydrolysis) and the oxidation of cinnamoylglycine gives only one phenylglyceryl- glycine OH*CHPh*CH(OH)*CO*NH*CH,*CO,H m. p. 144-145’ (corr,). However Baeyer has shown that Al-tetrahydrophthalic acid yields two stereoisomeric hexahydrophthalic acids by reduction whilst Fittig has obtained two dimethylsuccinic acids by the reduction of dimethyl- fumaric acid. c. s. Spectrochemical Differentiation between Hydroaromatic Compounds with Endocyclic and with Semicyclic Double Linkings. KARL AUWERS and PHILIPP ELLINGER (Annalen 19 12 38’7 200-239).-Unsaturated hydroaromatic hydrocarbons contain- ing semicyclic double linkings exhibit a moderate exaltation of the specific refraction and a marked exaltation of the specific dispersion. Unsaturated hydroaromatic hydrocarbons containing endocyclic double linkings are optically normal These statements are based not only on the spectrometric examination of the many alkylidenecyclo- paraffins which have been prepared by Wallach but also on a direct comparison of the alkylidenecyclohexanes (methylene- ethylidene- and isopropylidene-cyclohexanes) with the isomeric alkyl-A1-cyclo- hexenes (methyl- ethyl- and isopropyl-cyclohexenes) ; the latter are optically normal whilst the former exhibit an exaltation of 0.28-0.47 of SD and an exaltation of 6-10% of 2 - 8,.The spectrochemical method of differentiating between the two classes of isomerides has been utilised t o show t h a t Sitbatier and Mailhe’s alkylidenecyclohexane derivatives are really unsaturated endocyclic compounds and that Zelinsky and Gutt’s 3-methyl-1 - ethylidenecyclohexane must be on account of its optical normality 3-m e thy1 - 1 -ethyl- Al-cyclohexene. Al-cycZoHexenylacetic acid and its esters and their homologues containing a methyl group in position a 2 3 or 4 are optically normal.cycEoHexylideneacetic acid and its homologues containing a methyl group in position 2 3 or 4 have too high m. p.’s to be suitable for spectrometric examiuation but their methyl and ethyl esters show a marked exaltation 0.79-1.05 of the specific refraction BD and still more pronounced exaltation 31-40% of the specific dispersion S,-8,. These are due not only to the semicyr:lic b u t also to the conjugated double linking.Esters of the acids contain-i. 188 ABSTRACTS OF CHEMICAL PAPERS. ing a methyl group in the a-position contain a disturbed conjugation and therefore show smaller exaltations but even in these cases the exaltations are so pronounced that there can be no uncertainty in distinguishing such esters from those of a-substituted cyclohexenyl- acetic acids. The authors regard the spectrometric method as far safer than any chemical process for the determination of the constitution of such easily changeable substances as cyclohexenyl- and the cydohexylidene- acetic acids. The following new compounds are described; they have been obtained by Wallach's methods as a rule. 1 -isoPro~yZcyclohexccnol C9H,*0 b.p. 176.4-176-7' Dy'5 009142 nu 1.46064 n 1.46419 and ny 1.47387 at 15.5' ; eth$ A1-cyclohexenykctcelate C,H,*CH2*C0,Et b. p. 100'/12 mm. Di62 0,9829 n 1.46422 n 1.46906 ny 1-48017 at 16.2' ; methyl a-1-Aydroxycyclohexylpropionccte OH* C,H,,*CHMe*CO,Me b. p. 132'/18 mm. DY 1.0537 ; methyl a-A'-cyclohexenylpropionate C6H,*CHMe*C02Me b. p. 108-1 08*5'/18 mm. D:'" 0-9864 n 1.46373 n 1.46648 my 1.47885 at 18.3'; methyl 2-nzethylcyclo- Izexylidenecuetute C,H,Me:CH*CO,Me (prepared from methyl iodide and the silver salt of the acid m. p. GS') b. p. 119*9"/15 mm. D:'"'" 0.9'767 n 1.47681 n 1.48072 ny 1.49802 at 14.2'; the corre- sponding ethyl ester has b. p. 128-2'/13 mm. D:"'* 0.9587 n 1.47524 n 1.47906 and ny 1,49639 a t 14 8' ; methyl 3-metl~ylcyclo?~exylidm~- acetate C,HgMe:CH*CO,Me b.p. 117'/13 mm. Di55 0.9752 7~~1.47534 n 1.47926 ny 1.49668 a t 15.5'; the ethyl ester has b. p. 131.4'/ 18 mm. DY 0.9571 n 1.47347 n 1.47730 ny 1.49464 at 15'. c. s. Correlation of I o n i s a t i o n and S t r u c t u r e . 11. Negatively Substituted Benzoic Acids. C. G. YEHICK (-7. Amer. Chem. SOC. 1912 34 74-82).-1t mas shown in an earlier paper (Abstr. 1911 ii 713) t h a t the free energy of ionisation for negatively substituted monobasic fatty acids in aqueous solution at 25'is the sum of the mparate effects of each atom in the molecule. Hence it was demon- strated that the position of a negative atom or group in an acid can be determined if its a-" place factor" and the ionisation constant of the substituted acid a r e known. In the present pager i t isshown that the additive relationship in the free energy of ionisation is also true in the case of aromatic acids and t h a t i t is therefore possible to determine the structure of substituted benzoic acids containing negative groups or atoms if the ortho- meta- and para-'' place factors " are known for each negative radicle.The '' place factors " have been determined for benzoic acid for the acetoxy- carboxy- chloro- hydroxy- and nitro-radicles for the ortho- mettt- and para-positions ; for the aldehydo- benzoyl- bromo- carb- methoxy- carbet,hoxy- iodo- and methoxy-radicles for the ort ho-position ; and for the cyano- fluoro- and iodo-radicles for the meta-position. From these numbers the ionisation constants for the substituted benzoic acids were calculated and agreed closely with the experimental values in nearly all cases,3RGANIC CHEMISTRY.i. 189 There is no simple relation between the '' place factors" for the same radicle substituted in the ortho- meta- and para-positions in benzoic acid. Ionisation mill not differentiate between 2 3- and 2 5-di-substituted benzoic acids in which the substituting radicles in the 3- and 5-positions are the same and those in the 2-positions are also the same. The fact that the 3- and 5-positions are equivalent with respect to the 1-position has been proved in terms of the free energy of ionisation. E. G. Barium Hippurate. EYVIND B~DTKER (Chem. Zed. 191 2 38 105).-Analyses of this salt prepared by neutralising hippuric acid with barium hydroxide crystallising it from water aud drying the crystals between blotting paper show that it contains 5H20.The statement that it. contains only 1H20 may be due to the salt having been dried over sulphuric acid before analysis although the strontium salt. when similarly dried does not lose water. Attempts to prepare Preparation of Cinnamic Esters of Polyatomic Alcohols. Abstr. 191 1 i 858).-P-ChZoroethyZ cinnnnante CHPh:CH.CO,*C,H,Cl a colourless solid m. p. 31' b. p. 188-191'!20 mm. is prepared by the interaction of chloroethyl alcohol and cinnamic acid in the presence of concentrated sulphuric acid; when heated a t 140' with sodium acetate and dilute acetic acid it furnishes glycol cinnarnats b. p. 170-175°/15 mm. ferric hippurate were not successful. w. P. s. FARBENFABRIKEN VORM.FRIEDR. BAYER & CO. (D.R.-P. 239650. Compare y-ChZoro-P-hydroxypropyl cinnamnte CHPh:CH*C02*CH2*CH(OH)*CH2CI a yellowish viscid liquid b. p. 210-218'/20 mm. prepared from monochlorobydrin and cinnamic acid by similar treatment yields glycerol cinnamate. Other weak acids and their salts can replace acetic acid in this reaction. Sodium Phenyl Carbonate as I n t e r m e d i a t e Product of Kolbe's Synthesis for Salicylic Acid. CARL B. SLUITEB (Ber. 1912 45 59-62).-1t has been asserted (de Bruyn and Tymstra Abstr. 1905 i 209; Tymstra Abstr. 1905 i 439) that under the conditions of Kolbe's process sodium phenyl carbonate cannot be an intermediate step on account of its dissociation into carbon dioxide and sodium phenoxide; in their opinion the carbon dioxide molecule inserts itself directly between the carbon and hydrogen atoms in the ortho-position of the sodium phenoxide giving the phenolic sodium derivative of salicylic acid 1*272 Dloo 1.1032) and examines carefully t h e reaction products obtained by heating to 160' with an equimolecular quantity of dry sodium hydroxide (compare Hentschel Abstr.1883 588) in a current of nitrogen. The evolution of carbon dioxide ends after two to three minutes and the residue contains sodium phenoxide sodium carbonate and sodium salicylate with some unchanged diphenyl carbonate. Two reactions are therefore believed to occur concurrently F. M. G. M. The author takes diphenyl carbonate (m. p. 78*2-'78*4" (1) PhO*CO*OPh + 2NaOH = 2PhOH + Na2C0 ;i. 190 ABSTRACTS OF CHEMICAL PAPERS (2) PhO*CO*OPh + NaOH = Ph*OH + PhO*CO*ONa; the sodium phenyl carbonate then partly dissociates into carbon dioxide and sodium phenoxide and partly is rearranged into sodium salicylate.The alternative explanation given above for the formation of the last substance cannot hold in this case as the pressure of carbon dioxide would be quite insufficient for reaction with the sodium phenoxide. It appears therefore that under the conditions of Kolbe's synthesis sodium phenyl carbonate can undergo rearrangement I into sodium salicylat e. D. F. T. Two Phthaloximes and Some of Their Derivatives. WILLIAM R. ORNDORFF and DAVID S. PRATT (Amer. Chem. J. 1912,47,89-125). -It has been shown by R. Meyer (Abstr. 1905 i 440; 1909 i 652) that quinolphthalein yields three oximes of which two are coloured whilst the other is colourless.The coloured oximes were regarded as cis and irans-stereoisomerides and the group CNOH was considered to be the chromophore. In order to ascertain whether this group behaves as a chromophore when present in a five- membered ring a study has been made of phthalylhydroxylamine first described by Lassar-Cohn (Abstr. 1881 585) which the authors prefer to term phthaloxime. The compound was prepared by Lach's method (Abstr. 1883,1104) which consists of heating a mixture of phthalic anhydride hydroxyl- amine hydrochloride sodium carbonate and water for an hour a t 60'. As the reaction product cooled colourless crystals of phthaloxime separated in quantity equivalent to a 70% yield. When the mother liauor was heated a t 100' for one and a-half hours and then left to 1 cool lemon-yellow crystals of an isomeric phthaloxime appeared. These oximes C,H,@$Z?>O both melt a t 220-226' and are slowly decomposed when heated at 110'.Both forms dissolve in alkali hydroxides with the production of red solut'ions which gradually become coiourless owing to the formation of salts of the hydroxamic acid. If the colourless oxime is heated with a solvent containing a hydroxyl group it is partly converted into the yellow isomeride and if boiled for an hour with glacial acetic acid i t is quantitatively transformed into the yellow form. The yellow oxime can be quanti- tatively changed into the colourless variety by boiling it with acetic anhydride the same colourless acetate m.p. 183-185' being obtained in this case as when the colourless isomeride itself is acetylated. When the colourless acetate is treated with a solution of ammonia and afterwards acidified the white oxime is precipitated. A yellow acetate also of m. p. 183-185' can be obtained from the yellow oxime by the action of acetic anhydride at the ordinary temperature. Both oximes yield red ammonium sodium sodium hydrogen potassium hydrogen and silver salts from which the original oxime is regenerated in each case on treatment with acids. When the silver salts are treated with ethyl iodide that of the colourloss oxime yieldsORGANIC CHEMISTRY. i. 191 a colourless ethy2 ether and t h a t of the yellow oxime a lemon-yellow ethyl ether both melting at 95-100'. Each oxime has been submitted t o a crystallographic examination.The colourless oxime forms monoclinic needles elongated in the direction of the b-axis and usually flattened parallel to a pair of faces in the ortho-zone ; the crystals have n 1,522 in a direction parallel t o the elongation. The optical properties of the yellow oxime closely resemble those of the colourless form except in respect of colour. The colour of the yellow variety is due mostly if not entirely to fluorescence. A crystallographic study has also been made of the salts aketates and ethyl ethers. The constitution of these oximes is discussed and evidence is adduced to show that in all probability they are not structural isomerides but stereoisomerides of the formuh ,-co- ,-co- O-R-C,H and O-s-C',H,. E.G. H0.N N*OH RUDOLF PUMMERER and GUSTAV DORFM~LLER (Bey. 191 2 45 292-294).-The transformation of isophthalanil into phthalanil (?o'o>C:NPh -+ C,H4< >NPh takes place slowly at the ordinary temperature as indicated by the rise in m. p. of a specimen of the former compound from 116' to 150' after being kept for six months and also by the isolation of phthalanil from the product. When shaken with concentrated aqueoris sodium carbonate at the ordinary temperature isophthalanil undergoes complete trans- formation in the course of five hours. With dilute sodium carbonate i t is converted after several days mainly into phthalanilic acid only traces of phthalanil being produced ; phthalanil undergoes no change when subjected to the same treatment. The transformation has also been effected by boiling solutions of isophthalanil in pyridine quinoline and nitrobenzene ; with water and light petroleum no change occurs. isophthalanil reacts with benzene in the presence of aluminium chloride yielding o-benzoylbenzanilide.F. B. Simple Fatty Arnines containing Sulphur. WILHELM SCEINEIDER (Annulen 191 2 386 332-350).-The possibility that derivatives of aminosulphones other than cheirolin (met hyl-y-thio- carbimidopropylsulphone) (Abstr. 191 0 i 658) may occur in nature has led the author to prepare aliphatic aminosulphones and the corre- sponding thiocarbimides aliphatic aminosulphides and amino- sulphoxides. [With MAX MULLER and WILHELM BEcK.]-P-Pht~alimidoethyl methyl sulpliide CGEI,<~~>N*CH2*CH2*SMe m. p. 89' prepared from sodium methyl mercaptide and P-bromoethylphthalimide yields by hydrolysis methyl P-arninoethyl suZphide NH,*CH,*CH,*SMe b.p. 146-148O a colourless liquid having the odour of piperidine and strongly basic properties (hydrocldoride m. p. about 120' ; picrate m. p. >119' ; picrolonute decornp. 187' ; oxalate m. p. 197' ; beneoyl isophthalanil. co C,H,- COi. 192 ABSTRACTS OF CHEMICAL PAPERS. derivative m. p. 57'). By treatment with alkali and an excess of methyl iodide it yields not a n NS-dimethiodide as does methyl- y-aminopropyl sulphide (Zoc. cit.) but the methiodide of methyl P-dimethylaminoethyl sulphide SMe-CH,.CH,*N Me,I decomp. 220-5' colourless leaflets which is decomposed by warm alkalis with evolution of trimethylamine. P- PhthalimidodiethyZ sulphide C,H4<CO>N* co CH,* CH,*SEt m.p. 39' yields by hydrolysis fi-aminodiethyl sulphide C,HIINS b. p. 163' (hydrochloride m. p 147'; hydyogen oxalate m. p. 145.5'; picrate m. p. 148' ; pic.r*olonate dlxomp. 