125 Organic Chemistry. Chemical Action of the Electric Discharge at Low Tempera- tures. E. BRINEU and E. L. DURAND (J. Chim. Phys. 1909,7,1-30). -Most of the results described in this paper have been published already (Abstr. 1907 ii 759; 19OS ii 101 940). By the action of the electric spark on a mixture of nitrogen and ethane at -7S0 carbon hydrogen nitric acid ammonia and higher hydrocarbons ara obtained the latter being formed by polymerisation. I n siffiilar experiments with a mixture of nitrogen and acetylene similar products were obtained but in the latter case the proportion of hydrogen cyanide predominates over that of the ammonia. I n the action of the silent discharge on ethane alone at - 78O no carbon is liberated but there is considerable formation of higher hydrocarbons.Under similar conditions a mixture of equal volumes of nitrogen and ethane also gives a relatively high proportion of higher hydrocarbons and less hydrogen cyanide khan when the spark discharge is used. The effect of the electric discharge is very complicated and it appears that the laws of chemical stadcs are not applicable ; kinetic and atomic considerations afford a better guide to the phenomena. G. S. isoOctane [P-Methylheptane]. LATHAM CLARKE (J. Amer. Chern. Soc. 1909 31 107-116. Comparo Abstr. 1907 i 169).-/3-Methyl- heptane is the ninth hydrocarbon of the series C8H to be prepared. It may be easily obtaiued by either of the following processes (1) Me*CO*CH,*CO,Et -+ Me*CO*CH( CH,-CH,PrP)*CO,Et -+ Me*CO*[CH,],*PrP -+ CHMe(OH)-[CH,],*Pi P -+ CHMeI*[CH2]3-Prp -+ Me*[CH2],*PrS.CHPraI*CH,Prfl -+ h!fe*[CH,],*PrP. Methyl kohexyl ketone has b. p. 165'/764 mm.; Welt gives b. p. 167-168O (Abstr. 1895 i 202). It is reduced by sodium and ethyl alcohol to methylisohexylcarbinol b. p. 1 'i6'/765 mm. (compare Welt loc. cit.) and rnethylisohexylpinacme PI+*[CH,]~*CM~(OH)*CM~(OH)-[CH&*PI~ a liquid b. p. 293-295'/765 mm. by hydrogen iodide into +odo-/3(+?etramethyZdodecan-[-ol PrS*[CH,~,.CMe(OH)*CMeI.LCH,I,*PrP an unstable colourless oil (compare Clarke and Shreve Abstr. 1906 i 473). Methylisohexylcarbinol is converted by red phosphorus and iodine into l-iodo-P-rnethylheptane a colourless heavy oil which when reduced with a zinc-copper couple yields isooctam (/3-methylheptane) CH3*[CH2],*BrB a colourless liquid b.p. 116O/761 mm. Di 0.7035 fig 1.3944. The reduction may also be effected by acting on the iodo- octane with magnesium in dry ether and treating the organo-magnesium compound with water. (2) PraMgI + CH2Pr P*CHO -+ CHPra(OI-1) *CH,PrP -+ The latter compound is converted YOL. XCVI. i. k126 ABSTRACTS OF CHEMICAL PAPERS. Propyl magnesium iodide and isovaleraldehyde interact in dry ether forming an additive product which when treated with water yields P-met?~yZ-6-heptanoZ CH Pra(O€I)* CH,Pr~ a colourless liquid b. p. 164'/760 mm. If the reacting substances are not quite dry isoamyl alcohol and a glycol CH2Prfi*CH(OH)*CH(OH)*CH,Prf3 a colourless viscid oil b. p. 238-242"/760 mm. are formed. P-Methyl-8-heptanol is converted by red phosphorus and iodine into 6-iodo-/3-methyZheptane which is reduced by a zinc-copper comple to P-methylheptane.W. H. G . Production of Iodoform [from Carbon Dioxide]. GABRIEL QuPaIw (J. Pharm. Chim. 1909 [vi] 29 54-55).-Potassium hypo- chlorite added gradually to an aqueous solution containing ammonia potassium hydroxide 10% of potassium iodide and 5% of potassium carbonate forms nitrogen iodide which at first disappears on shaking. When the disappearance becomes slow a large excess of ammonia is added which causes an almost immediate precipitation of iodoform. G. B. Reactione between Iodoform and Silver Fluoride and Chloride. WILLIAM OECHSNER DE CONINCK (Bull. Xoc. chirn. 1909 [iv] 5 62-63. Compare Auger Abstr. 1908 i 494).-On gently heating silver chloride and iodoform in the correct proportions sus- pended in dilute alcohol the following interaction takes place 3AgCl+ C KI = 3AgI + CHCI,. No gas is evolved whereas if silver fluoride is taken (as Auger has shown) the products are carbon monoxide and hydrogen fluoride with a little carbon dioxide 3AgF + CHI + H20 = 3AgI + 3HF + CO.Preparation of Absolute Alcohol. M. EMMANUEL POZZI-ESCOT (BUZZ. Assoc. Chirn. sucr. dist. 1909 26 580).-Ninety to 95% alcohol is digested with aluminium foil in presence of mercuric chloride and then distilled. The product consists of absolute alcohol free from R. J. C. aldehydes and acetals. L. DE K. Butane-P-ol [Methylethylcarbinol] and its Tartrates. J. RICH^ (J. Pharm. Chirn. 1909 [vi] 20 57-60).-'l!his alcohol synthesised from acetaldehyde by Grignard's reaction could not be resolved into its optical antipodes by fractional esterification with tartaric acid.G. B. Pinacolyl Alcohols. MAURICE DELACRE (Bull. Xoc. chim. 1909 [iv] 5 109-1 13).-The author questions the accuracy of the follow- ing conclusions given in L. Henry's recent papers on pinacolyl alcohols (Abstr. 1907 i 374; 1908 i 881; this vol. i 79).- (1) That the haloid esters of sec.-pinacolyl alcohol (methy1tert.-butyl- carbinol) undergo isomerisation when heated yjelding haloid esters of tert.-pinacolyl alcohol (dimeth ylisopropylcarbinol) ; (2) that since on dehydration with acetic anhydride both pinacolyl alcohols yield a mixture of By-dimethyl-AS-butylene and By-dimethyl-ha-butylene in which the former largely preponderates it may be assumedORGANIC CHEMISTRY.127 gennera2Zy that the hydroxyl of a :C(OH)* group placed near a :CHo and a -CH,. Froup exhibits a marked but not exclusive preference for the H of the .CH* group and (3) that in the dehydration of dimethyliso- propylcarbinol by acetic anhydride containing aulphuric acid the anhydride acts by first forming dimethylisopropylcarbinyl acetate which is more readily dehydrated than the parent alcohol. The author contends that the first statement is refuted by the results given in his previous papers (Abstr. 1907 i 578; 1908 i 243) and that the second conclusion is inadmissible since the relative proportions of the two hydrocarbons formed vary with the conditions of the experiment. The validity of the third point he has examined by treating dimethylisopropylcarbinyl acetate with dilute sulphuric acid and finds that the acetate is scarcely dehydrated at all under conditions in which the alcohol undergoes complete dehydration (Abstr.1906 i 921). P. CLAESSENS (Bull. Soc. chim. 1909 [iv] 5 113-1 18).-$-Butylethylene (yy-dimethyl-ha-butylene CMe,*CH:CH,) described by Delacre (Abstr. 1902 i 79) furnishes a liquid dibromida b. p. 91-92'/14 mm. (approx.) 203'/762 mm. (decomp.) Do 1,616 which becomes coloured on keeping is readily soluble in organic solvents and when heated with potassium acetate and acetic acid in a closed tube at 200' is converted into bl.onto-yy-dimethyZ-A"-bztyZe~e b. p. 120-130° Do 1.165 which was not obtained pure. On oxidation with permanganate yy-dimethyl-ha-butylene yields trimethylacetic acid and is therefore an exception to Wagner's rule that on careful oxidation with permanganate ethylenic hydrocarbons yield the corresponding glycols (Abstr.1888 i 665). With iodine and yellow mercuric oxide the hydrocarbon yields the corresponding iodohydrin D 1.481 which decomposes at 1 loo but is volatile in steam. On treatment with potassium hydroxide solution this yields the corresponding gZyco2 CMe,*CH( OH)*CH,*OH D5O 0.940 b. p. 205-'206' m. p. 32-33' which is crystalline and hygroscopic. The glycol dissolves in hydrochloric acid from which it can be recovered unchanged. With acetyl chloride it yields apart from a small quantity of a chlorinated compound a dimetyl derivative b. p. 213-215O Do 1.014 which is a liquid of pleasant odour and readily soluble in water alcohol or ether.Couturier's hydrocarbon &di- methyl-ha-butylene (Abstr. 1893 i 244 and Delacre Abstr. 1902 i 79) can also be converted into the corresponding glycol through the iodohydrin. This glycol furnishes a chloroacetate on treatment with acetyl chloride and dissolves in hydrochloric acid yielding a chlorinated product which decomposes on distillation. T. A. H. +-Butylethylene Glycol. T. A. H. New Method for Preparation of Ethers. JEAN B. SENDEBENS (Compt. rend. 1909 148 227-229).-The author has recorded pre- viouslg the decomposition of alcohols into ethylenic hydrocarbons and water by the catalytic action of precipitated alumina at 300" (Abstr. 1908 i 494 495 ; ii 166). It is now found that this substance at a lower temperature can effect the quantitative dehydration of 11.2128 ABSTRACTS OF CHEMICAL PAPERS.alcohols with production of the corresponding ethers. Thus alcohol in the state of vapour is passed over alumina (prepared by acidifying a solution of sodium aluminate) at 240-260° and the products passed through a Y-tube cooled in ice. It is not necessary to use absolute alcohol. The products condense to a liquid which separates into two layers ; the upper layer consists of ethyl ether in :a state of greater purity than commercial ‘* rectified ether.” Methyl ethet and pr’opyl ether have been prepared in the same manner. W. 0. W. Action of Acids on Sodium Ethyl Thiosulphate. 111. AUGUST GUTMANN (Bey. 1909 42 228-232. Compare Abstr. 1907 i 671 ; 1908 i 497).-The action of alkalis on sodium ethyl thio- sulphate is represented thus NaEtS,O + KOH = NaKSO + EtSOH.Bunte (Bey. 1874 646) represents the corresponding acid hydrolysis in the following manner NaEtS,? + H,O = NaHSO + EtSH. The author finds that sulphurous acid is also produced whether the reaction is carried out in concentrated or dilute solution or in presence of much or little acid The other products are ethyl sulphide sulphuric acid and ethyl mercaptan. Probably the change in acid solution as in alkaline is a t first HEtS,O,+H,O=SO,+ H20 + EtS*OH. Subsequently in acid solution the sulphurous acid reacts with one or two molecules of thioethyl hydroperoxide thus EtS*OH + SO = EtSH + SO ; 2EtSoOH + SO = Et,S2 + H,SO,. That this explanation is correct is shown by the fact that if after alkaline hydrolysis a solution of sodium ethyl thiosulphate is rendered acid and kept sulphuric acid is formed.In view of these results thiosulphuric acid can no longer be given the constitution SO,<: ascribed to it by Bunte but it must exist as the two isomeric forms S 0 2 < ~ o E and S02<rr. O*SH . E. F. A. Acid Glycerophosphates. P. CARRS (Bull. SOC. chim. 1909 [iv] 5 109).-With reference to a paper by Self (Pharm. J. 1908 26 627) it is pointed out that the process described by that investi- gator for the preparation of barium hydrogen glyceryl phosphate namely the addition of sulphuric acid to barium glyceryl phosphate until the mixture is neutral to helianthin has been shown by the present author on a previous occasion to yield a mixture of the normal glyceryl phosphate and glyceryl dihydrogen phosphate (Abstr.1904 i 133 215 819). T. A. H. The Nitrogen of Lecithin and other Phosphatides. HUGH MACLEAN (Biochem. J. 1909,4 38-58).-The nitrogen of the com- mercial preparation of lecithin termed ‘‘ lecithol ” (Riedel Berlin) is probably all present as choline. I n the lecithin of heart-muscle there is probably another nitrogen- containing group in addition. The base of cuorin is probably not choline. W. D. H.ORGANIC CHEMISTRY. 129 Allylxanthic Acid. BERNARDO ODDO and GIOVANNI DEL Rosso (Gaxzetta 1909 39 i 11-23).-Study of allylxanthic acid and of its salts and other derivatives shows that in some ways the xanthic acids are comparable with hydrogen sulphide and with cyanic and thiocyanic acids. Potassium SK*CS*O*C,€I and sodium ccllylxccnthates SNa*CS*O*C,H obtained by the action of excess of carbon disulphide on a solution of potassium (or sodium) hydroxide in allyl alcohol at a low temperature form white gelatinous precipitates which dry in the form of faintly yellow silky needles.With copper sulphate these salts react accord- ing to the equations BSK*CS*O*C,H + CuSO = (C,H,*O*CS*S*),Cu + K2S0 and Z(C,H,*O*CS*S*),Cu = (C t3,*O°CS*S*)2Cu2 + C,H,=O*CS*S*S*CS*O*C,H (compare Ragg Ab;tr. 1908 i 604) the cupi*ous allylxantAate formed being insoluble. The allylxanthic radicle in the potassium and sodium salts may be estimated by titration with standard copper sulphate solution using s-diphenylcarbazide as indicator (compare Oddo Abstr. 1903 ii 758). The following salts of allylxanthic acid were also prepared silver C,H,OS,Ag zinc ( C,H,OS,),Zn lead (G4H2OSJ2P.b nickel (C4H50S2),Ni cobalt (C4H50S2)2C02 mercury cadmaurn tin bismuth iron platinum and gold.Allylmnthic acid SH*CS*O*CH2*CH:CH2 is obtained as a faintly ycllow unstable oil heavier than water and on distillation decom- poses into allyl alcohol and carbon disulphide. The methyl ester SMe*CS*O*C,H is a pale yellow oil b. p. 200-203° DZ4 1,1214 with an alliaceous odour and has the normal molecular weight in freezing benzene. The ethyl ester C,H,,OS is an oil b. p. 210-212° DB 1.0690 resembling the methyl derivative in odour and having the normal molecular weight in freezing benzene. The ally.! ester C,H,,OS is obtained as a brownish-yellow oil b. p. 231-253” having a very pungent garlic-like odour and exhibiting normal cryoscopic behaviour in benzene.T. H. P. Selenomercaptans and their Derivatives. LEO TSCEUGAEFF (Ber. 1909 42 49-54).-Ethyl propyl and butyl selenomercaptans have been prepared by heating on the water-bath a solution of sodium hydroselenide obtained by saturating a 10% alcoholic solution of sodium ethoxide with hydrogen selenide with about 5.h less than the calculated quantity of the alkyl iodide or bromide in an atmosphere of hydrogen. The selenomercaptans are heavy liquids with a foul persistent odour which are insoluble in water react in the usual way with mercuric oxide and yield coloured precipitates with the salts of heavy metals particularly of lead and thallium. Selenomercaptans are extremely autoxidisable in air yielding diselenides R-Se2*R.The hydrogen of the *SeH group reacts with magnesium methyl iodide methane being evolved quantitatively. Selenides R*Se*R” are obtained by treating an alcoholic solution of sodium ethoxide and the selenomercaptan with an alkyl iodide or bromide all in equal molecular quantities; in the absence of air the yield is nearly quantitative. Diselenides of the type R*Se*[CH,],,*Se*R result by the130 ABSTRACTS OF CEIXWCAL PAPERS. action of dihaloid hydrocarbons on the sodium selenomercaptides 2NaSeR + Br[CH,],Br = R*Se[CH,],*Se-R + 2NaBr. With ethylene dibromide however the main product is diethyl diselenide ethylene being evolved. R*Se* [CH,],*Se*R are colourless liquids somewhat stable in air whilst diselenides of the type R*Se,*R are yellowish-red liquids which distil undecom posed only in a vacuum.In the accompanying table the density refractive index and coefficient of expansion (a) are measured at the temperature 6O. The selenides and the diselenides of the type B. p. 1". D:. a. n,. EtSeH ........................ 53'5" 24 1.3954 0'0018 1.47715 PraSeH ........................ 84 20 1-3020 - 1.47560 BuaSeH ........................ 114 24-5 1'2352 0'0012 1-47446 MeSeEt ........................ 86 23 1'3134 - 1 -4820 MeSePra ..................... 114 20'4 1'2445 - 1-48121 MeSeBua 141 24'5 1'1875 - 1.47710 PraSePra ..................... 159 24-3 1'1427 0*00113 1-47494 PrclSe,'Pra ..................... 99/13 min. 22'2 1'4991 0.00127 1.55535 EtSe'{CH,],*SeEt ........... 135/15 mm. 24 1'4630 0*00129 154892 The atomic refraction of selenium in the selenomercaptans is 10.78 i n the selenides 10.91 and in dipropyldiselenide 11.33. C.S. Solidiflcation of Mixtures of Water and Soluble Fatty Acids. A. FAUCON (Compt. rend. 1909 148 3$-39).-The freezing-point curves of the systems water-formic acid water-acetic acid and water-propionic acid have been determined. The respective eutectic points and the molar composition of the eutectic mixtures are as follows H*CO,H + 1*14H,O - 48' ; Me*CO,H + 2*40H,O - 2'7" ; Et*CO,H + 0*57SH,O - 29.4'. In no case is there evidence of chemical combination. The system butyric acid and water is being further investigated. G. S. Behaviour of Fatty Acids in Arnold's Distillation Process. A. HEIDUSCHKA and K. PFIZENMAIER (Pharm. Zentr-h.1909 50 85-86).-With reference to the publications of Dons (Zsiteh. Ndw. Genussm. 1907 14 150) and Arnold (ibid. 1908 16 705) on the subject of the fatty acids of butter the author has investigated the behaviour of each of the acids formic acetic propionic butyric hexoic octoic decoic lauric myristic palmitic stearic oleic and linoleic when mixed with water and distilled. It was found that (1) the distillate may have a constant composition which has no relation to the composition of the mixture under distillation or (2) its composition may vary with that of the mixture under distillation or (3) it may exhibit a combination of (1) and (2) being of constant composition for a certain concentration of the mixture under distilla- tion and exhibiting a proportional composition for other concentrations.A table of experimental results is given in the original. ..................... T. A. H Total Asymmetric Syntheses. ALFRED BYK (Ber. 1909 42 141-242).-Mainly a criticism of Henle and Haakh's paper (this vol. i 6). J. J. S.ORGANIC CHEMISTRY. 131 General Method for the Preparation of Trialkylacetic Acide. ALBIN HALLER and ED. BAUER (Compt. rend. 1909 148 127-132. Compare Abstr. 1908 j 987; this vol. i 108).- Trialkylacetophenones of the type COPh-CRR'R are dissolved in benzene or toluene and boiled for five hours with sodamide. The ketone undergoes decomposition into benzene and an amide of the type C RRR"mCO*NH2 which is readily converted by nitrosyl sulphate into the corresponding acid CRRR'*CO,H. Attempts to bring about a similar reaction in the case of dialkylallylacetophenones however have not been successful.The following new compounds have been prepared in this way aa-dimethyl-n-bzctyramide CMe,Et-CU-N H m. p. 103-104' ; aa-dimethyl-n-valeramide CMe,Pra*CO*NH2 m. p. 95-96' ; aa-dimethyl-n-valeric acid CMe2Pra*C02H b. p. 10 1-102"/ 1 1 mm. 1 90-200' under ordinary pressure ; a-methyl-a-etl&yl-n-butyr- amide CMeEt,*CO*NH m. p. 78-79" ; aa-cliethyl-n-b~tyranzide CEt,*CONH m. p. 108' b. p. 148-149'/30 mm. ; aa-diethyl-n-butyric acid CEt,*CO,H m. p. 39.5' b. p. 119'/14 mm. 220-222' under ordinary pressure ; a-methyl-a-ethyl-n-valeramide CMeEtPra*CO*NH2 m. p. 464 b. p. 134-135"/12 mm. ; a-methyl-a-ethyl-n-valeric acid CMeEtPF*CO2€€ b. p. 215-220". w. 0. w. Further Applications of the General Method of Hydrogenation Bwed on the Use of Finely-divided Metds. PAUL SABATIER and ALPHONSE R~AILHE (Anlz.Chim. Phys. 1909 [viii] 16 70-107).-Mainly a resume of work already published (compare Abstr. 1905 i 571 635 ; 1906 i 561 ; 1907 i 458 488 490 587 747; 1908 i 36 278 529) but the following facts have not previorisly been recorded (1) unsatnrated acids of the aliphatic series yield the corresponding saturated acid when directly hydrogenated in the presence of nickel ; thus crotonic acid at 190' is reduced to butyric acid and oleic or elaidic acid at 280-300' is reduced to stearic acid to the extent of 90% of that required by theory; (2) unsaturated ketones are converted into the corresponding saturated ketone by direct hydrogenation in the presence of nickel ; thus mesityl oxide yields isopropylacetone (p-methylpentan-Bone) and phorone yields diiaobutyl ketone ; (3) when the ketonic acids are directly hydrogenated in the presence of nickel the ketonic group only is reduced; thus l=vulic acid yields valerolactone and ethyl acetoacetate undergoes (a) the normal reduction yielding ethyl butgrate; ( b ) scission of the molecule and subsequent reduction of the products yielding acetone isopropyl alcohol and propionic acid ; and (c) a molecular condensation yielding solid dehydracetic acid. Methyl tert.-butylamine has b.p. 54-56" and the oxalate has m. p. 166" (not 58-60" and 160' respectively as stated previously Abstr. 1907 i 490). M. A. W. Action of Ozone on Oleic Acid. CARL D. HARRIES [with WALTHER FRANK] (Bey. 1909 42 446-458.Ccmpare Molinari Abstr. 1908 i 849 and Harries ibid. 387).