184" ; benzoyl derivative b. p. 221-222'/40 mm. [decomp.]). The rnethiodide of /3-dimethyl- nminodiethyl sulphide decomposes a t 21 6.5'. By oxidising its hydrochloride with hydrogen peroxide and treating the product with alcoholic sodium ethoxide methyl P-aminoethyl sulphide yields methyl P-arnircoeth?yl sulphoxide CH,*SO*CH,*CH,*NH which cannot be distilled but is volatile with steam. It forms an oxalate m. p. 165' picrate m. p. 158" and picrolonnts decomp. 205' and is decomposed when treated with methyl iodide. P-Aminodiethyl sulphoxide prepared in a similar manner forms an ozalccte m.p. 176' picrate m. p. 138O picroloiaate decomp. 190° and when heated with the calculated quantities of methyl-alcoholic methyl iodide and sodium carbonate is converted into the methiodide of P dimethylaminodiethyl sulphoxide m. p. 168". Methyl y-arninopropyl suZphoxide CH,-YO*[CH,],*NH forms an oxulate m. p. 197' picrate m. p. 143' and picrolonate decomp. 2 1 O'. Methyl-P-aminoethylsui'phone obtained in the form of the hydro- chloride UH,*SO,*CH,*CH,*NH,,HCl m. p. 169' by oxidising the hydrochloride of the sulphide by potassium permanganate forms a picrate m. p. 167' picrolonate decomp. 325',.platinichloride decomp. 227' and benzoyl derivative m. p. 134' yields the methiodide of methy1.P-dimethylaminoethylsulphone m.p. 220° with methyl- alcoholic methyl iodide a t 120° and is converted into di-P-methyl- suZphonethyZthiocGcrbamide SC(NH.CH,*CH,-SO,Me) m. p. 1 41' by carbon disulphide and into methyl-fi-thiocarbimidoeth ylsulphone S0,Me.C H,*CH,*NCS m. p. 46-47' by Hofmann's method with carbon disulphide. P-Amirtodiethylsulphone prepared as the hydrochloride m. p. 101-102' in a similar manner forms a picrate m. p. 163" picrolonate decomp. 2 1 O' pptinichloride decomp. 227" aurichloride m. p. 197" benxoyl derivative m. p. 86' and thiocarbamide m. p. 141'; the thiocarbimide could not be isolated. [With W ILHELM L~HMANK. ] - Fhthcdimidodimeth y 2 sulphide C,H,<gz>N .CH,*SMe m. p. 114' is obtained from bromomethylphthalimide and sodium methyl mercaptide in alcoholic solution.It is oxidised by hot aqueous potassium permanganate t o the sulphone C,,,H,O,NS rn. p. 203'. Both the eulphido and the sulphone decompose completely when hydrolysed. c. s.ORGANIC CHEMISTRY. i. 193 Chemical Action of Light on Vanillin and its Ethers. ERNESTO PUXEDDU (Atti R. Accad. Lincei 1911 [v] 20 ii 717-723). -When vanillin in solution in alcohol benzeue or other solvents is exposed t o light dehydrovanillin is obtained in smill quantity and no other product can be detected except a viscous oil. Vanillin methyl and ethyl ethers behave differently when exposed t o light in benzene solution the corresponding methyl and ethyl ethers of vanillic acid being formed respectively. R e a c t i v i t y of the Carbonyl Group. HERMANN STAUDINGER (AnnaZen 1912 387 254-255).-A note explaining more fully the pictorial representation of the unsaturation of an atom by the length of the dotted line representing its residual affinity (compare R.V. S. Staudinger and Kon Abstr. 1911 i 876). c. s. Behaviour of A n t i m o n y Trichloride and Tribromide towards certain Oxygenated Organic Compounds. BORIS N. MENSCHUTKIN (J. Russ; Phys. Chem. Xoc. 1911 43 17%-1804).- The concentration-temperature diagrams given by acetophenone or benzophenone wit,h antimony trichloride or t r i bromide are all nearly identical each system being characterised by the formation of one molecular compound which contains 1 mol. of t h e ketone t o 1 mol. of antimony salt and melts unchanged. Each diagram consists of four branches corresponding with (1) the lowering of the m.p. of the ketone by addition of antimony salt (2) the solubility in the ketone of the molecular compound (3) the lowering of the m. p. of this compound by the addition of SbX and (4) the lowering of the m. p. of SbX on addition to it of the molecular compound. Each diagram exhibits two eutectic points. The melting points of the various compounds are SbCl,,COMePh 60.5' ; SbBr,,COMePh 37.5' ; SbCl,,COPh 76' ; SbBr,,COPh 48.5". The eutectic temperatures and the corresponding numbers of ketone mols. ( n ) per mol. of antimony salt are as follows 1st eutectic point. M. p. M. p. System. Ketone. Temperature. n. Temperature. n. SbX,. 2nd eutectic point. SbC1,-COMePh ...... 19.5" 1" 4.05 32" 0.36 73" SbBr3-COMePh ...... 19.5 1.5 3.17 31 0.6 94 SbC13-COPh ........ 48 35 4.63 39 0-26 73 Sb Br,-CO Ph . . . . . . . . 4 8 29 2.82 40 0.5 94 Benzoic acid (m. p. 120') forms a molecular compound with neither antimony trichloride nor tribromide the concentration-temperature diagram consisting in each case of two branches meeting at the following eutectic points SbC1,,0-52Ph-C02H 46' ; SbBr3,O-42Ph*CO,H 79". The system SbC1,-CH,*CO,H gives a molecular compound which forms only with dificulty. The first branch of the curve terminates at the eutectic point - go corresponding with the composition SbCI3,3.13CH,*CO,H. Then begins the curve of solubility of the molecular compound in acetic acid but this is observable only on seeding with the molecular compound; unless this is done branch 1 is prolonged below the eutectic point and probably meets branch 4 ini.194 ABSTRACTS OF CHEMICAL PAPERS. another eutectic point. Branch 1 shows no arrest corresponding with the eutectic point CH;CO,H-SbCl,,C H,*CO,H as the compound is not formed on cooling the solution. Branch 3 cuts branch 4 (lowering of m. p. of SbC1 on addition of CH,*CO,H) at the eutectic point about 19' corresponding approximately with SbC13,0-94CH3*C02H ; branch 3 can be followed below this eutectic point but then represents an unstable condition. The system SbBr,-CH,*CO,H forms no molecular compound the curve consisting of two branches meeting a t the eutectic point 4O which corresponds with SbBr,,4-34CH,*CO2H. Benzoyl chloride forms no molecular compound with antimony chloride or bromide each curve showing a single eutectic point SbC13,1.95Ph*COC1 - 33' and SbBr3,5.45Ph-C0C1 - 6'. T.H. P. The Reduction of Poly-unsaturated Ketones with Crossed Double Linkings by Paal's Method WALTHER BORSCHE (Ber. 19 12 45 46-53).-The author has already successfully applied Paal's reduction method to the preparation of saturated ketones from such unsaturated ketones as cinnamylideneacetone (Abstr. 191 2 i SSO) and now extends the investigation to ketones in which each of the two carbon atoms adjacent to the carbonyl group has a double linking. The results indicate that where there is only one double bond on each side of the carbonyl group the reduction proceeds smoothly but that in other cases there is considerable formation of resinous substances as by-products. The reduction of distyryl ketone yields di-/I-phenylethyl ketone b.p. 224'/18 mm. ; the oxime melts a t 95-96' (compare Diinschmann and von Pechmann Abstr. 1891 674) ; a small quantity of a substmce C34H3402 m. p. 126' was also obtained. Di-p-methoxystyryl ketone is reduced to a€-di-p-methoxyphenylpentan-y-one which crystallises in needles m. p. 52". Di-o-hydroxystyryl ketone gives aedi-o-hydroxyphenylpentan-y-one a viscid m a s which when heated loses water with the formation of tetra- hydrodibenxospiropyvan (compare Decker and Felser Abstr. 1908 i 906) which crystallises in needles m. p. l l O o b. p. 217"/16 mm. 1 3-Dibenzylidenecyclopentan-2-one gives 1 3-dibenzyZcyclopentan-2- one as an oil b. p. 232-233' which slowly crystallises in needles m. p. 47'. I n a similar manner 1 3-dibenzylidenecyclohexan-2-one and 1 3-dibenzylidenecycloheptan-2-one give the corresponding 1 3- dibenzylcgclohexan-2-one m.p. 11 4' and 1 3-dibenxyZcycloheptan-2-one b. p. 261-262'/28 mm. Yhenyl cinnamylidenemethyl ketone produces phenyl 6-phenylbutyl- ketone b. p. 225-226'; the oxime forms prismatic crystals m. p. 81-82' and by the Beckmann rearrangement changes into the aniEide of 6-phenyZvaZeric acid m. p. 84-90'. Styryl cinnamylidenemethyl ketone gives av-diphenylheptan-y-one b. p. 239'114 mm. ; the semicarbaxone is an oil whilst the hydrazone phenylcarbamate CH,Ph*CH,*C( N*NH*CO*NHPh) [CHJ,*CH,Ph has m. p. 122-123'. Dicinnamylideneacetone gives ai-diphenylnonan-€-one (6-phenylbutyl ketone) an oil b. p. 258-260'/13 mm. which solidifies in a freezingORGANIC CHEMISTRY. i.195 mixture ; the oxime and semicarbaxone are liquids whilst the hydrazone phenylcarbamate forms silky needles m. p. 129-130'. 2 6-Di-ciunamylidenecyclohexanone gives 2 6-di-w-phenylpvopy Z- cyclohexanone as a viscous oil b. p. 276-278'. D. F. T. Synthesis of Butin. A. GOSCHKE and JOSEF TAMBOR (Ber. 1912 45 186-188. Compare Abstr. 1912 1 30).-The authors have succeeded in transforming synthetic butein into butin (compare Perkin and Hummel Trans. 1904 85 1459) thus completing the synthesis of both these natural products. Butin triacetate has m. p. 123'. By the action of 3 4-dimethoxybenzaldehyde on resacetophenone and resacetophenone dimethyl ether respectively they have prepared the 3' $-dimethyl ether of butein (m. p. 203') and butein tetramethyl ether (m. p.89'). 2' 4' 2-Trihydrox~chc~Zkone prepared by condensation of salicyl- aldehyde with resacetophenone crystallises in orange needles + 1 H,O and has m. p. 185'. Its transformation into 3 2'-dihydroxyflavanone appears to be difficult. H. W. Preparation of Benzanthrone and its Derivatives. ROLAND SCHOLL (D.R.-P. 239761).-When aromatic mono- or poly-ketones containing a free peri-position with regard to the carbonyl group are heated at about 140-150' with either aluminium chloride or bromide or ferric chloride condensation occurs yielding benzan throne or py ran throne derivatives. The following compounds have been prepared Beneanthrone from phenyl a-naphthyl ketone. Naphthabenxanthrone f rom 1 1'-dinaph- thy1 ketone which can be prepared by the interaction of naphthoic acid with naphthalene in the presence of aluminium chloride.Uibenzoylpyvene (I) m. p. 155" and tribenxoylpyrene m. p. 235-237' are prepared by the action of benzoyl chloride on pyrene in the presence of aluminium chloride and separated by fractional crystallisa- tion from acetic acid; when the former is heated a t 160' with aluminium chloride it yields pyranthrone (Abstr. 1910 i 271). 2%-a-naphthoylpyrene m. p. 2 18-2 1 go prepared from pyrene and a-naphthoyl chloride furnishes naphthapyranthrow. Dibenzoyl-1 l'-dinaphthyl obtained from 1 1'-dinaphthyl and benzog 1 chloride furnishes uiokanthren (11) a violet powder whilsti. 196 ABSTRACl'S OF CHEMICAL PAPERS nap~~thylanthraqzcinony~ ketone (from anthraquinone-2-carbonyl chloride and naphthalene) gives phthaloylbenxanthrone and m-tolyl-1-naphthyl ketone yields methylbe~zxantl~rons brownish-yellow needles m.p. 164-1 65". F. 31. G. M. Ketones Derived from isoMyristicin. EVERARDO SCANDOLA (Atti R. Accud. Lincei 1912 [v] 21 i 47-54).-The author has prepared the a- and P-keto-derivatives of isomyristicin and has attempted to obtain the dimeric form of isomyristicin. The a-ketone is prepared by heating together for some hours the dibromo-derivative of isomyristicin (Thorns Abstr. 1904 i 47) and sodium methoxide removing the excess of methyl alcohol and distilling the residue with steam. After fractionation in a vacuum of the oil which passes over the pure a-keto-derivative of isomyristicin C,,H120 is preferably obtained by way of the semicarbazide or oxime.It crystallises in small silky needles m. p. 93". It yields a crystalline bisulphite compound which does not melt below 330". The oxime C,,H1,O,N crystallises in very small prisms m. p. 124". The semicarbaxone C12H,,04N has m. p. 180". The ketone does not give an hydroxamic acid with Piloty's acid. The /3-ketone of isomyristicin was prepared by Hoering's method (Abstr. 1905 i 902) When the dibromo-derivative of isomyristicin is heated with water and acetone in the presence of calcium carbonate (marble) for two hours the acetone solution separated and heated for a further two hours and then distilled P-bromo-a-~~yclroxydi17Lydroiso- myristicin C,,H,,O,Br is obtained. It is a very dense yellowish- brown oil with a pungent odour and it cannot be crystallised or distilled in a vacuum.On treatment of this substance with alcoholic potassium hydroxide a glycol OH*CHR*CHMe*OH should be produced from which the oxide Ar*CH*CHMe and finally its isomeride the P-ketone Ar*CH,*COMe could be obtained. Actually the raw product of the reaction does not combine with bisulphite and it gives analytical figures intermediate between those required by the glycol ClIH140 and the oxide Cl1Hl2O4 but when it is distilled i n a vacuum most of it passes over at 230-240°/30 mm. ; the distillate readily crystallises and has m. p. 44-45'. After recrystallisation it forms long silky needles m. p. 54-55",-and gives on analysis numbers corresponding with the formula C,,H1,04. This substance gives a bisulphite compound and is evidently the @ketone.The isomerisation of the oxide is best effected by heating the substance in glacial acetic acid with a few*drops of concentrated sulphuric acid and purifying the product by way of the bisulphite compound. The semicarbuaone C,,H?,O,N has m. p. 143-144". The ozime C,,Hl,04N crystal- lises in tufts of prisms m. p 111-112". The &ketone was also prepared by reduction of P-nitroisomyristicin and hydrolysis of the oxime produced. Numerous attempts were made by various methods to polymerise isomyristicin. I n only one case was any new product obtained. When isomyristicin is heated for five to ten minutes in glacial acetic acid solution with a trace of concentrated sulphuric acid a substance '0'ORGANIC CHEMISTRY. i. 197 is obtained which crystallises in small prisms m.p. 232-233* and may be the dimeric form of isomyristicin. The yield is less than 2%. R. V. S. Constitution of Chrysophanic Acid. EUGBNE LPGER (Compt. rend. 19 12 154,281-283. Compare Robinson and Simonsen Trans. 1909 95 1085 ; Oesterle Abstr. 1911 i 887).-In order to deter- mine the position of the methyl group in chrysophanic acid the tetra- nitro-derivative was oxidised with nitric acid (D 1.5). 2 4 6-Trinitro- 3-hydroxybenzoic acid was isolated from the products but chrysammic acid could not be detected. It follows that the nitro- and hydroxy- groups in tetranitrochrysophanic acid occupy the same positions as they do in tetranitroaloe-emodin and therefore that the methyl group in chrysophanic acid can only occupy the position assigned to it by Fischer Falco and Gross (A.bstr.1911 i 309). Chrysophanic acid is therefore 1 8-dihydroxy-3-metbylanthraquinone. This conclusion is confirmed by fusing the acid with potassium hydroxide when 5-hyclroxy- isophthalic acid is formed together with a much smaller amount of 4-hydroxyisophthalic acid and other substances. w. 0. w. Preparation of Anthraquinone Derivatives Containing Sulphur. EARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 239$62).-When d iazot.ised arninoanthraquinones are treated with thio- carbaruides intermediate compounds are formed which evolve ammonia on treatment with potassium hydroxide and furnish the corresponding mercap tan. Carbain yZtf&iola?zthrapuiizone C,,H,O,*S* CO-NH orange yellow crystals was prepared from a-aminoaithraquinone a,nd thio- carbamide whilst with phenylthiocarbarnide a similar compound was produced.F. M. G. M. [Preparation of Benzoylaminoan thraquinone Derivatives.] FAXBWERKE ,VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 240079).- The preparation of benzoylaminoan tbraquinones and their condensa- tion products has previously been described ; it is now found that more valuable colouring matters are produced by employing nitrobenzoyl chlorides subsequently reducing the nitro-group and combining with another molecule of benzoyl chloride before condensing to form the dye. BenxoyZ-p-anzinobenzoy?- 1 -annzinoant?waquinone yellow crystals m. p. 3 1 5 O is prepared by benzoylating p-aminobenzoyl- 1 -aminoanthra- quinon e in nitro benzene solution ; benxo yl-p-aminobenxoyl-2 -amino- anthraquinone has similar properties.The tinctorial properties of the following final condensation products are tabulated in the original ; p-aminobenzoyl-1-aminoanthraquinone with succinic acid m. p. above 300' with anthraquinonecarbonyl chloride m. p. 280° and with 2-anthraquinonylcarbamyl chloride m. p. above 300'. p-Aminobenzoyl-2-aminoanthraquinone with 2-anthraquinonylcarb- amyl chloride. na-Aminobenzoyl-1-aminoanthraquinone with 2-anthraquinonylcarb- amyl chloride m. p. 285'. VOL. CII i. 23i. 198 ABSTRACTS OF CEEMICAL PAPERS. 3 5-Diaminobenzoyl-1-aminoanthraquinone with 2-anthraquinonyl- Benxoy Zaminoanthraquinonecarboxy - 1 -aminoantlwaquinone has m. p. carbamyl chloride (2 mols.) m. p. 235'. above 300'. F. M. G. 31. Preparation of o-Aminodianthraquinonylamine Types of Compounds.FARBENFABRIKEN VORM. FRIEDR BAYER & Co. (D.R. -P. 240276).-The poduct (annexed formula) dark blue needles was prepared by boiling together l-amino- /\/CO\/\ 4-hydroxyanthraquinone (10 parts) I I 1 1 naphthalene (1 00 parts) anhydrous \ / \ c o / \ p sodium acetate (5 parts) copper NH I powder (0.2 part) and slowly adding /\/"\/\ 2 - bromo - 1 - aminoanthraquinore (5 I I ' parts); when the latter component is '\/""\/ replaced by 2-bromo-1-methylamino- anthraquinone a similar compound is obtained likewise from a-amino-4-hydroxyanthraqninone with 1 3-di- bromo-2-aminoanthraquinone and from a-aminoanthraquinone with 2- bromo-1-aminoanthraquinone. OH F. M. G. M. A Supposed Compound of Camphor and Naphthalene. JOUNIAUX (Bull.SOC. chim. 1912 [iv]. 11 129-132).-When naphthalene containing increasing quantities of camphor is melted and allowed to cool the temperature at which solidification begins falls steadily from 80' to 32-59 a t which point the mixture contains 58 mols. of camphor to 42 mols. of naphthalene ; a similar fall reaching the same point at the same composition occurs when increasing quantities of naphthalene are added to camphor. For every mixture the finishing point of solidification is 32.5'. I n view of these facts Girard's surmosed comnound of these two substances L L * ~ ~ l ~ ~ l ~ ~ ~ l * ~ m. p. 32.6O (J. Pharm. Chim. 1891 [v] 24 lOS) appears to have been a eutectic mixture. T. A. H. Constitution of isoFenchocamphoric Acid and of Some Compounds of the Fenchone Series.OSSIAN ASCHAN [with w. SJOSTROM and A. PETERSON] (Annulen 1912 387 1-85).-The fractions obtained from a very large quantity of pinolene b. p. below 150' (Abstr. 1907 i 630) have been separately oxidised by 8% potassium permanganate at 60-80' whereby carbonic oxalic and dl-camphoric acids are produced. From these facts and from the molecular refractions of the various fractions the author deduces that pinolene contains at least three hydrocarbons (i) r-bornylene b. p. 148-149O m. p. 40-42O which yields &Z-camphoric acid by oxida- tion; (ii) a-pinolene b. p. 144-146" a dicyclic terpene and (iii) p-pinolene (cyclofenchene) C10H16 a tricyclic terpene which probably contains a trimethylene ring on account of its stability towards potassium permanganate.P-Pinolene (cyclofenchene) obtained from the pinolene fractions b. p. 24@-142° and 142-144" by oxidation as above has b. p.ORGANIC CEEMISTRP. i. 199 141&-143.5° Dfo 0.8588 [.ID + 0-28' and n2,0 1.44769 ; its molecular refraction therefore exceeds by aboiit 0.6 the value calculated for a tricyclic terpene a fact which furnishes additional evidence for the presence of a trimethylene ring. By further prolonged oxidation with potassium permanganate P-pinolene yields a very small quantity of isophthalic acid. This may be due to the presence of a little a-pinolene ; its formation however shows that the pinolene hydrocarbons can be converted into benzene derivatives of the meta-series P-Piuolene in dry ether at - 15' forms an unstable crystalline hydrochloride a-Pinolene hydrochloride m.p. 38O has been previously described as pinolene hydrochloride (Eoc. cit.). a-Pinolene probably has the annexed formula; the halogen atom in its hydro- CRI,*CH-CH chloride is attached to the CMe group. I P-Pinolene is unchanged by eight hours' boiling I yMe2 1 with 2076 sulphuric acid but when heated for four CH,*C=-CMe hours with 96% alcohol and 96% sulphuric acid yields a dicyclic ether C,,,Hl7*OEt b. p. 1 97-200° DSo 0.8904 nz 1.45217. Fractions b. p. 144.5-146' and 146-148' respectively of un- oxidised pinolene purified P-pinolene and also isopinene have been separately treated at 60-7'0" with glacial acetic and 50~; sulphuric acids by Bertram and Walbaum's method and the resulting acetates have been hydrolysed. I n each case the main product is dE-isofenchyl alcohol (m.p. 43-44') identified as the phenylurethane m. p. 95-96'. I n the case of the fraction b. p. 146-148' a little isoborneol is obtained (produced probably from the r-bornylene) whilst from the purified P-pinolece a mixture of dl-isofenchyl and db-fenchyl alcohols is formed. By oxidation with potassium permanganate therefore the mixture yields dl-isofenchone and dl-fenchone in addition to the chief product dl-isofenchocsmphoric acid (Wallach Abstr. 1908 i 809). These facts prove that db-isofenchyl alcohol is the chief product of the hydratisation of the mixture of fenchenes (consisting mainly of isopinene) obtained from a- and P-pinolenes. A diagrammatic representation of the transformations is given. A description is given of the preparation in quantity and the purification of dl-isofenchocarnphoric acid.It is best obtained from the pinolene fraction b. p. 140-150" which is converted into iso- fenchyl alcohol as above; the alcohol is then oxidised by alkaline 5% potassium permanganate without warming. The constitution CH,< CH(Co2H)-~Me2 is ascribed to isofencho- CMe(C0,H) CH camphoric acid on the following grounds. The saturated dibasic acid readily forms an anhydride m. p. 94-95'' by distillation or by treatment with acetyl chloride ; the acid therefore has the cis-con- figuration From the anhydride the anilic mid C0,H*C,H,4;CO*NHPh rn p. 191-192' ethyl ester C,H,,(CO,Et) b. p. 267-268' Di0 1.0054 n 1.44626 methyl hydrogen ester M. p. 72-74' and ethyZ hydrogen ester b. p.289-292' (decomp.) are prepared. The distillation of the C,,-,H,,,HCl m. p. 27*5-29' P 2i 200 ABSTRACTS OF CHEMICAL PAPERS. calcium salt C10H1404Ca does not produce a cyclic ketone indicating that the acid is a substituted succinic or glutaric acid. When heated with acetic and hydrochloric acids at 180' for ten hours dl-cis-isofenchocamphoric acid is transformed into the less soluble trans-isomeride m. p. 169-1705' ; hence one of the carboxyl groups is attached directly to a ring carbon atom. When dl-cis-isofencho- camphoric acid is treated with phosphorus pentachloride and tlhe product is brominated as in the case of camphenic acid (Abstr. 1910 i 709) two stereoisomeric a-bromoisofertchocamp~oric acids C H Br(C02H)2 m. p. 208-210' and 1 6 0 s 1 f 2 ° respectively are obtained.(The author's explanation of the production of the two stereoisomerides is given below.) The former acid which is the main product yields an anhydride m. p. Y 7 O and an ethyl ester b. p. 155-156'/5 mm. Dii 1.2425 and by reduction with zinc and acetic acid regenerates &-cis-isofenchocamphoric acid. The introduction of only one bromine atom even when an excess of the halogen is employed indicates that there is only one hydrogen atom in the a-position to a carboxyl group whilst the formation of the two stereoisomerides is regarded as evidence that the carbon atom to which this hydrogen atom is attached forms part of the alicyclic ring. Other facts in harmony with the preceding constitution of isofenchocamphoric acid are the following. When heated with aqueous sodium carbonate or barium hydroxide the a-bromo-acid m.p. 208-2 1 Oo yields isofeencholauronolic acid co2H*C~~e<CH2.CMe,' m. p. 44-45' a-JLydroxyieofencJLocam- phoric acid C,H,,(OH)(CO,H) m. p. 185-1 86' (decornp.) and dehy~roisofenchocamphoric acid CsHI2( CO,H) m. p. 189-1 90' ; methods for the separation of these throe acids are described. The same three acids are produced by the action of aqueous barium hydroxide on the a-bromo-acid m. p. 160-162O. When heated above its m. p. or warmed with 50% sulphuric acid a-hydroxyisnfencho- camphoric acid is converted into the lactonic acid is0 fenchocamphanic CH=C]H acid C7H1,<C(C0 co-- HI>O m. p. 177' which is also produced by \ d I heating the a-bromo-acid m. p. 208-210° with quinoline at 160' (best method) and is re-converted into a-hydroxyisofenchocamphoric acid by boiling 10% potassium hydroxide.a- Hy droxyisofenchocamphoric acid is oxidised by lead dioxide and acetic acid to isofenchocanzplhononic acid m. p. 68-70' which forms a eemicar~~zo~e,*Cl~H1703N~ m. p. 221'. Finally the fusion of a-hydroxyisofenchocamphoric acid with potassium hydroxide at the lowest possible temperature yields formic acid and an acid C,H1,O m. p. 192-193O which is regarded as identical with Michailenko and Jaworski's aayy-tetramethylglutaric acid m. p. 185-189" on account of its stability towards bromine and the forma- tion of an anhydride m. p. 88O and p-toluidino-acid CO,H.C,H,;CO*NH*~,H m. p. 160-161'.ORGANIC CHEMISTRY. i. 201 alcohols by fission of the trimethyl- Although this explanation is equally applicable t o transformations of the maleic-furnsric acid type the author prefers in such cases Wislicenus' explanation because the additive capacity of an ethylenic linking sogreatly exceeds that of the carbony1 group in a carboxyl Constitution of Camphene.KARL AUWERS (Annalen 19 12 group. c. 8. 38'7 240-253).-See this vol. ii 214. The Constituents of Ethereal Oils (Derivatives of Natural Cedrene). FRIEDRICH W. SEMMLER and FELIX RISSE (Ber. 1912 45 355-360. Compare Semmler and Hoffmann Abstr. 1907 i 946).-Natural cedrene has been oxidised on a larger scale than previously by the action of ozone The main neutral products are a ketone C,,H2,0 or C,,H,,O b. p. 120- 1 30°/1 3 mm. (semicarbazone m. p. 218') and the ketonic aldehyde CI5HP1O2 (Zoc.c i t . ) ; the chief constituent of the acidic portion of the oxidation product is cedrene- ketonic acid (Zoc. cit.) b. p. 205-215°/10 mm. (methyl ester b. p. 165-170°/10 mm. D20 1.0509 nD 1.4882 aD - 32.4" at 20'). The ketonic acid is probably a methyl-ketonic acid as it is oxidisable by sodium hypobromite to the dibasic acid cedrenedicccrboxylic acid m. p. 182.5'; the methyl ester (Zoc. cit.) has b. p. 179-183'/13 mm. D20 1.07'78 n 1.48084 aD - 31.6'. C . J. ENRLAAR (Chern. Weekblad 1912,9 68-72. Compare Abstr. 1909 i 690)-A descrip- tion of a method for the preparation of labile hydrocarbons of the D. F. T. Synthesis of an Aliphatic Terpene.i. 202 ABSTRACTS OF CHEMICAL PAPERS olefine series from tertiary alcohols of the formation of a n aliphatic terpene by the dehydration of linalool and of the behaviour of this product on hydrogenation and ozonisation.When linalool is brought into contact with active copper at 130-140' in a rapid current of carbon dioxide the formation of a cyclic hydrocarbon is in large measure obviated the main product being an aliphatic hydrocarbon. The copper was obtained in a very active condition by reducing copper oxide with hydrogen the oxide being prepared by gentle ignition of copper nitrate. The excess of hydrogen was expelled by carbon dioxide a t 170'. The hydrocarbon was separat4ed from the unchanged linalool by repeated vacuum distil- lation filially over sodium. Acraldehyde geraniol and citral were by-products. The same hydrocarbon was obtained by heating linalool with phenyl- carbimide 2CO:NPh + CloH,,O = CO(NHPh) + C,,H + CO,.The yield is best with a slight excess of linalool and a temperature of 150-170° a non-volatile brown oil being obtained as by-product. When the carbimide was in excesg the proportion of this oil was increased by 50%. The hydrocarbon had D15 0*811. The substance was not obtained quite pure but the following physical constants are given D15 0.802 ng 1,470 b. p. 62'/14 mm. hence it is probably myrcene. Reduction with nickel and hydrogen a t 130' and fractionation of the product yielded a decane b. p. 159-160'/760 mm. (uncorr.) D15 0.739 identical with P[-dimethyloctane obtained from ocimene (Abstr. 1908 i 664). Reduction with sodium and alcohol yiolded a hydrocarbon with the odour and b.p. (165-167') of dihydromyrcene. This substance probably has the formula CIOHIS because bromination by Baeyer and Villiger's method yielded a crystalline bromide m. p. 88O which produced no depression in the m. p. of dihydro-ocimene tetra- bromide (compare Rec. trav. chim. 1907 26 167 and 2'7 448). Ozonisation of the terpene by the method previously described (ibid. 1908 27 422) precipitated an explosive oxonide inflamed by concentrated sulyhuric acid and decomposed by water with formation of acetone probably succinic acid and other products not identified. The impure hydrogenation product yielded an oxonide with similar properties. The liquid obtained by the action of water gave the pyrrole reaction distinctly and probably contained acetone peroxide. It is a liquid D15 0.804.A. J. W. Reduction of Sabinene. OTTO WALLACH (Chem. Zentr. 19 1 1 ii 1802 ; from Nachr. K. Ges. Wiss. Gottingen 191O7544).-In the presence of metallic catalysts sabinene takes up 2 atoms of hydrogen with the - - >CH having b. p. CH*CHMe CH2<t?pr-C H. formation of dihydrosabinene 1 156-157' D20 0.8120 Vt'$' - 2'2'. w. P. s. Leaf-Oil of the Washington Cedar (Thujs plicata). ROBERT E. ROSE and CARL LIVINGSTON (J. Amer. Chern. SOL 1912 34 201-202).-As only a superficial examination of the oil obtained from the leaves of Thuja plicata (Brandel Pharm. Rev. 26 248) has hithertoORGANIC CHEMISTRY. i. 203 been made [compare however Elasdale Abstr. 