-01eic acid ozonide,132 ABSI'ICACTS OF CHEMICAL PAPERS. after washing with sodium hydrogen carbonate solution and water has the same composition whatever the concentration of the ozone used may be. The formation of hydrogen peroxide by the decomposition of the ozonide with water is confirmed. The decomposition with water yields products containing 9 and not 18 carbon atoms and the primary products are aldehydes or their peroxides which are trans- formed into acids by a secondary reaction. These products have been re-investigated (compare Abstr. 1907 i 10). Nonaldehyde peroxide CgHlRO2 crystallises from light petroleiim in glistening plates m. p. 73" and hasall the characteristic properties of a peroxide.Its b. p. under reduced pressure is higher than that of nonaldehyde but lower than that of pelargonic acid. When boiled with water it yields nonaldehyde and hydrogen peroxide. The other products isolated were pelargonic acid and the semi-aldehyde of azelaic acid all of which are obtained from the original ethereal extract. The aqueous solution when acidiced yields an ethereal extract from which the peroxide of the semi-aldehyde of azelaic acid C9H,,0 and azelaic acid have been isolated. The peroxide crystallises from acetone in needles m. p. 98" and is completely soliible in hot water but is partly converted into the semi-aldebyde and hydrogen peroxide and paitly isomwised t o azelaic acid. Semi-aldehyde of Succinic Acid [P-Aldehydopropionic Acid].-cARr D.HARRIES and ERNST ALEFELD (Ber. 1909 42 159-165. Compare Harries Abstr. 1898 i 232).+?-Aldehydo- propionic acid has been described by Perkin and Sprankling as a thick dark yellow oil which is readily oxidised by atmospheric oxygen to succinic acid (Trans. 1899 75 11). von Ungern-Sternberg prepared P-aldehydopropionic acid from aconic acid and describes it ae an oil solidifying to a white crystalline mass m. p. 147O b. p. 234-236",760 mm. which is very stable towards oxidising agents but nevertheless has the properties of an aldehydo-acid; thus i t yields n phenylhydrazide-phenylhydrazooe m. p. 182'. The conclusion drawn by this author was that Perkin and Sprankling were either not working with P-aldehydopropionic acid or else that their statement as to the readiness with which the acid underwent oxidation was incorrect (Diss.Konigsberg 1904). The present authors have prepared P-aldehydopropionic acid by decomposing allylacetic acid ozonide with water. They obtained it as an oil which was readily oxidised by atmospheric oxygen forming succinic acid. The oil when kept for a few days however solidified to a white crystalline mass m. p. 147" identical with the substaxIce described by von Ungern-Sternberg. MoLmt. determinations show that the oily acid is unimolecular wbereis the solid acid is bimolecular (compare following abstract). prepared by the action of ozone on a solution of allylacetic acid in carbon tetra- chloride is a colourless syrup Dii 1.289 Dti 1.297 nil 1.46552 n," 1.47359; it is decomposed by water yielding formic acid form- J.J. S . Allylacetic acid oxonide O,< CH2 I CH C H,* C H,* C 02H'ORGANIC CHEMISTRY. 133 aldehyde succinic acid and P-aldehydopropionic acid ; it is probable that the peroxide of the latter substance is formed at the same time. The nnimolecular P-aldehydopropionic acid is a colourless viscid liquid b. p. 134-136O/14 mm. DZ 1.2568 ng3 1.44873 nz 1.44571 1.45911 ; it follows from these physical constants and from the absence of a ferric chloride reaction that the substance is the aldehyde form of the acid. NII,-NH*CO*N CH* CH,*CH,* CO,H crystallises in small prisms or needles m. p. 177-1 78" (decomp.) ; the p-nitroplmzylhydrazone C10H1104N3 forms golden-yellow leaflets IU. p. 158'. P-Aldehydopropionic Acid.CARL D. HARRIES and ALFBED HJXMELXANN (Ber. 1909,42 166-167).-The crystalline P-aldehydo- propionic acid prepared from allylacetic acid (compare preceding abstract) or from aconic acid (compare von Ungern-Sternberg Dim. Konigsberg 1904) is shown to have the bimolecular formula (C,H,O,),. It yields the unimolecular variety when distilled at 134-136" under a pressure of 14 mm. The stability of the polymerised form towards oxidising agents shows that the cocdensation occurs between the two carbonyl groups thus The 8enaicai*bazone W. H. G. CO,H* CH2*CH,*CH<~>CH*CH2*CH2*C02H. W. H. G . Molecular Rearrangements in the Camphor Series. I. Hydroxylauronic Acid and isoCampholactone. WILLIAN A. NOYES and A. W. HOMBERGER (J. Amer. Chern. Soc. 1909 31 278-281).-1t has been shown (Abstr.1895 i 295) that amino- lauronic acid is converted by nitrous acid into y-lauronolic acid laurolene and isocampholactone. When ethyl aminolauronate is treated with nitrous acid it yields a mixture of ethyl y-lauronolate and ethyl hydroxylauronate. Ethyl y-lauronolute C,H,,-CO,Et b. p. 110-115°/25 mm. has Di0 0,9514 and [a12 + 56.6'. Ethyl hydroxylauronate OH*C8El,*C02Et b. p. 150°/30 mm. has Di0 1.100 and [a]:'' + 6-73' Evidence is given t o shorn that hydroxylauronic acid has the v CH2-FH2 C&le,*CH* OH' which is supported by the fact formula CO,H*CMe< that the acid is oxidised by k t r i c acid to active camphoronic acid. The method of formation of isocampholactone suggests that it should be represented by the annexed formula. CO*CMe<CH2-$!H2 I n this case the corresponding hydroxy-acid OH-C,H,,*CO,H must be a stereoisomeride of l I hydroxylauronic acid.In order t o obtain evi- dence on this point isocampholactone was sub- 0 mitted to oxidation with nitric acid. The productas obtained were a Zccctone CsH1204 an acid m. p. 228O probably camphononic acid and a compound m. p. 11l0 which is probably a lactone. The Znctone C,H,,O m. p. 122O b. p. 272O is the chief product of the oxidation and crystallises in needles. These results do not justify any conclusion with regard to the structure of isocampholactone. CMe2*CH E. G .134 ABSTRACTS OF CHEMICAL PAPERS. Ethyl Nitrososuccinate. JULIUS SCHMIDT and KARL TH. WIDMANN (Be?.. 1909 42 497-501).-A general method for the production of nitroso-compounds is to pass the nitrous gases from tbe action of nitric acid on arsenious oxide into acylcarboxylic esters.The method gives especially good results when the acyl group is attached to a tertiary carbon atom. Ethyl acetylsuccinate when treated with the gas at 0' in a long narrow tube then after two hours evacuated in a dark glass desic- cator forms ethyl nityososuccinate CO,Et*CH(NO)*CH;CO,Et an azure-blue liquid which cannot be distilled and is decomposed quickly by light. It is however pure ; in a ethylene dibromide solution it is unimolecular (found 185 and 194 calc. 203) DIE 1.20 n 1.4419. The compound gives Liebermann's reaction is stable in ethylene dibromide but in alcohol or ether the cold solution is slowly decolorised quickly when warm. This change may be due either to polymerisation or isomeric change to oximino-compounds. Potassium permanganate Caro's acid or hydrogen peroxide (10%) oxidise it to ethyl nitro- succinate C,H,,O,N? a yellow viscous oil which could not be distilled unchanged under diminished pressure and explodes when quickly heated.On reduction with zinc dust and acetic acid ethyl aspartate is formed b. p. 126-127'/10 mm. 150-152'/25 mm. (compare Fischer Abstr. 1901 i 193) ; the picrolonate C,Hl,O,N,CloHsO,N forms yellow crystals m. p. 290O. W. R. Products of Hydrolysis of Ethyl Dioxalylsuccinate. GoPyromucio Acid. EDMOND E. BLAISE and HENRI GAULT (Compt. rend. 1909 148 176-179. Compare Abstr. 1908 i 713).-The authors consider that their experiments on the production of iso- pyromucic acid by the removal of 1C0 from the product of hydrolysis of ethyl oxalylsuccinate furnish evidence against the constitutions ascribed by Wislicenus to the substances this author obtained by the action of alkalis on the ester (Abstr.1895 i 506). Thus the compound t o which Wislicenus gave the formula CO Et $' C( C02E t ) CO,Et*CO* CH-CO>' >O; the CO,E t Q=C( C0,Et) CO,Et e:C(OH)-CO should be represented as a &lactone substance obtained from this by hydrolysis mould then have the formula C02H* C( OH) :C(CO,Et) C( CO Et) C( OH)*CO,Et which agrees more closely with the properties of the compound than the ketonic structure put forward by Wislicenus. w. 0. w. Laevulinaldehyde. CARL D. HARRIES and MAX BOEGEMANN (Ber. 1909 42 439-446. Compare Abstr. 1906 i 364 ; 1906 i 833).- The aldehyde was prepared by the action of water on methylheptenone ozonide (Abstr. 1906 i 226).It dissolves readily in water and reduces cold Fehling's solution. I t s molecular weight as determined by the cryoscopic method in benzene solution proves it to be uni- molecular and its molecular dispersion agrees with the ketoaldoic constitution. Its dielectric constant as determined by Nernst'sORGANIC CHEMISTRY. 135 method is high namely 32 at lSO whereas the constant for succin- aldehyde is 28.5 at 20’. The dioxime has m. p. 7 6 O ; the disemicarbmone C7HI4O2N6 crystal- lises from methyl alcohol in colourless plates or prisms m. p. The diphenylhydrazone has not been obtained ; phenylhydrazine reacts with an acetic acid solution of the aldehyde yielding an oil which with hydrochloric acid forms phenylmethyldibydropyridazine.As this compound is sparingly soluble it can be made use of in estimating the aldehyde. The di-p-nitrophenylhydrazom Cl:HI,O,N crystallises in brown plates m. p. 106O. The aldehyde reacts with an alcoholic solution of pyruvic acid and 178-1 80’. P-naphthylamine yielding kstobutylnup~t?~acinc?~onic &d N==C*CH,-CH,COMe 9 c,oH6<C( C0,H 1 jlH which is sparingly soluble i’n ah ordinary solvents. Lavulinaldehyde differs from succinaldehyde which also contains carbonyl groups in the as-positions in the following points (1) it does not polgmerise; (2) i does not give Angeli’s reaction with benzsulph-hydroxamic acid Ttr. 1904 ii 330)’ and (3) it is not readily converted into acetals b When reduced with a large e .cess of aluminium amalgam and ether it yields y-amylene glycol and Lipp’s methyldihydrofuran (Abstr.1889 843). laisen’s method. J. J. S. Certain Numerical Relations in the Sugar Group. C. S . HUDSON ( J . Amer. Chem. Xoc. 1909 31 66-86).