1907 i 6301 a detailed study has now been carried out. On distillation with steam the leaves and twigs yielded about 1% of light yellow oil which had a cedar-like odour Dm 0.913 n? 1.4552 [a] - 4.77O ; acid number 0.518 ; ester number 2-25 ; saponification number 2.8 and acetylation number 8.8.The product was free from phenols soluble in all proportions in 70% alcohol and about 55% of it boiled at 100-110°/40 mm. The oil contains tanacetone S0-55% pinene 3-5% tanacetyl acetate 1-2% and tnnacetyl alcohol 1-3%. E. G The Chemical Degradation of Chitin. Huao BRACH (Biochem. Zeitsch. 1912,38,468-491).-A description is given of the preparation of the material from Nephrops norvegicus. The analyses showed that the substance had a composition corresponding with the formula C32H54021N4. The estimation of the acetyl groups by a modification of Wenzel's method which is described by the author showed that for each nitrogen in the atom there exists an acetyl group.The results indicate that the simplest formula for chitin is one made up of a complex of four acetylglucosamine groups. Lenk's chitosan appears to be formed from chitin by the scission of half the acetyl groups. By the action of nitrous acid the whole of the nitrogen in the molecule can be eliminated a fact which the author shows does not contradict the assumption of the presence of acetylamino-groups. S. B. S. Constitution of Rhein. OTTO A. OESTERLE (Chem. Zentr. 1912 i 142-143 ; from Schweiz. Woch. Chem. Pharm. 1911 49 661-665). -Contrary to the view of the author and Riat (Abstr. 1909 i 946) that aloe-emodin and its most nearly related derivatives are derived from 1 8-dihydroxyanthraquinone (chrysazin) Robinson and Simonsen (Trans.1909 95 1085) regard 1 6-dihydroxyanthra- quinone (isozhrysazin) as the parent substance of rhein. The author therefore has converted rhein through rhein chloride yellow needles and the amide dark red needles into an aminodihydroxy- anthraquinone C,,H,O,N m. p. 255' or 25S0 red needles from which by elimination of the amino-group impure 1 8-dihpdroxyanthra- quinone m. p. 182-183° instead of 191-192' (acetate m. p. 232'). has been obtained. c. s. Phylloxanthin. LEON MARCHLEWSKI (Ber. 191 2 45 24-25).- The phylloxanthin described by Schunck (Abstr. 1885 1241) is shown to be identical with allochlorophyllan (Marchlewski and Marszatek Abstr. 191 1 i 735). Phylloxanthin yields 30.02% of phytol instead of 31.8%.On prolonged exposure to concentrated hydrochloric acid phylloxanthin is converted into basic products including a substance soluble in 20% hydrochloric acid. A more recent preparation of phylloxanthin gave a solid substance instead of phytol on hydrolysis. E. F. A. Tannin. VIII. MAXIMILIAN NIERENSTEIN (Annalen 19 12 386 318-332. Compare Abstr. 1910 i 265).-Purpurotannin thei. 204 ABSTRACTS OF CHEMICAL PAPERS. amorphous red oxidation product of penta-acetyl-leucotannin (Abstr. 1909 i 402) has the composition C,,H,O forms a puinoline salt C,,H,0,,2C,NH7 dark red needles and dissolves unchanged in boiling 2N-potassium hydroxide. It forms a tetra-acetate m. p. 324-3.27" (decornp.) tetrabenxoate m. p. 279-281' C0,H C0,H (decornp.) and tetramethyl ether C1,H,O,(O~~e),,H,O ene not naphthalene as stated (Zoc.cit.) by m. p. 242-244" (decomp.) and yields diphenyl- HO 0 OH distillation with zinc dust. It is shown to be 1 2 7 ; 8 - tetrahydroxydiphenyleneoxide - 4 5 - dicnrboxylic acid (annexed formula). When heated with piperidine (but not with quinoliue) a t 180° i t yields 1 2 7 8-tetrtchyh.oxy- diphenylene oxide CI2HSO5 red needles m. p. 334-338" (decornp.) (tetra-acetate m. p 247-251") whilst by reduction with hydriodic acid and phosphorus at 180" it is converted into diphenylene oxide. A course of formation of purpurotannin from leucotannin is suggested. The cause of its colour will be discussed later ; apparently i t is connected with the presence of hydroxyl groups in the peri- position to the oxygen of the furan ring.c. s. u Luteo-acid " (A Correction). MAXIMILIAN NIERENSTEIN (Ber. 1912 46 365).-l'he analytical results for the composition of " luteo- acid" (pentahydroxydiphenylmethylolidecarboxylic acid) (Abstr. 1908 i 897 ; 1909 i 174 ; 1910 i 265 389) were low in the percentage of carbon ; as the more carefully dried substance gives results agreeing well with the formula C,,H,O i t is proEable that the earlier discrepancies were due to occluded solvent,. D. F. T. Decomposition of Alkylidenehydrazines. Conversion of Furfuraldehyde into 2-Methylfuran. NICOLAI RI. KJJNER (J. Buss. Phys. Chem. SOC. 1911 43 1563-1565).-When heated in presence of a small quantity of potassium hydroxide fui furylidene- hjdrazino decomposes giving nitrogen ar;d 2-methylfuran a colourless liquid b.p. 64"/757 mm. D;'' 09159 n 1.4344. The constants given for this compound by Atterberg (Abstr. 1880 663) and by Harries (Abstr. 1898 i 232) are inaccurate doubtless on account of impure products being examined. T. H. P. Coumerandione the Oxygen Analogue of Isatin. KARL FRIES and W. PFAFFENDORF (Bey. 1912 45 154-162. Compare Abstr. 1910 i 186; also Stoermer ibid. 1909 i 174 and following aEstract,).-Coumaran-l 2-dioae C,H,<$>CO is readily prepared by heating a solution of o-hydroxpphenylglyoxylic acid in light petroleum with phosphoric oxide or by distilling the acid under diminished pressure. I t crystallises in large yellow prismatic plates m. p. l34" b. p. 142'/17 mm. and dissolves in concentrated sulphuric acid yielding a yellowish-red solution which gradually becomes colourless owing to the loss of carbon monoxide arid conversion of the diketone into salicylic acid.ORGANIC CHEMISTRY.i. 205 With o-phenylenediamine it yields 2-hydroxy-3-hydroxyphenyl- quinoxaline (Marchlewski and Sosnoweki Abstr. 1901 i 415). On exposure to air it takes up water with the formation of o-hydroxy- phenylglyoxylic acid or its hydrate m. p. 43'. When heated at 220' under ordinary pressure it loses carbon monoxide yielding a ruby-red glassy mass which sinters at 150° forms a transparent viscid liquid at 200° and finally becomes mobile at 240'. The latter substance is hydrolysed by alkalis i n alcoholic solution to salicylic acid and gives a colloidal solution in chloroform. It probably consists of a polymeric salicylide which however is different from the polymerides described previously.Ethyl o-hydroxyphenylglyoxylnte ClpH1004 prepared by boiling coumarandione in alcoholic solution IS a yellow 011y liqnid which solidifies in a freezing mixture m. p. 15'. It readily loses alcohol yielding the original ketone. Cowmcwan - 1 2 - dione-2-phenyZhyd~ccxone O<!bEf>C:N*NHPh obtained from its components in glacial acetic acid solution crystallises in lustrous yellow plates m. p. 185' and is hydrolysed by alkalis in alcoholic solution to the phenylhydrazone of o-hydroxyphenylglyoxylic acid C,,H,,O,N,. This crystallises in light yellow needles m. p. 148' (decornp.) and is also obtained by heating o-hydroxyphenyl- glyoxylic acid with phenylhydrazine in aqueous solution.It readily loses water yielding coumarandione-2-phenylhydrazone. The a i d of o-hydroxyphenylglyoxylic acid C,,H,,O,N prepared by heating coumnrandione with aniline in benzene or alcoholic solution crystallises in pale yellow plates m. p. 102" and shows no tendency to form a lactone ; the acetyl derivative has rn. p. 138'. The p-dimethyZaminonni2 OH*C,H,:C( :N*C,H,*NAfe,)*CO,H crys- tallises in dark red needles of a metallic lustre rn. p. 153'; the rnono- sodium salt and monohydrochloride crystallising in yellow prisms are mentioned. On treatment with phenylhydrazine the p-dimethyl- aniline residue is eliminated Kith the formation of the phenylhydr- azone of o-hydroxyphenylglyoxylic acid. With o-phenylenediamine i t yields 2 -by d roxy- 3-h ydrox y pheny lquin oxaline.When hydrolysed with aqueous alcoholic sodium hydroxide and the resulting solution neutralised with acetic acid coumaran-1 2-dione-l- p-dimethylarninoanil (Fries and Hasselbach Abstr. 1911 i 151) is converted into o - hydroxyphenylylyoxylo - p - dimeth ylaminoanilide OH*C6H4*CO*CO*NH-C/,H,*NMe which however could not be obtained in a pure condition and was therefore characterised by means of its benxoy2 derivat'ive C,,H,,O,N stout red prisms m. p. 138'. With excess of bromine in glacial acetic acid solution coumaran- dione yields 3 5-dibromo-2-hydroxyphenylglyoxylic acid which has m. p. 148' (decomp.) (compare Abstr. 1910 i 332) and forms a hydrate C,H,0,Br2,H20 crystallising in slender pale yellow needles m. p. 110'. l-Bromo-2-cournaranone C,H,O,Br prismatic needles m.p. 8 7 O and 1 :l-dibromo-2-coumar~none C,H,02 Br pale yellow needles m. p. 1 4 2 O are obtained by brominating 2-coumarmone in carbon tetra-i. 206 ABSTRACTS OF CHEMICAL PAPERS chloride solution. When warmed with sulphuric acid the dibromo- compound is converted into coumarandione and finally into salicylic acid. On treatment with o-phenylenediamine it yields coumaro- phenazine. 1 l-l)ichZoro-2-coumaranone prepared by chlorinating 2-coumaranone in glacial acetic acid solution forms white prismatic needles m. p. 70'. Coumarandione the Analogue of Isatin in the Coumarone Series. A Correction. RICHARD STOERMER (Ber. 1912 45 162-1 63. Compare preceding abstract).-The compound described previously (Abstr. 1909 i 174) as the hydrate of coumarandione is now found t o be the acetyl derivative of 1-oximino-2-coumaranone F.B. c,H,<_COCI>C:N*OA~. It is shown that the substance is formed by the action of acetic acid on aci-nitrocoumaranone and not by the oxidation of '' leuco- oxindigo," as previously supposed. With respect to the mechanism of the reaction the author imagines that an intermediate compound of the composition c,H,<-\~>cH*No(oH)~oA~ is first produced by the combination of acetic acid and aci-nitro- coumaranone and that t h i s is subsequently reduced by the nitrous acid formed by the spantnneous decomposition of the aci-nitro- compound loss of 1 mol. of water taking place simultaneously. F. B. Constitution of the Desaurins. C. KELBER and A. SCHWARZ (Ber. 1912 45 137-147).-By the interaction of carbon disulphide potassium hydroxide and ketones of the type R*CO*CH,*R Meyer (Abstr.1888 484; 1890 1144 ; 1892 340 1127) obtained a number of desaurins t o which he ascribed the constitution R-CO~CR:C<~>C:CR*CO~R (R a aryl). This forniula has now been confirmed by the synthesis of similarly constituted desaurins (11) by the removal of hydrogen sulphide from 2 mols. of the aryl PP-dithiolvinyl ketones of the formula I (I) R*CO*CH:C(SH) = (11) R*CO*CH:C<E>C:CH*COR + H2S. S A number of desaurins of the type R*CO*CMe:C<S>C CMe-COR have also been prepared by heating aryl ethyl ketones R*COEt with carbon disulphide and finely-powdered potassium hydroxide. The compound COPh*CH:C:S,:C:CH*COPh is obtained in small yield by heating phenyl PP-ditbiolvinyl ketone (Kelber Abstr.1910 i 390) at 100'. It is also produced together with carbon oxysulphide benzophenone and benzoyl sulphide by rapidly heating the dibenzoyl derivative of the ketone (Zoc. cit.) either alone a t 210° or in solvents of high b. p. such as ethyl benzoate or acetophenone. It crystal- lises from ethylene dibromide in yellow rectangular prisms m.. p. 212-214O (decornp.) and dissolves in strong sulphuric acid yielding orange-red solutions having an intense green fluorescence.ORGANIC CHEMISTRY. i. 207 The lead salt of phenyl PP-dithiolvinyl ketone C,H,OS,Pb is a heavy reddish-brown powder ; the mei*curic salt Cl,H,,OI,S,Hg is soluble in organic solvents and crystallises from toluene in orange needles which have m. p. 185-190' (decomp.) with previous darken- ing at 130-140'.When heated in solvents of high b. p. both the lead and mercuric salts are decomposed with the formation of metallic sulphide and the above-mentioned desaurin. The monothiourethane COPh*C,H,S,*CO=NHPh obtained from phenyl PP-dithiolvinyl ketone and phenylthiocarbimide in benzene solution crystallises in slender needles m. p. 94' (decomp.) and when carefully heated gives a small yield of the corresponding desaurin. The compound (C,H,S*CO*CH:U),S may be prepared from a-thienyl PP-dithiolvinyl ketone (Abstr. 191 I i 740) by methods similar to those employed in the case of the preceding desaurin. It crystallises in moss-like aggregates of slender yellow needles which decompose at 260' with previous*darkening and yields with sulphuric acid deep red solutions having a green fluorescence.The mercuric salt of a-thienyl PP-dithiolvinyl ketone C,H,OS,Hg is obtained from mercuric chloride and the. ketone in alcoholic solution. The thiourethane C,H,S*CO*C,H,S,*CO*NHPh prepared from the ketone and phenylthiocarbimide decomposes at 80'. The desaurin from p-tolyl PP-dithiolvinyl ketone (Zoc. cit.) crystallises in yellow rectangular prisms. The cornpouud COPh*CMe:C:S,:C:CMe*COPh prepared by heating phenyl ethyl ketone with carbon disulphide and potassium hydroxide crystallises in lustrous golden-yellow leaflets m. p. 225'; the compound (C6H,Me*CO*CMe:C),S from p-(?)tolyl ethyl ketone in strongly refractive yellow needles m. p. 263-265O. (C,H,S*CO*CMe:C),S from a-thienyl ethyl ketone forms yellow needles m.p. 258-260'; the cornpound (CloH,*CO*CMe:C),S from 8-naphthyl ethyl ketone crystallises in yellow leaflets which have m. p. 264' and decompose at 268-269'. F. B. The compound The Simplest Thiopyronine. FRIEDRICH KEHRMANN and L. LOWY (Bey. 1912 45 290-292).-The chloride of the simplest thiopyronine 3 6-diaminothioxanthinium chlovide (annexed formula) is obtained in small yield by the addition of a glacial acetic acid solution of di-p-acetyl- /\/\/\ aminodiphenylmethane to a solution of I I INH flowers of sulphur in fuming sulphuric acid HH'\/N/\/ at a temperature not exceeding lo' and subsequent hydrolysis of the resulting 3 6- diacetylaminothioxanthinium szclphate (not isolated). It crystallises from alcohol in metallic green needles or prisms which yield scarlet-red solutions having a greenish-yellow fluorescence.The carbonate acetate iodide diclwomate and also the nitrate cryetallieing in scarlet- red needles are described ; the platinichloride (C,,H,,N,SCl),P tCl was analysed. Elimination of one of the amino-groups from the preceding chloride CH S*Cli. 208 ABSTRACTS OF CHEMICAL PAPERS. by successive treatment with nitrous acid (1 mol.) and alcohol results in the formation of apothiopyronine (3-uminothioxccnthinizcm) chloride NH *U H < >C,H which was converted into a red crystalline nitrute and pZatinichZoride (C,,H,,NSCl),PtCl,. [Preparation of Ketonaphthathiophen.] KALLE & Co. (D. R. - P. 23 9 0 9 3) .- Derivatives of o-carboxy n apht hyl thiolacetic acids yield valuable dyes and the following series of compounds have been prepared a-Naphtbylamine-2-sulphonic acid is converted by diazotisa- tion and subsequent treatment with copper sulphate and potassium cyanide into sodium l-cyanonuphtl~alene-2-suZphonate leaflets which furnishes an acid chloride long needles or prisms m.p. 143’; this when reduced with zinc dust in sulphuric acid solution and treated with chloroacetic acid yields a mixture of 1-cyunonupl~thuZene-2-thioZacetic acid and 1 -carboxynaphthaZene-2-thioZacetic acid which can be separated by fractional crystallisation from water when the acid is obtained in long coloi~rless ‘7’S-\CH*C02H needles m. p. 93’ and (when anhydrous) Ketonaphth thiophencurbox y Zic acid (an- nexed formula) colourless aggregates is obtained by the fusion of the foregoing mixture with sodium hydroxide and is converted by treatment with mineral acids into naphthoxydhiophen glistening grey crystals m.p. 118-1 19’. KALLE & Co. (D.R.-P. 2 3991 ti).-When indoxyl oxythionaphthens or compounds of the same type (2 mols.) are condensed with a dialdehyde or diketone (1 rnol.) substances are obtained having the general formula CH 2 6 3 SCl F. B. 12 7-128”. F. M. G. M. [Preparation of Indigoid Compounds.] c6 H,<go>C CR’ R*CR” C<g!>C,H4 where R is a hydrocarbon ; R’ R,” hydrogen or hydrocarbon residues ; X and Y alike or different atoms or groups such as sulphur oxygen or the imino-group. The yellow crystalline compound c,H~<~~>c CH C,R,. CH C<-~~>C,H 4 was prepared from ketothionaphthen (2 mols.) and terephthalnldehyde (1 mol.) whilst the analogous compound obtained from the bisulphite derivative of glyoxal (1 mol.) forms brownish-yellow needles.The ketothionaphthens can be rsplaced by indoxyls in these reactions. F. M. G. M. [Preparation of ‘‘ Dihalogendimethylthioindigos.”] KALLE & Co. (D.R.-P. 239094).-The symmetrical ‘‘ dihalogendimethylthio- indigos ” of the annexed general formula (where R is a halogen atom and R’ a R / \ A /\/‘R methyl group or vice versa) are of 1 1 ’:’ I 1 technical value and in this connexion \/\/ ‘\/\( the following compounds have been S S R’ prepared.ORGANIC CHEMISTRY. i. 209 5-Cl~loro-3-anbino-o-tolzcic acid needles (prepared by the reduction of the corresponding chloronitrotoluic acid) when diazotised xantho- genated and treated tvit,h chloroacetic acid yields 5-cldoropheizyl-3- methyl -2-carboxyplie~zyIthio2cccetic ucid colourless needles which on fusion with sodium hydroxide furnishes 6-chZoro-3-h~d~oxy-4-methyl-( 1 )-thio- naphthen-o-carboxylic acid and subsequently on treatment with mineral acid 6-chloro-3-hydroxy-4-methyZ-( 1)-thionaphthen glistening colourless needles.The reaction is stated to be applicable to other halogenated nitro- toluic acids. F. M. G. M. [Preparation of " Naphthioindigo."] KALLE & CO. (D.R.-P. 2401 18).-" Naphthioindigo " (formula I) is prepared as follows S S 2-amino-3-naphthoic acid is diazotised and converted successively into 2-thion~pl~thol-3-carboxyEic mid a yellow powder m. p. 275-276' and 3-carboxynaphthyl-2-tl~iolacetic acid (11) a colourless crystalline powder m. p.203'; this wheu treated with alkali or acetic anhydride yields 3-keto-(l)-thioanthren and by subsequent oxidation with potassium ferricyanide the foregoing '' naphthioindigo." F. M. G. M. Bromo-derivatives of the Alkaloids of Peganum harmala and their Basic Uerivatives. V. HASENFRATZ (Compt. rend 19 12 154 225-217. Compare Fischer Abstr. 1889 730; lS9S i 160). -On treating harmaline harmine npoharmine and methylupoharmine with bromine in acetic acid the hydrobromides of the corresponding monobromo-derivatives are ob tained. BromoZmrrlrmZi.ne Cl3HI20N2Br crystallises in colourless slender needles in. p. 195' ; the ?hydro- cldoride and pbihichloride are yellow. I n the case of har'mine two isomeric compounds are formed and may be separated by heating the hydrobromides at 50° bvomohurmine hydrobrocmicle alone fusing a t this temperature.Bromoha~mine C,,H,,ON,Br occurs in orthorhombic prisms m. p. 275'; the salts crystallise from alcohol but form jellies with water. isoBromoharrnine crystallises in long needles m. p. 203' and its salts crystallise from water ; the pkati?ddoride is orange-red. Bvornoapoharminc C8H1N2B1. crystallises in long needles m. p. 229O and bromoniethylapoharnzine C9H9N2Br in needles IU. p. 196'. On brominating harmine in presence of sulphuric acid arid sus- pending the product Pischer's supposed tetrabromide in hot dilute alcohol slender needles of dibronzoharmine sizonohydi.obrornide are obtained ; when treated with ammonia this gives dibromohurmine C!,H,,ON,Br m.p. 209'. Fischer's compound appears to be the ciahydrobromide of this base. w. 0. w. Preparation of a Compound of Codeine with Diethyl- barbituric Acid. KNOLL & Co. (D.R.-P. 239313).-Codeinei. 210 ABSTRACTS OF CHEMICAL PAPERS. diethylbarbiturate . prisms m. p. 8 5 O is readily prepared by mixing molecular proportions of codeine and diethylbarbituric acid (veronal) in aqueous or alcoholic solution or by intimately mixing codeine hydrochloride with sodium diethylbarbiturate in the absence of solvents. F. M. G. M. Degradation of Sparteine. Formation of a Hydrocarbon Sparteilene. CHARLES MOUREU and AMAND VALEUR (Comnpt. rend. 1912,154 161-163. Compare Abstr. 1908 i 43 44 563).-When methylhemisparteine is treated with methyl iodide the product has the composition C,,H,,N,Me,I but appears to consist of a mixture of a t least two isomerides.On treatment with silver oxide it gives a quaternary ammonium base which on heating in a vacuum yields inactive dimethyZhemispayteiZene C15H21NMe2 b. p. 201-202°/27.5 mm. This substance forms a methiodide and a quaternary hydroxide ; the latter decomposes at 75' in a vacuum giving trimethylamine and sparteilene C,,H,,. The new hydrocarbon is a colourless odourless optically inactive liquid b. p. 157-159'/1S mm. showing a molecular refraction corresponding with the existence of six ethylenic linkings. Its production with trimethylamine taken in conjunction with the formation of methylsparteilene and trimethylamine from dimethyl- sparteine is sufficient to establish the symmetrical character of the sparteine molecule.Oxidation of sparteilene by means of potassium permanganate Ieads to the formation of an acid C,,H,,O m. p. 300-305° on the Maquenne block. w. 0. w. Strychnos Alkaloids. XIV. Derivatives and Decomposition Products of Brucinolon e. Decomposition of Dihydrobrucinonio Acid into isoBrucinolone and Glycollic Acid. HERMANN LEUCHS and J. F. RREWSTER (Ber. 1912 45 201-221. Compare Abstr. 1908 1,563 ; 1909,1,253 954).-For the preparation of brucinolone brucine dissolved in acetone was oxidised by potassium permanganate whereby brucinonic and dihydrobrucinonic acids were obtained The two acids are difficult to separate completely. Brucinolic acid was obtained by reduction of brucinonic acid (containing some dihgdro- brucinvnic acid).This latteracid appears to be formed even when the most carefully purified keto-acid is reduced and the authors have come to the conclusion that it is stereoisomeric with brucinolic acid since they were also able t o show that the two acids are similarly affected by sodium hydroxide. Since dihydrobrucinonic acid is formed by the direct oxidation of brucine it follows that the latter must contain a secondary alcoholic group. For the conversion of brucinolic acid into brucinolone the authors recommend the use of normal sodium hydroxide ( l a mols. instead of 14 mols. previously employed). The m. p. of brucinolone is now given as about 270° and [a] -34.79 The latter value is somewhat dependent on concentration and source of light used. By means of ice-cold nitric acid (D lea) brucinolone was converted into ~zik~obisapomethyZdeh~drobrzccinoZorne which forms orange-coloured leaflets.Bisapomethylbrucinolone (bisdemethylbrucinolone of Abstr. 1909,ORGANIC CHEMISTRY. i. 211 i 954) was converted into the triacetate by treatment with acetic anhydride and sodium acetate. It crystallises in colourless leaflets m. p. 260-261'. I n brucinolone hydrate I. (in which the ZN-GO- of brucinolone is supposed to have been transformed into =NH H0,C-) the presence of the imino-group bas been proved by the regeneration of brucinolone by the action of heat on the hydrate I. and by the formation of a derivutiue when treated with phenylcarbimide. The latter is a non- crystallisable amorphous white powder m. p. 192' (decomp.) after previous softening. The presence of the carboxyl group is shown by thezisolation of the hydrochlorides of the methyl ester m.p. 189-190' (decomp.) and of the ethyl ester m. p. 181' (decornp.). The isolation of a by-product CzlH,,O6N during the action of sodium hydroxide on brucinolic acid has been previously described (Abstr. 1909 i 954). This substance when heated with 5~V-hydro- chloric acid yields a hydrochloride which is completely melted at 255' after previous gas evolution. The free base obtained from this which has been named brucinolone hydrate II. separates from water with vary- ing amounts of water of crystallisation. It has m. p. 240' (decomp.) after softening at 190'. It differs from the hydrate I. in possessing less tendency t o lose water. When the by-product C21H2406N2 is heated with sodium hydroxide brucinolone is formed.I n order to gain further insight into t h e oxidation products of brucine brucinolone acetate (m. p. 253-254') was prepared by heating brucinolone with acetic anhydride and sodium acetate. This was oxidised in acetone solution by potassium permanganate. I n this manner an acid C2,H,,0,N21 was isolated which gave a brownish-red coloration with alcoholic ferric chloride and thus appears to be a keto- acid. When heated i t softens at 120° melts at about 160' (decomp.) then solidifies becoming yellow at 240° and melting again at about 275". When heated during ten minutes at 160-18U0 i t evolves carbon dioxide and leaves a neutral substance C20H2407N2 which has m. p. about 281'. During the oxidation? a neutralproduct C,,H,,O,N (m.p. about 312') is also formed. By the action of normal sodium hydroxide (18 mols.) on dihydro- brucinonic acid glycollic acid was obtained together with isobmcinolone. The latter forms yellow crystals my p. 308' (decomp.) and has [a32 + 26.9' in glacial acetic acid solution. H. W. Action of Acetic Anhydride on Some Benzylideneanthr- anilic Acids. JOHN B. EKELEY and PAUL M. DEAN (J. Amer. Chem. Xoc. 1912 34 161-164).-The products of the condensation of anthranilic acid with aromatic aldehydes (compare Wolf Abstr. 191 1 i 735) react with acetic anhydride to form a series of oxazines which are crystalline very stable and usually colourless. Benzylideneanthranilic acid m. p. l2fi0 yields 1 -keto-d-acetyZ-3-phen& 'O-? NAc*CHPh' m.p. lOS' which when dihydro-2 ; 4-benxoxaxine C6H,< heated with hydrochloric acid is decomposed into benzaldehyde and acetylanthranilic acid. m-Nitrobenzylideneanthranilic acid m. p. 202O and p-nitrobenzylideneanthranilic acid m. p. 164' yield 1-hto-i. 212 ABSTRACTS OF CHEMICAL PAPERS. 4-acetyl-3-m- and -p-nitvophenyldihydr0-2 4-benzoxccxines m. p. 192' and 199' respectively. When p-hydroxybenzylideneanthranilic acid m. p. 207O is heated with acetic anhydride l-keto-4-acetyl-3-p-acetoxypT~enyl- dihydro-2 4-benxoxcbzine m. p. l48' is produced. Salicylidene- anthranilic acid m. p. 195' similarly gives l-keto-4-acetyl-3-o-acetoxy- phenyldihydro-2 4-benzoxaxine m. p. I. 62'. Vanillylideneanthranilic acid m. p. 170° crystallises in lemon-yellow needles and when heated with acetic anhydride yields l-keto-4-acetyl-3-p-7ydroxy-m-methoxy- phenyldi?hydro-2 4-benxoxuxine m.p. 184O which forms pale straw- coloured needles. E. G. Thiazines. RICHARD MOHLAU HEINRICH BEYSCHLAG and H. KOHRES (Ber. 1912 45 131-137. Compare Abstr. 1910 i 337)- The authors have repeated the work of Kehrmann and Steinberg (Abstr. 1911 i 1034) and agree with them that the dinitrophen- thiazine obtained by the interaction of picryl chloride and o-amino- thiophenol has the constitution originally ascribed to i t by Kehrmann and Schild (Abrjtr. 1900 i 61). The synthesis of the isomeric 2 4-dinitrophenthiazine is also described. Di-o-aminodiphenyl disulphide is best prepared by reducing di-o-nitro- diphenyl disulphide (Blanksma Abstr. 1901 i 460) with hydrazine hydrate in alcoholic solution The dzbenxoyl derivative (NHBz*C6H4),S2 crystallises in pale yellow needles m.p. 141° and is reduced by aqueous sodium sulphide to o-benzoylaminophenyl mercuptan which reacts with picryl chloride in the presence of sodium acetate yielding trinitrophenyl o-benxoylamino- phenyl sdphide NHBz*C6H,*S*C,H,(N0,),. The latter compound crystallises in yellow prisms m. p. 169O and when boiled with sodium hydroxide in aqueous alcoholic solution is converted into 2 4-diyzitro- phenthiuxine (annexed formula) which crys tall ises in almost black lustrous prisms m p. 218O /\/\/\NO (appearing reddish-brown by transmitted light) I 1 1 1 dissolves in alcoholic sodium hydroxide yielding \/\/\/ bluish-violet solutions and on reduction with stannous chloride and hydrochloric acid is converted into 2 4-diamino~her~thi~xine stannichloride NH This forms brownish-yellow needles and is oxidised by ferric chloride in alcoholic solution in the presence of hydrochloric acid to 2 4-di- - _ aminophenazthionium chloride c6 H,<:>C,H,( NH,),.The ferri- chlovide C,2H,,N,SC1,Fe,H,0 forms greenish-black microscopic crys- tals which lose their water of crystallisation at 110'; the p l a t h i - chlo~ide chromate caybonate and the thiazonium base itself are briefly mentioned. Kehrmann and Steinberg's 1 3-dinitrophenthiazine has m. p. 187'. F. B. Decomposition of Alkylidenehydrazines. NICOLAI &I. EIJNER (J. Buss. Phys. Chem. Soc. 1911 43 1554-1562).-The autlhor hasORGANIC CHEMISTRY. i.213 been able to pass from carone through carylidenehydrazine t o carane (compare Abstr. 191 1 i lOZS) the hydrocarbon thus obtained being structurally identical with that prepared from pulegone but exhibiting a laevo- instead of a dextro-rotation. the action of hydrazine hydrate on caroie is a &ous liquid b. p. 131°/20 mm. Di0 0.9683 n 1.5082 [a] + 375.7-378.8O (absolute alcohol). Its thioureide NHPh*CS*NH* N:CloH16 forms hexagonal plates m. p. 100-101'. Hydrolysis of carylidenehydrazine by either boiling dilute sulphuric acid or hydrochloric acid at the ordinary temperature yields a product showing all the physical properties of carvenone with the exception of a slight laevo-rotation apparently due to admixture of a small quantity of an intermediate compound in the hydrolysis.I-Camme C10H18 has b. p. 169-169*5'/761 mm. Dto 0.8411 n 1*4,569 [a] -47.06' is very stable towards permanganate and combines with generation of heat with halogen hydrslcids and bromine. The bromo-derivative CloHl,Br obtained by the action of hydrobromic acid has Dto 1.1774 nD 1.4910 [a] - 6-40' and yields A8(g)-m-merithene and a"@)-m-menthene in the same way as d-carane (ZOC. cit.). 