-0n the assumption that the known a- and p-forms of dextrose and the related mutarotating sugars are the partial stereoisomerides indicated by the lactonic formula of Tollens it is shown (1) that the difference between the molecular rotations of the a- and p-forms of all the aldehyde sugars and all their derivatives in which the added substance is not joined directly to the end asymmetric carbon atom is a nearly constant quantity; (2) that the a- and @-forms of those derivatives of any aldose sugar in which only the end carbon atom is affected (a.g.glucosides) have molecular rotations the sum of which is equal to the sum for the a- and p-forms of the aldose and it is shown from the available data that these deductions are valid. On this basis the following rules are proposed for the naming of the a- and p-forms of the sugars The names are to be so selected that for all sugars which are genetically related to &-glucose the subtraction of the rotation of the p-form from that of the a-form gives a positive difference and for all sugars genetically related t o I-glucose a negative difference. When the end carbon atom is affected the above rule is modified as follows The names of the a- and p-forms are t o be so selected that the difference of their molecular rotations is equal to aud of the same sign as the similar difference for the forms of the similar derivative of that glucose (d or I ) to which the first sugar is genetically related.136 ABSTRACTS OF CHEMICAL PAPERS.The equilibrium constant for the reversible reaction between the a- and /3-forms of the aldohexoses and allied disaccharides is approxi- mately constant and equal to 1.5 a rule which permits of the calcula- tion of the rotation of the unknown forms of certain sugars. From measurements of the " thermal lag " (compare Abstr. 1908 ii 665) it is shown that in all cases the a-form of the sugar is favoured by an increase in temperature. A formula is deduced which allows of the calculation of the rotatory power of the unknown forms of many of the natural and synthetic glucosides.The influence of t h e end groups of the gliicosides on the rotation of the carbon atom to which they are attached depends mainly on the weight of the group. G. S. Preparation and Properties of P-Glucoheptitol. L. H. PHILIPPE (Compt. rend. 1908 147 1481-1483).-The author has submitted Fischer's P-glucoheptose (Abstr. 1892 1164) to the prolonged action of sodium amalgam; he thus obtains P-gluco- heptitol OH*CH,*Y -$J-? -$J-y*CH2*OH. ?H ?H ?H H H H OH H OH This compound forms small rectangular tablets m. p. 130-131O on the Maquenne block ; [a] + 48' in aqueous solution. I t s rotatory power serves t o distinguish it from the isomeric a-glucoheptitol (loc. cit.). Acetic anhydride in presence of zinc chloride converts it into a resinous heptu-ucetyl derivative C,H,(OAc) m.p. about 50' ; [ a3E + 34.8'. The Aeptabenxoyl derivative C,H,(OBz) forms prismatic needles m. p. 183'. The tpibenzylidene derivative C7H1007( C7H& crystallises in very slender needles m. p. about 230O. Aformulacetal w. 0. w. derivative has also been prepared. Hydrolysis of Maltose by Citric Acid. JOSEPH PIERAERTS (Bull. Assoc. CAim. SUCT. dist. 1909 26 562-573).-Hydrated maltose may be converted completely into 2 mols. of dextrose by boiling 50 C.C. of a 290h solution with 10 C.C. of 20% citric acid for about thirty hours in a reflux apparatus. The time may be reduced to two hours and a-half by heating at a pressure of 14 atm. As soon as the maltose is converted into dextrose the liquid assumes a yellow colour which dnrkens on prolonged heating.L DE K. Formation of Hydrocelluloses by m e a n s of Sulphuric Acid. CARL G. SCHWALBE (Zeitsch. usagew. Chem. 1909 22 155-156. Compare Biittner and Neuman (this vol. i 86).-The author claims that elementary analyses are not sufliciently accurate t o serve for the clear diagnosis of different hydrocelluloses. The reducing powers are much more accurate criteria. Both acids and alkalis hydrolyse hydrocelluloses. J. J. S. Acid Haloid Salts. FELIX KAUFLEB and E. KUNZ (Ber. 1909 42 355-392. Compare Scholl and Escales. h b s t r 1898 i 182; Korczyriski this vol. i 123).-lt is shown that a large number ofORGANIC CHEMISTRY. 13'7 mono-amines combine with dry hydrogen chloride or bromide at the ordinary temperature forming dihydrochlorides and dihydrobromides.The stability of the dihydrochloride depends largely on t h e degree of alkylation ; thus tertiary and quaternary bases regularly form dihydrochlorides whilst of the secondary bases only dimethylamine forms a dihydrochloride. Dihydrochlorides of methylamine methyl- aniline aniline acetanilide methyl-o-toluidine diphenylamine and tribenzylamine could not be obtained at the ordinary temperature. When a compound contains several nitrogen atoms i t is found that each nitrogen atom reacts independently. The conclusion is drawn that the compounds are in all cases ammonium salts of perhalogen hydrides. This is supported by the fact that the change of p-nitrosodimethylaniline hydrochloride into the di- hydrochloride is not accompanied by a change of colour as in the forma- tion of the former from the base itself.The following formulation y X N -+ If N j G l - - + [; N4[Cl2H] shows that in the conversion of the hydrochloride into the dihydro- chloride 'only the colourless anion undergoes alteration whilst the ammonium part of the molecule which imparts the colour to the substance remains unchanged. The following salts were prepared by passing the dry halogen hydride over the base or its normal haloid salt. They are all hygro- scopic substances and readily part with hydrogen chloride or bromide. Dimethylamine dih ydrochloride is a white cryst d i n e subs tance. Tetrcumethylammonium chloride hydrochloride NMe,Cl,HCl forms a white crystalline mass. m-NitrodinLethylaniline dihydrochloride C,H,o0,N2,2HCl i ; a yellowish-white crystalline mass.p-Nitroso- dimethylaniline dihydvochloride is a yellow powder. Dimethyl-o- toluidine dihydrochloride was obtained as an oily liquid. Diethyl- aniline dihgdvochloride C,,H1,N,2HC1 forms colourless crystals which solidify at 47O. p-Nitrosodieth3/laniline dihydrochloride is a yellow powder. Pyridine dihydrochloride C5H,N,2HCl forms large white prisms m. p. 46.7O. Quinoline dihydrochloride C,H,N ,2HC1 is a crystalline mass having the same freezing point as the pyridine compound. Tetramethgldiarninodiphenylmethane tetrahydrocidoride C17H22N,,4HCI is a brown solid. ~etramethyldiami~nodip~r~yZ ketone tetrahpdrochhide is obtained only at Oo. pAzotoluene dihydro- chloride C,,H1,N2,2HCl is a chocolate-brown solrd. Diethylamino- axobenxene dihydrochlorida has the same red colour as the mono- hydrochloride Dieth~lamiwaxobenzene-P-naphthdene psntahydro- chloride resembles potassium permanganate in colour. Pyridina dihydro bromide C H,N 2H Br .pinoline dih ydro bromide and diethylccminoaxobenxene pentahydvobromade were also prepared. W. H. G d-Propylenediemine and Derivatives of the Optically Active Propylenediamines. LEO TSCHUCIAEFF and W. SOEOLOFF (Ber. 1909 42 55-58. Compare Xbstr. 1907 i 896).-The data138 ABSTRACTS OF CHEMICAL PAPERS. previously given for I-propylenediamine are to be corrected to Cobalt-tri-1-propylenediamine iodide [ CoPn,]I prepared in a similar manner to the racemic iodide (Pfeiffer and Gassmann Abstr. 1906 ii 614) separates from hot water in brownish-yellow needles contain- ing 2H,O is much more soluble than the racemic iodide and for a sample dried a t 100" shows [.ID + 23.63' for p 3.38 and DT 1.0156.d-Propylenediamine separated from the racemic base or from the non-crystalii*able syrup remaining after the preparation of the I-isomeride (Zoc. cit.) by means of the d-propylenediamine hydrogen Ltartrate has b. p. 120*5" Di5 0.8584 and [.ID + 29*78" and yields like the I-isotneride (loc. cit ) a platinum di-d-~opylenediarrLi~e chloride [PtPn,]Cl which has [ u J D - 46-45' for p 8.27 and Df" 1.0445 from which the nitrate [PtPn,](NO,) is obtained having [.ID - 40 55" for Degradation of a-Amino-acids to Aliphatic Aldehydes by means of Sodium Hypochlorite. KURT LANQHELD (Ber. 1909 42 392-393).-Raschig has shown (Abstr. 19OS ii 30) that chloro- amine is formed by the interaction of sodium hypochlorite and ammonia.A similar reaction appears to take place between sodium hypochlorite and a-amino-acids ; an intermediate product is formed which does not colour aqueous aniline and decomposes when the solution is warwed at 40-50" yielding ammonia carbon dioxide and an aliphatic aldehyde containing one carbon atom less than the acid. The reaction probably takes place thus R*CH(NQ,)*CQ,H + NaOCl -+ K*CH(NHCl)*CO,H -+ DF 0.8612 and [ a ] D -29.65". p 8-36 and Di6 1.0465. c. s. &KJ R*CH:NH + CO + HC1-+ R*CHO + NH,. Internally Complex Salts. HEINRICH LEY (Ber. 1909 42 354-376).-1n the internally complex copper salts of a-amino-acids the union of the metal to oxygen by a principal and to nitrogen by a supplementary valency linking (Abstr.1905 i 175) causes the properties especially the colour and the dissociation of these complex salts to differ from those of ordinary salts. The electrolytic and the hydrolytic dissociation of copper glycine and of copper a-alanine are very small ; the solutions can be boiled without deposition of copper hydroxide. Such stability is not shown by the copper salts of all a-amino-acids those of piperidinoacetic or diethylaminoacetic acid (of the type NR,*CH,*C02H) being slightly electrolytically but considerably hydrolytically dissociated ; a complex nickel piperidinoacetate cannot be prepared by reason of its great hydrolytic dissociation. The complex copper salts of 6-amino-acids are moderately hydrolytically dissociated and in dilute solutions precipitation of copper hydroxide occurs.Complex copper salts of 6-amino-acids the formation of which would require the production of W. H. G. a seven-membered ring CH2<gZ%S!>Cu cannot be obtained (compare Tschugaeff Abstr. 1907 i,&392)f The fact that glycine can displace the metal from salts of strongerORGANIC CHEMISTRY. 