2'. H. P. Refutation of Bulow's Views Concerning Pgrazoline- carboxylic Acids. EDUARD BUCHNER (Ber. 1912 45 117-lZl).- Many arguments are advanced to disprove Bulow's view (this vol. i 134) that a niixed azine CHX:N*N:CX-CH,X not a pgrazoline cx-?Hx is produced by the action of ethyl diazo- NH*CHX' derivative N< acetate on an unsaturated ester of the type CHXICHX (X = C0,Et).c. s. Derivatives and Decomposition Products of Methyl Methoxy- benzoylacetates. ANDRB WAHL and C. SILBERZWEIG (Bull. Soc. Chim. 1912 [iv] 11 61-69).-The methoxybenzoylacetates are convertible into ap-diketonic esters and as these may react with various reagents giving compounds identical with those obtainable from the initial P-ketonic esters the following compounds have been prepared and characterised so that they may be readily identified. Methy I a-oximino-o-methoxp benxoylacetate OMe*C',H,-CO-C(NOH)* CO,Me m. p. 146-147" produced by the action of nitrous P-ketonic ester in acetic acid crystallises from ether. ester reacts with phenylhydrazine to form Tahara's - - - N=~*C,H,-OMe methoxyphenyl-5-pyrazolone PhN< CO*CH 9 acid on the The original 1 -phenyl-3-0- p.133-1 34O yellow needles and with p-nitrophenylhydiazine t o form 1 -p-mitro- phenyZ-3-o-methoxyphenyZ-5-pyraxoZone m. p. 2 17-2 1 BO brown needles. OMe*C,H,-CO*C(:N*NHPh)*CO,Me Methy I a-phenylhydraxornoazo-o-methoxgbenzo ylacetate VOL. CII. i. 4i. 214 ABSTRACTS OF CHEMICAL PAPERS. m. p. 138-139' obtained by the action of benzenediazonium chloride on the ester in the cold forms yellow crystals from alcohol and reacts with phen ylhydrazine t o form 4-phen ylh ydruxono- 1 -phenyl-3-o-methoxy- phenyl-5-pyraxolone m. p. I39' orange crystals and with p-nitrophenyl- hydrazine to form 4-phenylhydrazono-I-p-nitro;~henyl-3-o-methoxyphe~yZ- 5-pyrazolone m. p. 200' red crystals from pyridine. Methyl p-nitropl~enylhydruxono-o.metl~oxybenxoylucetute m.p. 1 TO" obtained by the action of the sodium derivative of p-nitrophenylnitroso- amine on the P-ketonic ester forms yellow crystals and reacts with phenylhydrazine to give 4-p-nitrophenylhydrazono-l-phenyl-3-o-methoxy- phenyl-5-pyrazolone m. p. 267' red crystals. Methyl oximino-rn-wthoxybcnxoylacetute m. p. 115-1 16" forms colourless needles from ether and light petroleum and on treatment with phen yl h y drazine gives 4-o~imino- 1 -phenyl-3 -m-rnethoxyphen yl-5- pyruzolone m. p. 1 5 7 O which forms red crystals from acetic acid. Methyl phenylhydruzono-m-methoxybenzoykccetute m. p. 72-73" forms yellow crystals; the free acid m. p. 118-120° forms yellow needles. Methyl p-nitrophenylhydrazono-m-methoxybenzoylacetate m. p. 155-156" crystallises in yellow needles.1-Phenyl-3-m-methoxy- phenyl-5-pyraxolone m. p. 124O forms pale yellow crystals. 4-Phenyl- hydrazono-1 -pheny1-3-m-rr~ethoxyp?~enyl-5-pyrazo20ne7 m. p. 137' and the corresponding 4-p-nitrophenylhydruzone m. p. 235" both form red crystals. Methyl oxirninoanisoylacetate m. p. 1544 forms colourless crystals from boiling methyl alcohol. Methyl phenylhydraxonounisoylucetate m. p. 121-1 22" forms orange crystals ; thefree acid m. p. 149-150° is yellow. The ucetyl deriv- ative of the ester has m. p. 116' crystallises in colourless needles and on reduction furnishes some acetanilide whence it is believed to have the constitution OMe*C6H,*CO*C( :N*NPhAc)*CO,Me (compare Auwers Abstr. 1909 i 222). Methyl p-nitrophenylhyd~uzonoanisoylucetate m. p. 175' forms yellow crystals; the free acid m.p. 236-238' is also yellow but dissolves in alkalis with an intense red colour. l-PhenyZ-3-p-rnethoxyphenyl-5-pyraxolone has m. p. 137-138' ; the 4-0xirnino-derivative~ m. p. 244" forms red crystals. p-Nitrop?Aenyl- 3 ~p-methoxyphenyZ-5-pyraxolone m. p. 204-205' is brown. 4-Phenyl- hydruzono-l -phenyl-3-p-methoxyphenyl-5-pyraxolone m. p. 177" is red ; the corresponding p-nitrophenylhydrazone 111. p. 2 13-2 14' separates from acetic acid in violet crystals and the isomeric 4-phenylhydraxono- 1-p-nitrophenyL3-pmethoxyphenyl-5-p~ruzolone m. p. 239O is red. The methoxybenzoylacetic esters are hydrolysed by boiling with 20% sulphuric acid into the corresponding 0- m- and p-methoxyaceto- phenones. The semicarbazone of m-methoxyacetophenone has m. p.195-197" (compare Klages Abstr. 1904 i 45) and that of the p-compound melts at 197'. T. A. H. Quinazolines. XXVIII. 4-Quinazolone-2-phthalones and Certain of their Derivatives. MARSTON T. BOGIERT and MICHAEL HEIDELBEHGER (J. Amer. Chem. Xoc. 1912 34 183-201).-An account is given of certain phthalones obtained by the action ofORGANIC CHEMISTRY. i. 215 phthalic anhydride on 2-methpl-4-quinazolone (2-methyl-4-hydroxy- quinazoline) and its derivatives. These compounds like the quino- phthalones behave as yellow dyes but are inferior to the latter in tinctorial power. Q-Qui~xolo~ae-2-phthcclone 14- hydroxyquinaxoline -2-phtha Zone 2-in- dandionyl-4-quinaxolone or p- (4'-quinanolon yl-2')-diketohydrindene] ~6H4*N>C*CH<co>06Hg m. p. 318' (corr.) obtained by heating a CO-NH CO mixture of 2-methyl-4-quinazolone and phthalic anhydride to about 200° forms pale yellow prismatic needles or hexagonal plates and when heated above 200' sublimes in woolly masses of minute needles.In one experiment in which a large excess of phthalic anhydride was used on extracting the reaction product with hot water 2-methyl- 4-quinazolone phthalnte was obtained which crystallises in pale yellow fluorescent needles with 1H20; the anhydrous salt has m. p. 171' (corr.). The di-sodium salt of the phthalone is orange-red whilst the mono-sodium and silver salts are pale yellow. On reducing the pht hnlone with zinc dust and sodium hydroxide 4-quincczoZone-2- N=Y-QH*YH CO NH CO-CAR,' is obtained which forms olive- hydrindone C6H4< yellow microscopic crystals subli&es above 160° and melts at about 328' (decomp.).When the phthalone is heated with anilite in Dresence of zinc chloride the anil. m. p. 284-285O (uncorr.) is produced which crystallises in brilliant scarlet needles ; its sodium salt and compound with zinc chloride are described. From the product of this reaction a small quantity of another anil m. p. 258' was obtained which forms red crystals and appears to be acondenaation product of 1 mol. of aniline with 2 mols. of the phthalone. 4-Quina~olone-2-phthalonemonophenyZhydrazone m. p. about 225' (uncorr.) was obtained as an orangsbrown micro- crystalline powder. 4-Quinaxolone-2-phthalone-6-sulphonic acid m. p. about 355-360' (uncorr.) crystallises in minute plates or needles ; its mono- and di-sodium and barium salts are described.Solutions of the di-sodium salt dye wool or silk light yellow shades. By the action of bromine on the sulphonic acid there were formed a di- and a penta- bromo-2-methyl- 4 - quinazolone a bromo - 2 - methyl - 4 - quinazolone- sulphonic acid phthalic acid and sulphuric acid. Dibromo-%methyl- 4-quinmolone m. p. about 293' (decomp.) forms masses of delicate colourless needles. Pentabromo-2-methyZ-4-quinazoZone m. p. about 243.5' (decomp.) crystallises in colourless prismatic needles. Bromo- 2-methyl-4-puinaxoZones~~hoic acid m. p. 285-286.5' (uncorr.) forms a grey amorphous solid containing lH20; its barium salt crystallises with 4&H20. Attempts to prepare 4-quinazolone-2-phthalines by heating the ammonium salt of the phthalone with alcoholic ammonia in sealed tubes did not meet with success.Bis-(4-q?~i~,axoEone-2)-P-pht~aZ~ne C,H,ON,.CH:C<~~~>C:CH.CBH,ON obtained by heating a 6 4i. 216 ABSTRACTS OF CHEMICAL PAPERS. mixture of phthalimide and 2-methyl-4-quinazolone is an orange-brown substanre which darkens gradually when heated ; its solution in dilute acetic acid acts as a powerful yellow dye. 4-QuinazoZone- %P-phthuZine C,H,0PLT2*CH:U<NH>C,H co- m.p. about 349' (decomp.) is also produced in t h i s reaction and forms orange-brown microscopic pi Lms. 2-Methyl-4-quinazolone reacts with succinic anhydride with production of a tarry mass from which a small quantity of tt substance m. p. 274-277" (decomp.) was isolated in the form of thin colourless lustroiis plates.6-Nztro-4-quinaxolone-2-phthc~lone obtained by heating 6-nitro- 2-methyl-4-quinazolone with phthalic anhydride a t about 210" forms minute yellow crystals and does not melt below 355'. 7-Acet~lamino-4.quislccxolone-2-p?~thalone resultiog from the action of phthalic auhydride on 7-acetylamino-2-methyl-4-quinazolone crystallises in bright yellow lustrous plates and does not melt below 356". N=$?Me 2-iCiet?~yl-3-et?~yl-4-quinaxolone C,H,<CO. NEt m. p. 67' (corr.) obtained by heating acetylanthranil with excess of an aqueous solution of ethglamine in presence of a little potassium hydroxide forms colourless slender needles ; its ptatinichloride decomposes at about 229". I n one experiment in which potassium hydroxide was not added anthrunilethylumide NHEt*CO*C,H,*NHAc m.p. 139.5-140.5' (corr.) was isolated in the form of transparent prismatic plates. 3-Ei%yZ-4-puinaxolone-2-p?~thaZone m. p. 19 8.5O (corr.) obtained from 2-methyl-3-ethyl-4-quinazolone and phthalic anhydride forms bright yellow lustrous prismatic needles with a slight green fluorescence. E. G. Formation of Pyrimidines by Use of Nitromalonaldehyde. WILLIAM J. HALE and HARVEY C. BRILL (J. Amer. Chem. Xoc. 1912 34 82-94).-Hill and Torrey (Abstr. 1899 i 788) have shown that nitromalonaldehyde reacts readily with primary amines. This work has now been extended to other amino-compounds. When carbamide is allowed to react with the sodium derivative of nitromalonaldehyde in presence of a few drops of piperidine the mono- ureide and 6-nitro-2-hydroxypyrimidine are produced.Nitromalonaldehyde mono-ureide NH,*CO*N:CH*CH(N02)*CH0 m. p. 154" (corr.) forms pale yellow crystals; its sodium salt crystallises with 3H,O. The a d NH,*CO*N:CH*CH(NO,)*CH:NPh m. p. 211" (corr.) crystallises in lustrous red needles. The oxirne NH,*CO*N:CH*CH(N02)*CH:NOH m. p. 174-175' (corr.) forms yellow leaflets. 5-Nitro-2-h~droxypyrimidilnir O H * C < ~ ~ ~ ~ > C * N O m. p. 203.5" (corr,) crystallises in small yellow plates ; the sodium potassium,ORGANIC CHEMISTRY. i. 217 barium and silver salts are described. The methyl ether m. p. 168-169' (corr.) forms colourless plates. 5-Nitr0-2-phenyZpyrirr~idine CPh<E ~ ~ ~ > C * N O m . p. 2 19" (corr.) obtained by the interaction of benzamidine hydrochloride and sodium nitromalonaldehyde crystallises in white plates.5-Nitvo-2-aclninopyrimidine7 N B * C < ~ ~ ~ ~ > C * N O m. p. 236' (corr.) prepared by the action of guanidine carbonate on sodium nitromalonaldehyde forms colourless slender needles and whea heated with solution of alkali hydroxide is converted into &nitro- 2-hydroxypyrimidine ; the acstyl derivative N H A ~ - C < ~ ~ ~ X - N O N*CH\ m. p. 172.5' (corr.) crystallises in long colourless needles. When a small quantity of potassium hydroxide is added to a mixture of 5-nitro-2-aminopyrimidine and carbon disulphide at 60° 5 5'-di- nitro- 2 2' - dip yrinzicEyk?~ioca~bamide CS[ N H C<z ;g>C*NO,] m. p. 230-231' (corr.) is produced which forms a mass of glistening leaflets. NitromaZonaldeiyde phenyluraide CHO*CH(NO,) * CH :N *CO*NHPh m.p. 1'76-177' (corr.) was obtained by the condensation of nitro- malooaldehyde with phenylcarbamide. The corresponding benzyl- ureide m. p. 150-151' (corr.) and methylureide were also prepared E. G. Chlorides of Amino-acids. CARL MANNICH and R. KUPHAL (Ber. 1912 45 314-322).-By the internal condensation of benzyl- sminoacetyl chloride and of similar amino-acid chlorides in the presence of aluminium chloride the authors hoped to prepare derivatives of isoquinoline CH',Ph*NH*CH,*COCl -+ C,,H,< It was found however that the chlorides readily lost hydrogen chloride even in the absence of aluminium chloride with the formation of d i ketopiperazines. Ethyl banzylarninoacetate prepared by the interaction of ethyl chloroacetate and benzylamine is a colourless liquid of aromatic odour b.p. 153-154'/13 mm. and is readily hydroiysed by hydrochloric acid to benzylaminoacetic acid (Mason and Winder Trans. 1894 67 187). It is accompanied by a substance which crystallises from dilute alcohol in lustrous white leaflets m. p. 2%- 239O consistiiig probably of benxylaminoacetobenzylamide hydrochloride C,H7*N H*CH,*CO-NH-C,H7,HC1. The amino-acid is converted by the action of phosphorus pentachloride and acetyl chloride (Fischer Abstr. 1905 i 263) into benxylamino- acetyl chloride hydrocldoride C,H7*NH*CH,-COC1,HCI which forms slender white needles and when heated in nitrobenzene solution yields 3 6-diketo-1 4-dibenzybiperazine C ? H ~ * N < ~ ~ ~ ~ ~ ~ > N . C ; I I crystallising in white needles m.p 1172-173'. CN,*TH CO-CHH,'i. 218 ABSTRACTS OF CHEMICAL PAPERS. 3 4-MethyZennsdioxybsnxylamine CH,:0,:C,H,*CH2*NH2 prepared by reducing piperonaldoxime with sodium amalgam and alcohol the solution being maintained continually acid by the addition of acetic acid is a colourless liquid b. p. 138-139"/13 mm.; on exposure t o air i t forms a solid carbonate ;. the hydrochloride lustrous white leaflets has m. p. 227'; the benxoyl and chloroacetyl derivatives crystallise in slender white needles m. p. 117-118O and 107-108' respectively. It reacts with ethyl chloroacetate yielding ethyl 3 4methylenedioxy- benzylaminoacetate CH,:0,:C,H,-CH,*NH*CH2*C0,Et which forms a hydrochloride white needles m. p. 157-158" and is hydrolysed by aqueous potassium hydroxide t o the corresponding acid.This has m. p. 206-207° and is converted by acetyl chloride and phos- phorus pentachloride into 3 4mctl~ylenedioxybenzylaminoacetyZchloride hydrocitloride C,,H,,O NCl ,. 3 6-Diketo-I 4-di-( 3 4')-met~ylenedioxybenzyl~i~~*azine CH, 0, C,H,.CI~~.N<~~~~~>N*CH,.C,H,:O:CH prepared by heating the preceding chloride hydrochloride in nitrobenzene solution forms white needles m. p. 234-235'. Ethyl benxylmethylaminoacetate C7H7*NRle*CH,-C02Et obtained from ethyl chloroacetate and henzylmethylamine has b. p. 1 38'/ 13 mm. ; the syrupy hydrochloride the orange platinichloride and the picrate crystallising in stout yellow needles m. p. 122-123" are described. When hydrolysed with concentrated hydrochloric acid it yields the corresponding acid C,,H,,?,N which forms a hydrochloride sintering at 174O m.p. 180-181 and a chloride hydrochloyide C7H7*NMe*CH,*COCI,HCl. The latter compound reacts with aluminium chloride at loo' yielding carbon monoxide formaldehyde and benzylmethylamine together with s-dibenzyldimethylmethylenediamine CH2(NMe*C7H7) a pale yellow oil b. p. 172-175'/8 mm. The coiistitution of the last-named compound has been established by its synthesis from benzyl methy lamine and f ormaldehyde. F. B. Preparation of Halogenated Dehydroindigotin Salts their Nuclear Eomologues and S u b a t i t u t i o n Products. BADISCHE ANILIN- Jz SODA-FABRIK (D.R.