139 (NH,*R*CO,),M + 2HX where M = Cu Ni Go or Zn proceeding almost entirely from left to right in consequence of the very slight electrolytic dissociation of the complex salt. (The equation only partly represents what occurs; in addition the acid HX forms a salt with the amino-acid. Since the salt formation is very small with acetic acid the author uses acetates in the following experiments.) Conductivity measurements give bome idea of what is happening i n the reaction.The difference A between the conductivities of the metallic acetate before and after the addition of the amino-acid is approximately a measure of the complex salt formation because if (NH,-R*CO,),M is largely formed the conductivity of the solution will approach that of acetic acid whilst the conductivity mill be mainly due to the metallic acetate if complex salt formation is only small. In this way it is shown that barium manganese and cadmium have little tendency to form complex salts and copper and nickel have a great tendency; the tendencies of cobalt and zinc are about the same and much smaller than that of nickel. With nickel acetate and different amino-acids the formation of internally complex salts decreases from glycine through a- and P-aminopropionic acids to piperidinoacetic acid ; with copper acetate and y-aminobutyric acid negative values of A that is an increase of the conductivity are observed which is explained by the fact that a partial formation of basic copper acetate occurs in consequence of the large basic k value of the amphoteric electrolyte.The abnormal colour of complex salts has been examined spectro- metrically. The complex copper salts of glycine P-aminopropionic acid methylglycine benzylglycine aa-dimethylglycine a-phenyl- glycine diethylglycine and piperidinoacetic acid are all blue in the solid state and violet-blue in solution. The substitution of methylene hydrogen by phenyl does not produce any essential colour change. The replacement of aminic hydrogen by an aromatic group causes a great change in the absorption internally complex coppzr anilino- acetate and its homologues being intensely green in the solid and the dissolved states. The addition of ammonlum hydroxide to copper anilinoacetate causes a colour change from green to blue probably by reason of the conversion of the internally complex salt into an ordinary complex salt ; a similclr conversion occurs with ammonium hydroxide and copper glycine although here no essential colour change is observed O*CO* H2 O*CO*CH,*NH I cu e:c<NHz + 2NH = H,N..-,du 0. COO CH H,N*’* I 0.CO C H,*NH I T H 2 The decomposition of metallic acetates by amino-acids is accom- panied by colour change when internally complex salts are formed; nickel acetate become3 distinctly blue by the addition of glycine or a- or P-aminopropionic acid.It is noteworthy that the colour of cobalt acetate is unchanged by the addition of glycine and also that solid cobalt anilinoacetate has the normal red colour. It is well known that the strengths of amino-acids are increased by140 ABSTRACTS OF CHEMICAL PAPERS. the introduction of acyl groups. The metallic salts of aceturic acid (acetylglycine) are strongly dissociated and do not behave as internally complex salts copper aceturate and nickel aceturate having the normal blue and green colours respectively. The ultraviolet absorption spectra of aqueous copper acetate in the presence of increasing amounts of ammonia indicate that Cu( NH,),(C2H,02)2 and Cu( NH,),(C2H,0,) respectively are present according as the concen- tration of the ammonia is small or large thus confirming the results of the partition experiments previously described (loc.cit.). The paper concludes with some remarks on the migration of cations Some Derivatives of 6-Aminocaproic [Hexoic] Acid. AUGUST ALBERT (Ber. 1909 42 556-558).-Ethyl 6-phthaliminobutyl- malonate (Abstr. 1899 i 595) which crystallises from petroleum in needles m. p. 4 6 O is converted into the acid C,H402:N*[CH2]4*CH(C02H)2 by warming for a short time with hydriodic acid; it crystallises from a mixture of ethyl acetate and benzene in needles m. p. 127O decomposing into r-phthaliminohexoic acid (Abstr. 1908 i 649). As the yield of the latter was only 16% another method for its preparation was devised.r-Chlorohexonitriles is obtained in 32% yield by heating pentamethylene chloride and potassium cyanide in aqueous alcohol solution for seven hours (compare von Braun and Steindorff Abstr. 1905 i 206). The portion b. p. 242-250° when heated with potassium phthalimide at 210° is converted into crude r-phthaliminohsxonitrile. This oil when heated with double its volume of sulphuric acid for ten minutes at looo yields a mixture of c-phthaliminohexoamide C,H,O :No[ CH,] 430 NH which crystallises from alcohol in leaflets m. p. 1 5 8 O and the corresponding acid. The yield from the pentamethylene chloride is 12%. Red phosphorus and bromine convert phthaliminohexoic acid into a- bromo-r-phthaliminohexoic acid C,H,O,:N* [C R2],=CHBr*C02H which forms crystals m.p. 153-153P. An attempt to prepare a€-diaminohexoic acid from this failed through lack of material. of type CO,H*R*NH,. c. s. W. R. The Nature of Hofmann’s Bromoacetamide. MAURICE FRAN~OIS (Compt. rend. 1909 148 173-176 ; J. Phamn. Chim. 1909 [vi] 29 145-151. Compare this vol. i 13).-The substance t o which Hofmann (Abstr. 1882 950) ascribed the constitution CH3*CO*NHBr,H20 has been prepared by evaporating below 30° an aqueous solution of acetamide and pure hypobromous acid. The con- clusion is drawn that the compound is acetamide hypobromite CH,* CO NH,,HOBr and that Hofmann’s bromoacetamide which arises from this bv dehydration should be regarded as a secondary amide of hypobrornois acid. w. 0. w. Action of Nitrogen on Commercial Barium Carbide. OTTO E~HLINCI and 0.BERKOLD (Zeitsch. angew. Chem. 1909 22? 193-1 97).-The influence of barium chloride on the absorption ofORGANIC CHEMISTRY. 141 nitrogen by a heated mixture of barium carbonate and charcoal has already been determined (Abstr. 1908 i 143) and the investigation has been extended to barium carbide. Moissan (Abstr. 1894 i 314) has already shown that this compound only combines with traces of nitrogen at 1200" but the effect of other substances was not ascertained. The barium carbide used in the experiments had the following composition Ba 49.86; Ca 17.11 ; Fe+Al 2.62; '' carbide " carbon 7.62 ; Na 0 85 ; C1 0.18 ; insoluble matter 9.76 ; P S 0 and CO 12.00% (by difference) and the material therefore probably contains both calcium and barium carbides as well as their oxides. The absorption of nitrogen with this material begins at 500-600° and there is an increase in the nitrogen absorbed as the temperature rises to 920-930° when the maximum amount is absorbed the percentage of cyanide formed at 920-930' being 18.4 that of cyanamide 19.4.With 10% barium chloride the maximum absorption is attained at this temperature also but with 20 and 30% of added chloride the maximum had not been reached at 1120-1130°. With the larger amount of chloride a t the latter temperature the yield of cyanide was somewhat greater (21*6%) the yield of cyanamide some- what less (17.9%). W. R. Preparation of Cyanuric Acid from Carbamide. REINHOLD VON WALTHEB (J. p . Chem. 1909 [ii] 79 126-128).-Cyanuric acid is obtained in 62% yield by heating carbamide with twice its weight of anhydrous zinc chloride at 220° decomposing the cold product with hydrochloric acid and recrystallising the precipitate from hot water.c. s. Molybdenum Hexathiocyanate Saltrs. ARTHUR ROSENHEIM (Ber. 1909 42 149-152).-Largely polemical A reply to Maas and Sand (Abstr. 1908 i 961 ; compare also ibid. i 397 513 614). It is suggested t h a t many of the thiocyanate values obtained by Sand and Maas are low owing to the oxidising action of the nitric acid used. When a thiocyanate is boiled with sodium hydroxide solution a small amount of ammonia is liberated but the amount is so small that the error introduced into the estimation of ammonia would scarcely affect the formula deduced from the experimental data. The sodium salt Na3Mo(SCN),,12H,O forms golden-yellow crystals and agrees in composition with the sodium salts of other complex thiocyanates.J. J. S. CARL W. H~~BNER (J. pr. Chem. 1909 [ii] 79 66-71).-This investigation was carried out with the object of filling some gaps in the chemistry of the dinitriles. Only one of the three condensation products obtained by von Meyer (Abstr. 1895 i 582) by the action of phenylcarbimide on diacetonitrile LP-imino- butyronitrile] in benzene namely that having m. p. 148O (von Meyer gives m. p. I5Oo) is formed when ether is employed as the solvent. Bsnzacetodinitrile [P-iminophenylpropionitrile J and phenylcar bimide Dimolecular Nitriles. VOL. XCVI. i. I142 ABSTRACTS OF CHEMICAL PAPERS also interact at the ordinary temperature in ethereal solution yielding the analogous additive product m.p. 190' (compare von Meyer Zoc. Phenylthiocarbimide reacts in a similar manner with P-iminobutyro- cit.). nitrile at 140-150° yielding the additive product which crystalliees in small orange-yellow needles m. p. 1 9 2 O . P-Imino- phenylpropionitrile yields the analogous additive product CN*CH,* CPh:N* CS*NHPh small lemon-yellow needlos m. p. 166' which when heated under pressure at 140-150O with alcoholic ammonia and lead oxide yields the guanidine derivative C,,H,,!,:NH white leaflets m. p. 1 7 8 O and when treated with nitrous acid yields the nitroso-derivative CN*CH,*CPh:N*CS*NPh-NO lemon-yellow needles m. p. 231'. The additive product obtained by heating P-iminobutyronitrile with dicyanodiamide a t 150' (compare von Meyer Zoc.cit.) has the formula C6HqON,. ; it f orrns a platinichloride (C,H,ON,),,H,PtCI which crystallises in golden-yellow needles m. p. 240' (decornp.). CN.CH,*CMe:N*CS*NHPh W. H. G. Action of Cyanogen on Sulphurous Acid. DANIEL VORLA~DER (Verh. Ges. deut. ATaturforsch. Aerxte. 1907 ii 92).