-P. 239314).-Halogenated dehydro- indigotin salts have previously been described and the preparation of higher halogenated derivatives is now recorded.l'richlorodehydroindigotin acetate a canary-yellow powder is prepared by passing chlorine into a cooled acetic acid solution of dehydroindigotin acetate until the product has completely separated ; when nitrobenzene is employed as solvent a tetrachlorodehydroindigotirt hydrochloride is obtained whilst under these conditions indigotin yields trichlorodehydroindigotin hydrochloride (isolated in the form of its bisulphits compound) and 5 5'-dibromoindigotin in acetic acid solution furnishes dichlorodibromodshydroindigotin hydrochloride. Other solvents such as acetyl chloride or carbon tetrachloride can be employed and the formation of other halogenated indigotins is discussed. F. M. G. M.ORGANIC CHEMISTRY. 1. 219 Action of Alkyloxides and Amines on Benzoyl isocyano- chloride [ Benzoylcarbylamine Chloride].TREAT B. JOHNSON and LEWIS H. CHERNOFF (J. Amer. Chem. SOC. 1912 34 164-170).- Benzoylcarbylamine ~hloride,~C~H,*CO*N:CCl obtained by Johnson and Menge (Abstr. 1904 i 949) by the action of chlorine on benzoyl thiocyanate is decomposed by water with formation of hydrochloric acid benzamide and benzoic acid. It combines with sodium alkyl- oxides to form compounds of a new class the acylimidocarbonatee and reacts with amines with produqtion of substituted guanidines which yield stable salts with mineral acids and are hydrolysed by alkali hydroxide with formation of the free guanidines and benzoic acid. Diethyl benxoylimidocarbonate NBz:C(OEt)2 b. p. 93-100'/20 mm. and 1 10-120°/32 mm. was prepared by the action of benzoylcarbyl- amine chloride on sodium ethoxide.Dimethyl benxoylimidocarbonate b. p. 95-102"/20 mm. is a colourless oil. Benzoyl-ay-diphenylgucmidine NBz:C( NHPh) m. p. 2 12' (decornp.) obtained by the action of benzoylcarbylamine chloride on a solution of aniline in benzene forms colourless needles. p-Benzoyl-ay-di-o- and -m-tolylguanidines NBa:C(NH*C,H,Me) have m. p. 126' and 177-1 78" respectively. Di-m-tolylguanidzne NH:C(NH*C,H,Me) m. p. 108-log" was obtained from the benzoyl compound by hydrolysis with potassium hydroxide. ,3-Benzoyl-ay-di-p-tolylguanidine m. p. 1 90° yields a hydrochloride m. p. 190-1 91" (decomp.). The following guanidines were also prepared benzoyltetraphenylguanidine m. p. 142-1 44' ; P-benzo yl- a y-diphen yl-a y-dirnethylguanidine m.p. 1 35' ; P-6en,xoyl-ay-di- p-anisylguanidine m. p. 12S0 and di-p-anisylguanidine m. p. 153' ; P-benxo y l-a y-di-a-naphth ylguanidine m. p. 1 62" and di-P-naphth yl- guanidine m. p. 197' (decomp.). E. G. Reduction of SernicarbazoneB. SIDONIUS KESSLER and HANS RUPE (Ber. 19 12 45 26-30).-Semicarbazones are readily reduced by sodium amalgam in dilute alcoholic solution at a slightly elevated temperature. In some instances for example those of cinnamaldehyde and styryl methyl ketone the influence of the constitution of the semicarbnzone prevents reduction to semicarbazide. Banz ylsernicarbaxide CH,Ph-NH*N H CO-NH from benzaldeh yde- semicarbazone crystallises in lustrous platelets m. p. 155'. It is distinctly basic dissolving in cold dilute acids and reduces Fehling's solution on boiling.The hydrochloride forms silky lustrous needles m. p. 17s-180'; the sulphate yields slender needles m. p. 158'; the picrate gives slender yellow needles m. p. 161-162' and the oxabate has m. p. 178-179' (decomp.). The acetyl derivative crystallises in beautiful colourless plates m. p. 207"; a diacetnte could not be obtained ; the benxoyl derivative forms colourless needles m. p. 230". 1YitrosobenxyZsemicarbccxide CH,Ph*N(NO)*NH*CO*NH prepared by the action of sodium nitrite and hydrochloric acid on benzyl- semicarbazide crystallises in long needles m. p. 1 3 3 O (decomp.). p-Methylbenxylsemicarbaxide crystallises in slender colourless needles m. p. 158'; the hydrochloride forms colourless needles m. p. 138' (decomp.) ; the rrulphate decomposes at 187" ; the picrate yields yellow needles m.p. 178' (decomp.) and the acid oxalate decomposes ati. 220 ABSTRACTS OF CHEMICAL PAPERS. 175'. The acetyl derivative crystallises in glistening colourless platelets m. p. 225' (not decomp.). Nitroso-p-inethyl6enxy~sem~ca;rbaz~de separates in colourless platelets and decomposes a t 126-127'. When cinnamaldehydesemicarbazone is reduced P-phenylprop- aldehydesemicarbazone m. p. 12S0 is the sole product. Similarly from the semicarbazone of styryl methyl ketone the product is the semicarbazone of phenylethyl methyl ketone. E. F. A. Reduction of Semicarbazones and the Preparation of Some Hydroxytriazoles. HANS RUPE and E. OESTREICHER (Ber. 19 12 45 30-38. Compare preceding abstract).-The property of semicarb- azones of being reduced to semicarbazide is closely dependent on their constitution.A phenyl residue must be attached directly to the group C:N. Aliphatic hydrocyclic and compounds i n which phenyl is replaced by benzyl cannot be reduced. The seniicarbazones of benzoy lpropionic acid and of p-benzoquinone could not be reduced. The semicarbazides vary considerably in their basic properties ; those from benzophenone aceto- phenone and deoxybenzoin dissolve in dilutle acids in the cold whereas those from salicylaldehyde or piperonal dissolve only when boiled with acids. 3 4-MethyZe~dioxybenx?/lse?nicarbazide CH,O, C,H3 CH,*NH*NH*CO-NH from piperonalsemicarbnzone forms transparent prisms m. p. 184'. The acetyl derivative crystallises in slender transparent needles m.p. 203-204O ; the formyl derivative forms long transparent rhorribic plates m. p. 204-205'. 3-Hydroxy-(rnp-rnethylenedioxyben=yl)-5-methyl-l 2 4-triazoZe CXle:N CH$j02:C(3H3* CH,"<~ ~ - - b 09 prepared by boiling the acetyl derivative with 30% sodium hydroxide and decomposing the sodium salt formed with hydrochloric acid forms opaque square crystals with stunted ends m. p. 190'; i t forms characteristic metallic salts. From the formyl derivative of the semi- carbazide 3-hydroxy-(mp-mclthylenedioxybenxyl)-l 2 4-triaxole is ob- tained ; it crystallises in stout transparent plates m. p. 246-24'7'. a- Phenylethylsemicarbaxide CH MeP h NH- N H - CO NH from acet o- phenonesemicarbazone crystallises in four-edged transparent prisms m. p. 142-143O. The acetyl derivative forms platelets m.p. 228-230° the formyl derivative crystallises in slender matted needles. m. P. 187" 3 - Hydrox y - 1 - a-phen y Zeth y 2-5 -meth y 2 tqiazo Ze CMe' CHMePh*.N<F-LC .OH crystallises in short well formed prisims m. p 146-147O. 3-Hydro~y-l-a-phanyZetAyltriaxo/e is obtained in transparent slender intergrown prisms m. p. 140'. Diphen ylmethylsemicarbaside CH Ph NH*NH* CO N H cry s fa1 I ises in long lustrous transparent needles m p. 164-165O; it gives anORGANIC CHEMISTRY. i. 221 in tense yellow coloration with concentrated sulphuric acid. The acetyl derivative crystallises in small transparent prisms m. p. 23'7' ; theformyl derivative yields small colourless needles m. p. 182'. The nitrosoamine CHPh,*K'(NO)*NH-CO*NH forms slender faintly yellow-coloured needfes A.p 122'. CMe:r 3-Hydroxy-l -diphen ylrnethyl-5-methyltriazoZe CHPh,*N<N== c. crystallises in glistening needles which appear under the microscope as prisms with two superposed pyramids. 3-Eydroxy-l-diphenylrnethyltriazole forms slender matted needles m. p. 253'. ap-D;phcnylethylsemicarhazide prepared from deoxybenzoinsemicarb- azone crystallises in long slender transparent needles grouped in st.ellar aggregates m. p. 139'. The acetyl derivative forms slender woolly needles m. p. 196'; the formyl derivative gives small trans- parent prisms m. p. 194'. o-Hydroxybenzyt?semicarbazide from salicylaldehydesemicnrbazone crystallises in four-edged prisms m. p. 128'. The acetyl derivative separates in slender needles m. p. 204'; the formyl derivative forms flat transparent plates m.p. 183-184'. 3- Kydroxy- 1-04 ydroxp benz yl-5-rnethyltriazole forms crystals m. p. 192' and gives a reddish-violet coloration with sulphuric acid. 3-Hydrozy- 1-0-8 ydroxy benzyltriaxols forms platelets of silvery lustre m. p. 211' (decomp.). 3-Hydroxy-5- bcnxyl- 1 -meth yltriaxole crys tallises in transparent prisms m. p. 168'. 3- Hydyoxy-1-benzyltriaxole forms lustrous nacreous platelets m. p. 147-148'. * E. F. A. DFtermination of Configuration of Stereoisomeric Hydr- azones. MAX BUSCH (Beq-. 19 12 45 73-85).-Stereoisomeric diphenylsemicarbazones of unsymmetrical esters of dithiocarbonic acid NHPh*CO*NPh*N:C(SR)-SR' analogous to the stereoisomeric phenylhydrazones (Abstr. 1911 i 811) have been obtained. Ethyl d ithiocarbonate-diphen ylsemica bazide NHPh*CO-NPh*NH*CS,Et stout needles m.p. 149-150° obtained from equal molecular quan- tities of phenylcarbimide and ethyl phenyldithiocarbazinate in warm benzene dissolves readily in aqueous alkalis and is decomposed by prolonged boiling with alcoholic potassium hydroxide yielding ethyl mercaptan and after acidifying 3-thiol- 1 4 - diphenyltriazolone (Abstr. 1911 i 689). By treating its alcoholic solution with equi- valent quantities of potassium hydroxide and methyl iodide i t yields (a) methyl ethyl dithiocarbonatediphenylsemicarbazone NHPh*CO*NPh-N :C(SMe)*SEt m. p. 93-94' rhombic needles. The stereoisomeric ( b ) methyl ethyl dithiocarbmate-diphmylsemicarbaaone m. p. 87-88' monoclinic needles or prisms is prepared in a similar manner from methyl dithiocarbonate- diphenylsemicarbazide ethyl iodide and potassium hydroxide.Thesei. 222 ABSTRACTS OF CHEMICAL PAPERS. two stereoisomeric semicarbazones behave very similarly. However when warmed at 80-60° with alcoholic potassium hydroxide the former yields ethyl mercnptan and the methyl thio-ether of 3-thiol- 1 4-diphenyltriazolone whilst the latter yields methyl mercaptan and the ethyl thio-ether m. p. 111-112° of the same triazolone; in both cases the alkyl group which was introduced first is eliminated as a mercaptan. Another pair of stereoisomeric semicarbazones are described. p:Nitrobenzyl phenyldithiocarbazinate and phenylcarbimide in benzene yield p-nitrobenxyl dithiocarbonate-diphenylsemicarbaxide NHPh* CO*NP h*NH*CS,* C,H,*NO m.p. 11 9-120" colourless needles which is converted by alcoholic potassium hydroxide and methyl iodide into (a) p-nitrobenxyl methyl dithiocarbonate-diphen ylsemicarbazone NHPh CO*NPh-N :C( SMe)-S*C7H,*N0 m. p. 126" stout yellow needles. The stereoisomeric ( b ) p-nityobenzyl methyl clit~iocarbonate-~~p7~e~ylse~~carbaxon~ m. p. 1 47" colourless plates is prepared in a similar manner from methyl dithiocarbonate- diphenylsemicarbazide and p-nitrobenzyl chloride. Either of these semicarbazones is converted when fused or heated in alcohol for one to two hours into an equilibrium mixture of approximately equal quantities of both forms. When warmed with alcoholic potassium hydroxide the yellow form yields the methyl thio-ether of 3-thiol- 1 4-diphenyltriazolone whilst the colourless form yields methyl mercaptan and the p-nitrobertxy2 thio-ether m.p. 178-179O of the same triazolone; in both cases again the nlkyl group which was first introduced is eliminated by the action of the alkali. c. s. Influence of the Acridine Ring on the Colour of Certain Colouring Matters. A. E. PORAI-KOSCHITZ Y. I. AUSCHKAP and N. K. AMSLER (J. Russ. Phys. Chem. Xoc. 1911 43 15S7-1603).- I n order to decide between the chromophore and dynamic theories (compare von Baeyer Abstr. 1907 i 757) of the colour of triphenyl- methane colouring matters the authors have prepared and studied acridylmalachite-green and acridylpyronine. The results obtained are distinctly in favour of the latter of the two hypotheses since the absorption spectra of the two colouring matters scarcely differ from those of malachite-green and rosamine the absorption bands being displaced towards the red end of the spectrum to an extent approxi- mately such as is usually observed with any more or less considerable increase in the molecular weight.A further consequence of the replacement of the benzene ring by an acridine nucleus consists in a marked diminution in the " permanency " of the spectral bands this being expressed in a decrease in the dyeing properties of the colouring matters. I n the case of acridylmalachite-green the quinonoid base was obtained in the pure state. The action of 5-aldehydoacridine (compare Abstr. 1911 i 688) on dimethylaniline in presence of zinc chloride and subsequent treatment with dilute hydrochloric acid followed by oxidation of any leuco- compound with lead dioxide yield a small quantity of a violet colour-ORGANIC CHEMISTRY.i. 223 ing matter which mas not investigated further and dimethylaminophenyl- acr~dylmethylensqu~nonodimethp~~mon~um chloride NqC s 4 H C6.H4*NMe2 ’ which is a green colouring matter with a bronze lustre dissolving slightly in water and readily in alcohol. It dyes cotton a somewhat bluer green than malachite-green whilst wool is dyed only very faintly in neutral solution but more strongly in presence of borax or ammonia. The first portions of wool immersed are coloured green with a slight blue tinge but if successive portions are introduced into the same bath the colour approaches more and more nearly to blue; this is found to be a result of the presence of alkali.TetramethyZdia~ninodiphenylacridylmethane (leuco-base of acridyl- malachite - green) N~CGH4~C.CH(C6H,*NMe2~2 C H forms yellow acicular crystals m. p. 171-172O insoluble in water but readily soluble in acids or organic solvents. forms The qzcinonoid base N%6H4 H ;NMe greenish-golden plates. In neutral aqueous solution the maximum intensity of the absorp- tion band of acridylmalachite-green lies at X = 64’2 pp whilst according to Formanek that for malachite-greeu is a t X = 618.5 pp ; the displace- ment caused by the sirbstitution of an acridine nucleus for a benzene ring is hence 23.5 pp. Acridylp yi*onine N<22>G* C<C6H3(N C6H3( :NEt,*OH) ‘2)- >O obtained by condensing 5-aldehydoacr%d;ne with m-diethylaminophenol in presence of sulphuric acid dissolves in very dilute acids giving a violet-red colour changing to cherry-red on addition of concentrat,ed acid.It dyes silk and wool reddish-violet and cotton blue with a red tinge no mordant being necessary. The absorption bands are almost identical in aqueous and in alcoholic solution and in both cases little change is produced by acidification with nitric acid or addition of potassium hydroxide ; this behaviour is characteristic of all colouring matters of the pyronine series. The absorption spectrum of acridine lies in the ultra-violet close to the visible part of the spectrum and the introduction of the pyronine residue results in the displacement of this absorption into the violet. The maximam intensities of the absorption bands lie a t 580 pp and 534.8 pp whilst Biehringer (Abstr.1897 i 73) found for tetra-ethylrosamine 563.5 and 527.5 pp; the displacements caused by the replacement of the benzene ring by an acridine residue are hence 16.5 pp and 7.3 pp. Relation between Constitution and Phototropy. MAURIZIO PADOA and F. BOVINI (Atti R. Accad. Lincei 1911 [v] 20 ii 712-717. Compare Padoa and Graziani Abstr. 