-The action of cyanogen on sulphurous acid is similar to t h a t of the halogens but occurs more slowly C,N + H,SO + H,O = 2HCN + H,SO,. IVith equivalent quantities in 0.1 to 0.2% solution the amounts of cyanogen reduced and of sulphurous acid oxidised are initially equivalent. With a large excess of cyanogen 94% of the sulphurous acid is oxidised after four t o five days but when the acid is in excess only 23% of the cyanogen is reduced in seven to eight days.c. 8. Production of White Ferrous Ferrocyanide. ROBERT L. TAYLOR (Mem. Manchester Phil. Xoc. 1908-09 53 vi).-A creamy- white precipitate is obtained on adding potassium ferrocyanide t o a solution of a ferrous salt which has been thoroughly reduced by hypo- sulphurous acid or sodium hyposul phite Na,S,O,. Hyposulphurous acid will even reduce [precipitated Prussian blue to the white ferrous compound. R. J. C. Prussian Blue and Turnbull's Blue. I. ERICH M~~LLER and THEOPHIL STANISCH (J. pr. Chem. 1909 [i$ 79 81-102).-1n a solution containing ferric and ferrocyanogen ions or ferrous and ferri- cyanogen ions the value of the equilibrium constant K(= [Fe"'] [FeCy,""]/[Fe"].[FeCy,"']) calculated from electrochemical data (Abegg Abstr. 1903 ii 628 ; Schaum Abstr. 1900 ii 2) is about and therefore either solu- tion will contain practically only ferrous and ferricyanogen ions.Consequently the precipitates obtained from ferric chloride and potassium ferrocyanide or from ferrous chloride and potassium ferri- cyanide should be identical. The preceding reasoning however is inaccurate since it assumes that all the ions remain in solution TheORGANIC CHEMISTRY. 143 authors agree with Hofmann (Abstr. 1905 i 38) that the preceding precipitates are ferrocyanides but deny that soluble and insoluble Prussian blue are identical respectively with soluble and insoluble Turnbull's blue. They object that Hofmann actually isolated the pre- cipitates which probably changed during the process and only deter- mined the iron and cyanogen or the ratio Fe CN which-cannot give accurate information as to the composition of these complex and very similar blue ferrocyanogen compounds (compare Illessner Abstr.1895 i 486). The authors determine the compositions by a method which does not involve the separation of the precipitates from the mother liquor and also estimate the ratio of ferrous to ferric iron and of ionised and non-ionised iron. I n definite volumes of for example standard ferric chloride and standard potassium ferrocyanide the amounts of Fe"' and of (FeCyJ"" are estimated by standard potassium permanganate before and after mixing 0.1-molecular solutions being used to minimise the error due to any volume change on mixing. The decrease in the concentration of the ions represents the amounts which have disappeared from the solution to form the precipitate but in consequence of the reaction Fe"' + (FeCy,)"" Fe" + (FeCy,)"' it is not allowable to assume that the for example ferric iron whici has disappeared from the solution occurs as such in the precipitate.However the ratio of ferrous to ferric iron and of ioriised to non- ionised iron can be estimated in the precipitate and hence conclusions drawn as to its constitution. The authors find that ferric chloride and potassium ferrocyanide in proportions exceeding 4 3 give insoluble Prussian blue Fe1114( Fe11Cy6)8 whilst in proportions less than 1 1 the precipitate is a mixture of KFelll(FellCy,) + K,Fel'(Fel'Cy,) ; ferrous chloride and potassium ferricyanide in proportions exceeding 4 3 yield insoluble Turnbull's blue KFe11EIe1rr3(Fer'Cy,)3 whilst in proportions less than 1 1 I(Fe1'I(Fe1'Cy6) is formed.The Roman numerals denote the valency of the iron. c. s. cycZoPropane. ALFRED PARTHEIL ( Verh. Ges. deut. Naturforsch. Aerxte. 1907 ii 159).-cycZoPropane can be prepared by heating together finely-divided zinc arnyl alcohol and trimethylene bromide. c. s. Introduction of Iodine into the Benzene Ring. ADOLF OSWALD (Zeitsch. physiol. Chem. 1908 58 290-294. Compare Abstr. 1903 i 450 ; Messinger and Vortmann 1889,1150 ; Wheeler and Jamieson 1905 i 35O).-Fiirth and Schwarz's statement (P'liiger's Archiu 1908 124 113) that phenylalanine can yield an iodo-derivative when treated by Messinger and Vortmann's method is refuted. Unaltered phenylalanine alone was recovered.Phenyl- acetic and phenylpropionic acids behave in a similar manner. The formation of iodo-derivatives only occurs when the benzene nucleus contains one or more hydroxyl groups. I n certain reactions the pyrrole ring behaves as a phenol for example yields a tetraiodo- 2 2I44 ABSTRACTS OF CHEMICAL PAPERS. derivative and it is possible that the re-activity of tryptophan to iodine is due to the presence of the pyrrole group. J. J. S. [Nitronitrosotetramethyldiaminophenylbenzylsulphone.] ARTHUR I ~ N Z (Ber. 1909 42 385).-The formula NMe,*C,H,(NO,)*CH,*SO,*C,H,(NO)~NMe or a similar one in which the positions of the nitroso- and the nitro- groups are interchanged is in better agreement with the analytical data for the nitroso-derivative obtained from tetramethyldiamino- benzylphenylsulphone than that originally given (A bstr.1908 i 940). c. 8. The Action of Arsenites on Toluenesulphonyl Chloride. AUGUST rGUTMANN (Rev. 1909 42 480-483).-An aqueous solution of trisodium arsenite reacts with p-toluenesulphonyl chloride yielding sodium toluenesulphinate and trisodium arsenate. It is suggested that the chloride first reacts with the alkali yielding sodium hydro- peroxide NaO*OH which then oxidises the arsenite to arsenate. The formula R*SO*OCl for the sulphonyl chloride is accepted. Sodium arsenite has no action on sodium p-toluenesulphonate. An alkaline solution of sodium sulphite reacts with the sulphonyl chloride in much the same manner as the arsenite and is oxidised t o sulphate. J. J. S. p-Tolueneaulphinic Acid. A.HEIDUSCHKA (Verh. Ges. deut. Naturforsch. Aerzte. 1907 ii 170-172).-When ammonia is passed into an alcoholic or ethereal solution of p-toluenesulphinic acid the corresponding ammonium salt is formed whilst in benzene the reaction yields p-tolyl disulphoxide p-toluenesulphonic acid and water It is suggested that the ammonia acts as a base in the former more concentrated solutions whilst in the dilute solution in benzene it acts as a catalyst. Primary amines show a similar behaviour ; in equal molecular quantities they react with p-toluenesulphinic acid t o form salts whilst if the amine is present in less than equal molecular quantity the acid decomposes in accordance with the preceding equation. p-Toluenesulphinic acid decomposes in the same way in boiling water or by melting.The decomposition may throw some light on the nature of the highly-coloured products which are obtained by fusing amine toluenesulphinates (compare Meyer Abstr. 1901 i 3C,K,*SO,H = C7H7*S02*S*C,H7 + C,H,*SO,H + H20. 264). c. s. Triphenylmethyl. XVIII. Tautomerism in the Triphenyl- methane Series. MOSES GOMBERG (Ber. 1909 42 406-417).-1t was stated previously that triphenylmethyl chloride and its analogues exist [in a benzenoid form and a quinonoid form (compare Abstr. 1907 i 504). This statement has been combated however by von Baeyer (Abstr. 1907 i 691) and by Tschitschibabin (Abstr. 1907 i 1022). Evidence is brought forward in the present communication in support of the author’s view. A solution of tri-p-bromotriphenyl- methyl chloride in liquid sulphur dioxide which has been kept forORGANIC CHEMISTRY.145 some time at 45-55' and then cooled deposits colourless crystals which analyses show to be composed of a mixture of tri-p-bromo- triphenylmethyl chloride and 4-chloro-4' 4"-dibromotriphenylmethyl bromide In one experiment the isomorphous mixture contained about ,85% of the latter substance. There is little doubt that the transformation of the carbinyl chloride into the isomeric carbinyl bromide takes place owing to the intermediate formation of the quinonoid modification thus C(C,H,Br),Cl C(cGH,Br),:cGH4<~~ C(C6H4Br)2<~~H4ul. Attempts t o separate the pure carbinyl bromide by repeated crys tallisa tion of the mixture were unsuccessful. The action of liquid sulphur dioxide on 4-bromotriphenylmethyl chloride 4 4'-dibromotriphenylmethyl chloride 4-chloro-4' 4"-di- bromotriphenylmethyl chloride and 4 4'-dichloro-4"-bromotriphenyl- methyl chloride has also been studied.It is found in each case that a certain amount of the carbinyl chloride is converted into the isomeric carbinyl bromide from which it follows that (1) part of the chlorine changes place with the bromine through the intermediate quinonoid form ; (2) when the compound contains a brominated and a chlorinated benzene nucleus it is the former which primarily changes into the quinonoid form under the influence of sulphur dioxide. 4-Chloro-4' 4"-dibromotriphenylmet?q/l bromide forms colourless crystals m. p. 174'. W. H. G. Action of Nitrosobeneene on Secondary Aminea. PAUL FREUNDLER and JUILLARD (Compt.rend. 1909 148 289-290. Com- pare Bamberger Abstr. 1896 i 222).-Nitrosobenzene and secondary amines readily react to give azobenzene together with smaller quantities of nitrobenzene aniline and possibly azoxybenzene. The greater part of the amine remains unaltered but a portion is converted into the corresponding secondary hydroxylamine RR'N*OH. This reaction may be applied t o differentiate between primary secondary and tertiary aliphatic amines. About 0.5 gram of the amine is mixed with nitroso- benzene and when a red coloration appears the product is distilled below 150' in a vacuum if necessary. I n the case of secondary amines the distillate reduces silver nitrate solution in the cold whilst with primary or tertiary amines no reducing agent is formed.A secondary hydroxylamine however appears to be formed when nitrosobenzene is heated for a long time with a tertiary amine. w. 0. w. Preparation of Esters of the Cyclic Series. AUGUSTE BIHAL (Compt. rend. 1908 147 1478-148 I).-Cyclic halogen derivatives react with organic acids liberating hydrogen chloride and giving rise to a cyclic ester. Thus for example benzyl chloride is converted into benzyl acetate when boiled for several hours with glacial acetic acid. The reaction proceeds more rapidly in presence of certain chlorides notably those of antimony bismuth manganese copper and cobalt. The chlorides of iron zinc and tin have a similar action but altjo146 ABSTRACTS OF CHEMICAL PAPERS. bring about the formation of res,inous condensation products.The chlorides of magnesium nickel cadmium mercury chromium barium and strontium have no action or else exercise a retarding effect. Curves are given showing the influence of varying amounts of bismuth chloride and of acetic acid on the velocity of the reaction. w. 0. w. Formation of Hydrogen Cyanide in the Action of Nitric Acid on Phenols and Quinones. ALPHONSE SEYEWETZ and L. POIZAT (Compt.rend. 1909,148 286-288).-Phenols and quinones containing an unsubstituted ortbo- or para-position yield hydrogen cyanide when boiled with nitric acid (20%). With the exception of dimethylaniline and diethylanilhe no other aromatic compounds have been found to give the reaction which is probably due to nitrous acid since in preseiice of carbamide or aniline no hydrogen cyanide is evolved.A theoretical explanation of the reaction based on this fact is suggested. w. 0. w. 1-Methylcyclohexan-2-01 and its Derivatives. MURAT (Ann. Chirn. Phys. 1909 [viii] 16 lOS-l26).-A detailed account of the preparation and properties of certain esters ethers tertiary alcohols and ethylenic hydrocarbons obtained from 1-methylcyclohexan-2-01 (Sabatier and Mailhe Abstr. 1905 i 275). The hydrobromide is less stable than the corresponding hydro- chloride (Sabatier and Mailhe Zoc. cit.) and has b. p. 118-120°/35 mm. and Do 1.240 ; the bccrium salt of the sulphate (C,HloMeO*SO,),Ba has m. p. 120'; the propionate has b. p. 189-190° D20 0.9225 n 1.443 ; the butyrute has b. p. 104'/20 mm. Do 0.941 D20 0.930 nz 1.55; the isobutyrate has b. p. 10Z0/20 mm. Do 0.940 DZo 0.926 ng 1.441 ; the valerate has b.p. 112-113O/24 mm. Do 0.93'3 D20 0.926 n 1.448 ; the isovulerate has b. p. 110-112°/20 mm. Do 0.9375 9 2 1 0.926 mg 1.447; and the belnxoute has b. p. 200°/55 mm. Do 1.0325 Dl* 1,047 m'," 1.521. The ethers are readily obtained by the action of the alkyl iodide on the sodium derivative of che alcohol and the following compounds were prepared 2-ethoxy-l-methyZcyclohezune b. p. 156-158"/760 mm. Do 0.9221 D20 0.912 nz 1.470 ; 2-arnyZoxy-l-methylcyclohexu~ze b. p. 177" Do 0,936. When l -methylcycZohexan-Z-one is heated with acetic anhydride during several days it yields the ucetyl derivative of a tetrahydro- cresol CH2<2zH,$&>COAc b. p. 178" ; the tetrubromo- derivative of the ketone C,H,MeBr,:O crystallises in needles and has m.p. 76'. By the action of organo-magnesium derivatives on 1-methyl- cyclohexan-2-01 the following tertiary alcohols were prepared 1-methyl-2-ethylcyclohexan-3 01 C H 2 < ~ ~ ~ ~ ~ ~ ~ > C E t * O H b. p. 181-182"'745 mm. Yo 0 9356 D20 0,9235 w 1.458 forms an ucetylORGANIC CHEMISTRY. I47 derivative which has b. p. 196-198' DO 0.946 and on dehydration by means of zinc chloride yields R mixture of methylethylcyclohexenes b. p. 149-153' Do 0.829 D12 0.821 which is reduced by direct hydrogenation in the presence of nickel at 200° yielding the methyl- ethylcyclohexane b. p. 151° DO 0.7945 D20 0.784 % 1.432; 1 -methyl- 2-pop y Zc y clo hexan - 2 -oZ C H2< CH2*CHMe>CPr*OH CH2-CH2 b. p. 97-98'/34 mm. DO 0.9276 D20 0919 ng 1.48 forms an acetyl derivative b.p. 107-110'/30 mm. DO 0.9650 D20 0.956 n 1.465 and on dehydration yields a mixture of ethylenic hydrocarbons b. p. 167-170' Do 0.861 1 D20 0.848 n 1.469 ; l-metl~yl-2-tert.-butyZcgclo- >C(OH)*CMe b. p. 93-96'/25 mm. Do 0.9218 D26 0.908 ng 1.465 yields on dehydration a mixture of ethylenic hydrocarbons b. p. 183-lS6'/750 mm. DO 0.864 D27 0,836 nz 1 -46 2 ; 1 -methyl- 2 -isoam$c yclohexan-2-0 2 C H,. C HMe 7Mxan-2-01> CH2<(TH,-CH b. p. 118-120°/22 mm. D O 0.913 D17 0.902 n z 1.462 yields on dehydration one or more ethylenic hydrocarbons b. p. 205-208' DO0.85LY D17 0.845 n" 1.471 which on direct hydrogenation in the presence of nickel at 230-250' is converted into a methylisoamylcyclo- hexaae,b. p. 204' Do 0.825 D17 0.812 ng 1.454 ; 2-cyclohexyZ-1-methyZ- cyclohexan-2-ol CH2<~~2*CHMe>C(OH)*C,FIl b.p. 146-147'/ 30 mm. with decomposition DO 0.978 D1* 0.969 ng 1.501 is converted by the action of zinc chloride into an ethylenic hydrocarbon b. p. 113-116'. Attempts to prepare corresponding tertiary alcohols by the action of 1 -methylcycZohexan-2-01 on phenyl- benzyl- or tolyl- magnesium iodide were unsuccessful the ethylenic hydrocarbon being the only product isolated 2-phenyl-1 -methyl-A2-cgclohexene 2-CH2 C"2<CH2--CH CH2*C=Me>Cpll b. p. 1 28'16 mm. ; 2-6enzyl-l-meIhyl-A2-cyclohexene b. p. 170'142 mm. DO 0.99 Dls 0.981 nz 1.453; 2-o-toZyZ-1-methyl- A2-cyclohexene C H < ~ ~ ~ ~ H ~ ~ > C * C 7 H f b. p. 158-160"/12 mm. DO 0.985 D20 0.961 nto 1.541. The following derivatives of l-methyl-A2-cyclohexene are described the dichloro-derivative obtained by direct chlorination has b.p. 123-125'/20 mm. DO 1.2300 ; the dibromo-derivative similarly pre- pared b. p. 128'/35 mm. Do 1.905 ; Knoevenagel has described a dibromo-derivative of hexahydrotoluene b. p. 1 lSo/20 mm. (Abstr. 1897 i 608) ; the nitrosate C H 2 < ~ ~ ~ ~ ~ ~ ~ > C = * O N 0 2 ; forms brilliant prisms m. p. 104' ; the nnitrosiie '148 ABSTRACTS OF CHEMICAL PAPERS. forms small yellow plates m. p. 103' ; the nitrosochloride CH,-CHMe>(YRCI CH2<CH_-C*(NO) is unstable. 1 -Methyl-Al-cyclohexene yields a dichloro- derivative b p. 1 20°/ 20 mm. DO 1.240; an unstable dibromo-derivative b. p. 126-130"/ 28 mm. ; a nitrosate m. p. 104' ; a nitrosite m. p. 102O and a liquid nitrosoch loride.2-Chloro-1-methylcyclohexane reacts with magnesium and the product condenses with acetaldehyde to form a secondary alcohol which on hydration yields the ethylenic hydrocarbon CH2<C CH2*CHMe>C:CHRle €3,-CH b. p. 158"/760 mm. DO 0.S23 D20 0.81 ng 1.47. ni. A. w. Chromo-isomeric Salts of o-Nitrophenols. ANTONI KORCZY~~~SKI (Bev. 1909 42 167-177).-Hantzsch has shown (Abstr. 1907 i 207 500) that the alkali salts of nitrophenols can be obtained in yellow orange and red modifications; the yellow and red salts are probably true isomerides whereas the orange salts are solid solutions of the red and yellow varieties; however the number of such isomeric salts prepared hitherto has been small. It is shown by the present investigation that the number of yellow salts of o-nitrophenols is quite as large as that of the red salts.The salts with amines are as a rule yellow and do not differ appreciably from one another in shade; on the contrary the red salts exhibit various shades of colour depending on the nature of the alkali metal. Hantzsch has shown recently that the colour of the anion is not altered by union with an alkali metal in salt-formation; consequently the yellow salts which have precisely the same colour must be chemically homogeneous whereas the majority of the red salts of variable colour must be solid solutions of the red isomeride with small quantities of the yellow isomeride. It has been found possible by careful crystallisation from water or dilute alcohol t o separate the orange lithium salt of 2 4-dinitronaphthol into its red and yellow components. The red and yellow salts are undoubtedly structurally identical having the formula C,H,<O->M ; they are '' chromo-isomerides," the exact nature of the isomerism being still unknown.The rubidium (8 H,O) and litihm (&H,O) salts of o-nitrophenol are orange ; the anhydrous salts are red. PhO,N*NH prepared by passing ammonia into the molten substance is red and quickly passes into the orange salt which is also obtained by the absorption of ammonia in Ley and Wiegner's apparatus (Abstr. 1905 i 749) at the ordinary temperature ; a t - 20° the yellow salt PhO,N*NH,,NH is obtained. The methylamine dimethylamine trimethylumine ethylumine dipopplunaine and benzylarnine salts precipitated from ethereal solution all have the same yellow colour ; NO2 The ammonium salt,ORGANIC CHEMISTRY.149 the pipmidine salt forms yellow leaflets ; the pipeyazine salt crystallises in yellow needles m. p. 74-75O. The anhydrous lithium sodium potassium rubidium and silver salts of p-bromo-o-nitrophenol are red ; the lithium salt containing H20 is orange and the sodium salt ($H,O) is yellow when first precipitated ; ammonium salts similar to those of o-nitrophenol were prepared. The salts with the organic bases mentioned above with the exception of trimethylamine have the same yellow colour ; the trimethylumine salt is orange. The alkali salts of 2 4-dibromo-o-nitrophenol are of a brighter red colour than the corresponding salts of p-bromo-o-nitrophenol ; the piperidine and methylcmine salts are yellow; the ammonium trimethylamine dimethylamime ethylamine dipropylamine and benzyl- amine salts are orange ; the piperaxine salt C6H,0,NBr2,C4H1,,N2 m.p. 160° is orange ; the piperaxhe salt (C6H,o,NBr2),,C,H1,N2 m. p. 185O is scarlet. The lithium and sodium salts of o-nitro-p-cresol when prepared a t - 203 are orange ; the potassium ($H20) rubidium and ccesium (IH20) salts are red as is also the sodiuin salt when prepared at the ordinary temperature ; the thallium and ummonium salts are orange ; the salts with organic bases are yellow. The lithium (2H,O) and potassium (1H,O) salts of bromo-o-nitro-p- cresol are blood-red; the anhydrous lithium salt is yellow ; the sodium benzylamine piperazine and ethylamine salts are orange ; the methylamine dimethylamine trimethylamine and piperidine salts are yellow.The lithium salt of p-chloro-0-nitrophenol is orange but the sodium (1 H20) salt is red ; the methyZamine dimethylamine trimethykamane ethylamine piperidine and piperazine salts are yellow. The sodium salt of a-nitro-/3-naphthol precipitated a t low tem- peratures is yellow but quickly changes into the stable orange form. The dimethylamine ethylamine and bemylamine salts are yellow. The lithium (1H20) and sodium salts of 3 :d-dinitro-p-cresol are orange ; the anhydrous potasrrium rubidium and ccesium salts are red. The ammonium methylamine ethylamine benzylamine dimethylamine and trimethylamine salts of 2 4-dinitronaphthol are yellow ; the pipwaxine salt crystallises .in large orange prisms but the powdered substance is yellow ; the sodium potassium rubidium ccegium and thallium salts are ‘orange; the lithium salt (1H20) is orange and loses its water at 160° without changing colour; the anhydrous salt absorbs lH20 from the air and becomes carmine-red.When a solution of the salt in dilute alcohol is cautiously concentrated at 70° it deposits at first a carmine salt lH20 as microscopic leaflets or needles after which a yellow salt lH,O crystallises out in needles; both salts when dehydrated pass into the orange variety ; the yellow modification generally passes spontaneously into the red form. Equivalent solutions of the two salts have the same colour and are equally intense. W. H. G.150 ABSTRACTS OF CHEMICAL PAPERS. Derivatives of 2 3 4-Trinitrortnisole.JAN J. BLANKSMA (Chem. Weekblad 1909 €3 85-88. Compare Abstr. 