1910 i 778 ; Pitdoa and Srtnti Abstr. 1911 i 693 1029).-The phototropy of the com- pounds described in t h e present paper r”ol1ows the regularities previously discovered. ~-~s?~z~Z-a-naphtAyZosazone C,Ph,( :N*NH*CloH7)2 obtained by C6H4>C. C<C6H4:NMe2C1 6 4 C6H4>(3.C<C6 C €I 4 :NMe,*OH T. K. P.1. 224 ABSTRACTS OF CHEMICAL PAPERS. Purgotti's method (Abstr.1893 i 354) forms lemon-yellow crystals m. p. 175O and is not phototropic. /3- Pipei*il-a-naphth,ylosaxone C,(C,R,:O,:CH,),( :N*NH*CIoH7) pre- pared by MacNair's method (Abstr. 1890,1245) crystallises In yellow needles m. p. lS9" and is prototropic. P-An~sil-a-naphth yloaaxono C,(C,H,*OMe),( N *NH *C nH7)2 prepared like t h e preceding compound cryst,allises in golden-yellow needle@ m. p. 155" and is prototropic. Piperonaldehyde-a-naphth y Mpdrazone CH, 0, C,B,*CH N*NH*CloH7 cry~tallises in greenish-yellow needles m. p. 147" and is not phototropic. HO*C,H,*CH:N*NH*CloH7 forms lustrous golden-yellow needles m. p. 134" and is not phototropic. Vc~niZZin-a-naphth~Z~ydr~zon(J OMe*C,H,(OH)*CH:N*NH*Cl~H7 is an unstable yellow crystalline powder which i R not phototropic.p - ToZuddahyde - a - naphthylhydrazone C,II,Me*CH:N*NH*Cl,H7 crysttsllises in greenish-yellow needles m. p. 152" and is not pbototropic. /3-BanziZ-1 3 4-xyl~Zosazone C,Ph,( :N-NH*C,H,hle,) is an orange- yellow crystalline substance m. p. 7 1 -72" and is phototropic. Piperil- I 3 4-xyZylosaxone C2( C,H,:O,:CH,),( :N*NH*C,H,Me,) forms lemon-yellow prisms in. p. l87" and IS phototropic. A n i d - I 3 4-xylyZosazone C2(C,H,*OMe),( :N*NH*C,H,Me,) is an orange-yellow crystalline substance m. p. 75" and is phototropic. Cunzinil-1 3 . 4-xyZyZosnzone C,( C,H,PrP),( :N*NH* C,H,Me,),,. is a yellow crystalline substance m. p. 64-70" and is not phototropic. R. V. S. Salicylaldehyde - a - naphthylhydrazone Researches on Purines. IV. 2-Oxypurine and 2-0xy-8- methylpurine.CARL 0. JOHNS (J. Biol. Chem. 1912 11 67-72).- 6-Oxypurine (hypoxanthine) was first isolated by Scherer in 1850 and nearly fifty years later was synthesised by Fischer. 8-Oxypurine was prepared by Pischer and Ach. 2-Oxypurine was prepared by Tafel and Ach from guanine but they did not offer any proot of its structure. In the present research it was prepared from 5 6-di- amino-2-pyrimidone and the product agrees in all respects with that of Tafel and Ach. When 5 6-diamin0-2-pyrinriidone is heated with formic acid a morwformyl derivative i u obtained; this yields a potassium salt which when heated gives off water and changes to the potassium salt of 2-oxypurine ; 2-oxypurine cryhtallises with 1H20 and does not lose it until heated t o 120". The picrate nitrate and hydrochloride were prepared.When 5 6-diamino-2-pyrimidone is boiled with acetic anhydride i t forms chiefly a monoacetyl compound together with some of the diacetyl compound. When the potassium salt of the former is heated it yields the potassium salt of 2-0xy-B-methylpurine ; this substance forms a picrate decomp. 250° and a nitrate decomp. 205O which may be used for its identification. W. I). H.OHGANlC CHEMISTRY. i. 225 Preparation and Reactions of Aeo-acyl Compounds. ROBEHT STOLLL~ [with J. MAMPEL J. HOLZAPFEL and I(. C. LEVERKUS] (Ber. 1912 45 273-289).-Azodiacyls of the type R*CO*N:N*CO*R (where R = H Me CHEt,,. Ph C,H,Cl and a-CIoH7j have been pre- pared by the action of iodine or bromine in ethereal solution on the mercury or silver salts of symmetrical diacylhydrazides K*CO*NH*NH*COK.The azodiacyls prepared from hydrazides of aromatic acid3 are com- paratively stable whilst those derived from aliphatic acids are unstable and could only be obtained iu ethereal solution or in a n impure condition as red oils. They are converted by reducing agents such ae hydriodic acid hydrogen sulphide and phenylhydrazine into the original hydrazides. When treated with water they yield tri- acylhydrazides the decomposition taking place according t o the following scheme 2N,(CO*R) + H,O = R*CO,H + N2 + R*CO*NH*N(CO*R),. It is supposed that the first stage in the reaction consists in the partial hydrolysis of the azodiacyl t o the compound (I) which instantly decomposes thus (I) NH:N*CO*R -+ H + N + *CO*R ; this is foliowed by addition of H and *COX to a second molecule of the azodiacyl with the formation of a triacylhydrazide.Evidence in support of this view is furnished by the production of triacyl- hpdrazides by the reaction of azodibenzoyl and azodi-a-ethylbutpryl with benzaldehyde and also by the formation of benzoylhydrazobenzene NPhBrNHPh by heating azobenzene with benzaldehyde for fifteen hours a t 110'. The decomposition of the azodiacyls by heat has not yet been thoroughly investigated but with azodibenzoyl and azodi-a-naphthoyl the decomposition occurs t o a small extent as follows COR-N:N*CO*R -+ COR*COR + N,. Azodicarboxylimide and several of its derivatives of the formula (I) below (where R=H P h NH N:CHPh) have also been prepared by the action of iodine in ethereal solution on the silver salts of the corresponding hydrazo-compounds (11) ; they are decomposed by water as follows Ph*CHO + R*CO*N:N*CO*R -+ R*CO*NBz*NH*CO*K #::~>NR + ZH,O = ;YH"!O>~~ + N + zco + R-NH,.NH*CO (1.) (11.1 The mercury salt of 8-dibenzoylhydrazide CPh<gZ.g>CPh obtained by the action of mercuric chloride on the hydyazide and sodium ethoxide in alcoholic solution is converted by bromine in etbereal solution into azodibenzoyl (Stoll6 and Benrath Abstr. 1900 i 531; 1904 i 935). When heated at 270' i n an atmosphere of carbon dioxide this decomposes yielding small quran tities of benzil and 2 5-diphenyl-1 3 4-oxadiazole. It combines with benzaldehyde at llOo to form tribenzoylhydrazide a small amount of the above-i. 226 ABSTRACTS OF CHEMICAL PAPERS.mentioned oxadiazole being produced simultaneously. aniline yielding benzanilide and s-dibenzoylhydrazide thus It reacts with (1) NBLNBz + NH2Ph = NHPhBz + N2 + 2H (2) 2H + NBLNBz = NHEz*NHBz and with dimethylaniline to form 8-di benzoylhydrazide the dimethyl- aniline being oxidised to tetramethyldiphenylinpthane and other products not yet investigated. s-Bi- p- chlorobenzoylh ydrazide prepared from h y drazine sul phate p-chlor obenzoyl chloride and aqueous sodium hydroxide crystallises in felted needles m. p. 289" and reacts with sodium hydroxide in aqueous alcoholic solution to form the sodium salt C6H4C1*C( ONa) N * NH*CO*C6H4CI which crystallises in lustrous pale yellow leaflets and is oxidised by iodine in ethereal solution to uxodi-p-chlorobensoyl N,(CO*C,H,Cl) yellow needles m.p. 147" (decornp.). s-Di-a-naphtiLoylhydraxide prepared in a similar manner has m. p. 260° and forms a silver salt C,,H,*C(OAg):N*NH*CO-CloH7 which is oxidised to uxodi-a-waphthoyZ N,(CO-C1,H7)2. This crystallises in orauge-red needles m. p. 1484 and when heated at 140-150° loses nitrogen yielding di-a-naphthyldiketone C,,H7*CO*CO*CIOH7 m. p. 187" ; it reacts with water to form a-naphthoic acid s-di-a-naphthoyl- h j drazide and tri-a-naphthoylhydraxide C,,H CO* NH*N( CO C,,H7) which has m. p. 188O and has also been prepared by the action of a-naphthoyl chloride on the silver salt of s-di-a-naphthoylhydrazide. The sodium salt of s-benzoylacetylhydrazide CgHg02N2Na is converted by mercuric chloride in alcoholic solution into the mercury salt C,H,O,N,Ng.Benxoylccxoacetyl NAcZNBz obtained in an impure condition as a red oil by the interaction of iodine and the preceding mercury salt in ethereal solutioo is decomposed by water yielding benzoic acid s-di benzoylhydrazide and dibe?zxoyZacetylhydraxide NAcBz*NH Bz m. p. 171". 2-Phenyl-5-mtetl~y/E-l 3 4-oxadiaxole CMe<F.y>OPh prepared by heating s-benzoylacetylhydrazide with phosphoryl chloride crystallises in lustrous plates m. p. 67"; it forms with silver nitrate an additive compound crgstallising in lustrous needles m. p. 185"; a n additive compound with mercuric chloride is also described. Dibenxoyldiacetyl~~ydruzii~e N AcBz*NAcBz prepared either from acetyl chloride and the mercury salt of s-dibenzoylhydrazide or from benzoyl chloride and the mercury salt of s-diacetylhydrazide crystallises in leaflets m.p. 109". s-Diformylhydrazide yields a crystalline silver salt C,H202N2Ag2 which explodes when heated and a rnercurw salt Azodvyormyl N,(CHO) prepared from the preceding mercury salt could not be isolated on account of its instability; its ethereal solutions have a raspberry-red co our. The mercury salt of s-diacetylhydrazide C,H602N,Hg prepared fromORGANIC CHEMISTRY. i. 227 the hydrdzide sodium ethoxide and aqueous mercuric chloride reacts with iodine in ethereal solution in the presence of magnesium or barium oxides yielding azodiacetyl NAcINAc in an impure condition as a dark red oil. s- Di-a-ethylbutyrylthydruzide N,H,(CO*CHEt,) prepared from the corresponding acid chloride and hydrazine hydrate in the presence of sodium carbonate crystallises in white needles m.p. 230O. Azodi-a-ethylbutyryl N,(CO*CHEt,) obtained from the mercury salt C,,H,,O,N,Hg of the preceding compound as a red oil is decomposed by water into a-ethylbutyric acid and tri-a-ethylbutyryl- hydrazide CHEt,*CO*NR*N(CO*CHEt,) which crystallises in colour- less prisms m. p. 95O and has also heen prepared by the interaction of a-ethylbiityryl chloride and s-a-diethylbutyrylhydrazide in pyridine solu- tion at 100'. It combines with benzaldehyde yielding benzoyldi-a-ethyl- butyrylhydrazide CHEt,*CO*NBz*NH*CO*CHEt crystallising in small prisms m. p. 123O. The latter compound may also be prepared from benzoyl chloride and s-di-a-ethylbutyrylhydrazide in pyridine solution. N-CO N*CO Axodicarboxylimide [diketodihydro-1 3 4-triaxole] I I >NH ob- tained as a violet oil by the action of ethereal iodine on the silver salt of hyclrazodicarboxy limide in the presence of barium and magnesium oxides is instantly decomposed by water yielding nitrogen carbon dioxide and hydrazodicarboxylimide.Hydrazodicarboxylphenylimide yields the silver salts C,H,O,N,Ag and C8H,0,N3Ag of which the latter is converted in the usual manner into azodicarboxylphenylimide. This forms carmine-red crystals (compare Thiele and Stange Abstr. 1895 i 251) gives violet solutions in ether and decomposes when heated into phenylcatbimide and hydraxotetracarboxyldiphen yldi-imide * " co q? co>Np h Ph<Co N co which crystallises from glacial acetic acid in lustrous white leaflets subliming in needles without melting. Axodica?.boxylccmi~oi~ide (axodicai.box~l~~ydrazide) [I - amino - 2 5- fj*c0>N*NH2 prepared from the silw N-CO diketodihydro-1 3 4-triaxoZe] salt of aminourazole (Curtius and Heidenreich Abstr. 1896 i 143) C,H,O,N,Ag is an unstable violet powder ; it explodes at 7 2 O and is slowly converted by water into aminourazole. Azodicarboxylbenxylidmeh ydraside R'co>N*K CHPh obtained N-CO from the silver salt of benzylideneaminourazole (hydrazodicarboxyl- benzylidenehydrazide) C,H,O,N,Ag forms carmine-red crystals which become colourless when heated (at 135-138') owing to loss of nitrogen and conversion into hydraxotetracarboxyldibenxylide.necEihyds.- nxide CHPh N"<,O. The mercury salts of ethyl hydrazodicarboxylate yields with iodine in ethereal solution ethyl azodicarboxylate (Cur tius and Heidenreich CO*N*CO CO>N*N CHPb m. p. 2 85'.i. 228 ABSTRACTS OF CHEMICAL PAPERS. Zoc. cit.) and when heated with benzoyl chloride in carbon tetra- chloride solution at 1 OOO form8 ethyl diben,nxoyZhydrasodicar~ox~Za~ C20H2,,06N2 which forms white crystals m. p. 83'. F. B. Enzymic Decomposition of Hydrogen Peroxide. 11. PERCY WAENTIG and OTTO STECHE (Zeitsch. physiol. Chem. 19 12,76 177-2 13. Compare Abstr. 1911 i 759).-The behaviour of both animal and vegetable extracts in decomposing hydrogen peroxide is very similar and in far closer agreement with Senter's haemase than is generally stated. This is illustrated particularly by the influence of hydrogen and hydroxyl ions on the rate of reaction-any shift in equilibriurri from that prevailing in distilled water free from carbon dioxide causes a retardation. The reaction is however less sensitive when relatively large amounts of impurity are present in the extracts ; this may be due to the amphoteric character of the proteins in retaining acids or bases or t o a definite protective action of the impurities analogous to that of the so-called '' protective colloids." This insensi- tive character is specially marked in catalase solutions prepared from the alcohol precipitate of an aqueous extract of germinating barley. The enzyme extracts behave similarly at 0' and a t 30' ; at the higher temperature the hydrogen ion has less the hydroxyl ion more influence on the rate of change. The influence of temperature on the rate is very small. The course of change does not quite correspond witb the simple mass-action law; the value of K falls off even in very dilute hydrogen peroxide solutions at 0". Dialysis yields weaker extracts but with these a more constant value of R is obtained. The amount .of enzyme is roughly proportional to the rate of change. Exposure to ultra-violet light weakens the enzyme activity ; the effect is greater in alkaline than in neutral or acid solution. Complete precipitation of the enzyme from extracts of liver fat barley etc. requires an alcohol concentration of 55%. Animal extracts show a decline in activity when the concentration of hydrogen peroxide exceeds a certain point; this is not the case with plant c s t rac t s. It would appear that the active substance which brings about the decomposition of hydrogen peroxide is the same irrespective of origin. E. F. A. Preparation of Mercury p-Aminophenylarsinates. AKTIEN- GESELLSCHAFT FUR ANILIN-FABRIKATION (D.R.-P. 237787).-&fercury hydrogen p-arninophenylarsinate [NH,-C,H,*AsO( OH)*O],Hg a colour- less powder sparingly soluble in water islprepared by stirring together an aqueous paste of p-aminophenylarsinic acid (2 mols.) and mercuric oxide (1 mol.). The basic salt NH,*C,H,*AsO(OH)*O~Hg*OH is obtained when equimolecular proportions of the amino-acid and mercuric chloride in the presence of alkali (2 mols.) are employed. F. M. G. M.