19@8 i 978 ; Meldola Trans. 1902 81,993).-Derivatives of 2 3 4-trinitroanisole are described. The parent substance was prepared by treating 2 %di- nitroanisole with a mixture of sulphuric acid and fuming nitric acid. Crystsllised from alcohol it has m. p. 155". Its constitution was determined by conversion into 2 4-dinitro-m-anisidine by heating in alcoholic solution with the equivaIent quantity of ammonia in a sealed tube in the water-bath. It separates from alcohol in yellow crystals m. p. 16'7". When this compound is diazotised in sulphuric acid solution and the diazo-solution poured into boiling alcohol 2 4-dinitroanisole is obtained proving that the parent substance is 2 3 4-dinitroanisole.With methylamine in alcoholic solution 2 3 4-trinitroanisole yields 2 4-dinitro- 3 -meth ylanainoanisole OMe C,H,( NHMe)( NO,) 2 which separates from alcohol in yellow crystals m. p. 130". When this compound is dissolved in a mixture of nitric and sulphuric acids and the solution poured into water 3-nitromethylamino-2 4 6-tri- nitroanisole OMe-C,H(NMe*NO,)(NO,) separates as a sticky mass which crystallises from methyl alcohol in colourless crystals rn. p. 99O (Romburgh Abstr. 1889 971). When 2 3 4-trinitroanisole in alcoholic solution is boiled with the equivalent quantity of aniline 2 4-dinitro-3-aniZinoanisoZe OMe*C,H,(NHPh)(NO,) is formed. It crystallises from alcohol in reddish-brown cryi;ta,ls m. p. 152". When 2 3 4-trinitroanisole is heated with aqueous sodium car- bonate the nitro-group at 3 is replaced by hydroxyl yielding the monomethyl ether of 2 4-dinitroi.esorcino2 OMe*C,H,(NO,),*OH which separates from water in light yellow crystals m.p. 108". The nitro-group a t 3 in 2 3 4-trinitroanisole is replaced by methoxyl by heating with sodium methoxide in methyl alcohol solution with formation of theIdimethy1 ether of 3 4-dinitroresorcinol identical with that obtained by Kauffmann and Franck (Abstr. 1907 i 1092). When freshly prepared it is colourless but direct sunlight turns it reddish-brown. Treatment of 2 3 4-trinitroanisole with sodium ethoxide with a view to replacing the nitro-group at 3 by ethoxyl resulted in a complex reaction which is under investigation. OMe*C,H,(NH,)(NO,) Crystallised from alcohol i t has m. p.73". A. J. W. Derivatives of 8-Amino- P-naphtbol. FRIEDRICH KEHRMANN and E. F. ENGELHE (Bey. 1909 42 350-353).-During the course of unsuccessful attempts to prepare 8-ncetylamino-$-naphthaquinone the following new compounds have been obtained. 8-Acetylurnino-P- naphthol OH*C,,H,*NHhc m. p. 164-165" obtained from the aminonaphthol and acetic anhydride is converted by sodium nitrite and dilute sulphuric acid into 1 -nit~oso-8-acety2amino-~-na$thol m. p. 133-134" (decornp.) which separates from boiling water in golden-yellow needles. The nitroso-compound by treatment with 8 parts of stannous chloride in 20% hydrochloric acid for twelveORGANIC CHEMISTRY. 151 hours yields yellow crystals of the hydvochloride of 9-hydroxy-2-methylperimidine {formula I ; compare Sachs Chem.Zeit. 1908 30 IX for nomenclature). Oxidation of an aqueous solution of the salt by sulphuric and chromic acids at Oo yields a substance C,,H,ON m. p. 175' {decomp.) (1.1 which crystallises in orange-yellow prisms is re-converted by reducing agents into the original salt and is probably 9-quino-2-methplperimidine (formula 11). Me \/\/ c. 8. N-P\ -\ / Substitution of Zinc by Magnesium in the Synthesis of Unsaturated Alcohols. \-/ W. JAWORSKY (Ber. 1909,- 435-438. Com- pare Abstr. 1908 i 753).-It is found that much better yields are obtained by substituting mag- (11.) nesium for zinc in the preparation of unsaturated alcohols by Saytzeff's method. A mixture of allyl bromide and the ketone in equivalent proportions is slowly added to magnesium ribbon (which has previously been treated for a short time with an ethereal solution of allyl bromide) immersed in absolute ether.The reaction product is subsequently treated with dilute acid and the alcohol dried and fractionally distilled. DipAenyZcclZyZcar6inoZ C ,H1,O prepared from benzophenone allyl bromide and magnesium is a colourless liquid b. p. 182-183'/32 mm. The following substances were also prepared a viscid yellow oil b. p. 169'/27 mm. from piperonaldehyde; an oil b. p. 266-272"/ 760 mm. from furfuraldehyde; a limpid liquid b. p. 168-170"/760 mm. (decomp.) from mesityl oxide; a yellow oil b. p. 165'/760 mm. (decomp.) from benzylideneacetone ; a viscid yellow oil decomposing when boiled under 22 mm. pressure from benzil. - W. H. G.Action of Magnesium on a Mixture of p-Tolyl Methyl Ketone and Ally1 Iodide. E. GRISHKEWITSCH-TROCHIMOWSHY (J. Buss. Phys. Chem. SOC. 1908 40 16S5-1691).-p-Z'oZyZmethyZalZyZ- carbinol C,H,Me-CMe{C,H,)*OH obtained together with a small proportion of diallyl by the action of magnesium on a mixture of p-tolyl methyl ketone with allyl iodide or bromide is a viscous colourless liquid with a camphor-like odour and an intensely bitter taste b. p. 128'/15 mm. 132.5-133'/30 mm 237-240°/760 mm. DY 0.9807 Di4 0.9832 ng 1.5236. The alcohol readily unites with bromine (2 atoms) giving a syrupy compound which rapidly decomposes with evolution of hydrogen bromide. p-p-ToZyZpentame-p&-trioZ C,H,Me*CBle(OH)*CH,*CH(OH).CH,. prepared by oxidising p-tolylmethylallylcarbinol by 1 ns of 1% potassium permanganate solution crystallises from a mixb of ether and light petroleum in colourless needles m.p. 101-103°. p-p- ToZyZ-p-meth yZh ydyacrylic acid C,H,Me*C~~e( OH)-CH,. d2H obtained by oxidising p-tolylmethylallylcarbinol by means of 4% potassium permanganate solution forms acicular crystals m. p.152 ABSTRACTS 102-104°. The silver salt and the colcium and barium ( OF CHEMICAL PAPERS. which is readily solrible in + 2H,O) salts were prepared. hot water T. H. P. Distribution of Cholesterol and its Allies. CHARLES DORJ~E (Bio-Chent. J. 1909 4 72-106).-Cholestorol is widely distributed in the animal kingdom being found in representatives of all classes examined. In one or two cases analogous substances take its place spongosterol in sponges and so forth.The amount present varies and the results are stated quantitatively. The same wide distribution of the phytosterols is found in the vegetable world and these sub- stances are probably the source of cholesterol in animals. The whole group consists of isomeric or closely related substances exhibiting the unsaturated linking and the hydroxyl group which are necescary for their antitoxic action. W. D. H. Fatty Acid Combinations with Cholesterol. CHARLES P. WHITE (Proc. Physiol. SOC. 1908 vi ; J. Physiol. 38).-Cholesterol forms loose combinations with fatty acids which differ from true esters. Those with the fatty acids higher than hexoic can be obtained as fluid crystals and give '' myelin forms " and,finally an emulsion of anisotropic globules on the addition of water.Similar combinations are formed by cholesterol with lecithin cetyl alcohol glycerol mono- and di-palmitin but not with triglycerides. The globules found in certain tissues (adrenal cortex) are of similar nature. Cholesterol may thus assist in the emulsification absorption and transference of fats. W. D. H. Agrosterol a Cholesterol Substance in Soils. OSWALD SCHHEINEB and EDMUND C. SHOREY (J. Amer. Chern. SOC. 1909 31 11 6-1 1 S).-The authors have isolated a cholesterol substance from Marshall clay (a soil containing 10.6% of organic matter and 0.51% of nitrogen) cbtained from North Dakota by extraction with alcohol and suitable treatment of the extract with ether and alcohol. The substance crystallises from ether in colourless needles m. p.237O and from 80% alcohol in flat plates containing water of crystallisation. It is proposed to name t h i s substance agrosterol since it gives Lieber- mann's cholesterol reaction and has the formula C2,H,,0. W. H. G. New Synthesis of Adrenaline and Allied Compounds. KARL BOTTCHER (Ber. 1909 42 253-266).-Barger and Jowett (Trans. 1905 87 970) were unable to convert up-dibromo-3 4- methylenedioxyphenylet hane by means of phosphorus pentachloride into a chlorinated compound which could be decomposed to a dihydroxy-compound on hydrolysis with water ; they obtained in addition to P-bromo-a-hydroxy-3 4-methylenedioxyphenylethane a dibromohydriu m. p. 158'. When however 24 to 3 mols. of phosphorus pentachloride are allowed to act on the dibromide for a considerable time at 105" a chlorinated product is obtained which is decomposed by water intoORGANIC CHEMISTRY.153 P-bromo-a-3 4-trihydroxyphenylethane. The halogen in this compound may be replaced by the NHMe-group forming adrenaline. By a similar series of reactions $-safrole CH2:O,:c6H,*CMe:CH and isosafrole CH,:O,:C,H,*CH:CHMe or their dichlorides or chloro- hgdrins can be converted into methyladrenaline. A monobromo- adrenaline is obtained from the dibromohydrin m. p. 158'. Thesg three substituted adrenalinee exhibit no pharmacological activity. P-Cldoro-a-hydro-3 4-methyylenedioxyphenyylethne CH,:O,:C,H,*CH( OH)*CH,CI crystallises in long needles m. p. 95'; it is prepared by acting with chlorine on a cooled solution of vinylcatechol methylene ether in carbon tetrachloride whereby the ap-dichloroethane is first obtained as a reddish-coloured oil and this is subsequently hydrolysed by means of a mixture of acetone and water. /3-Chlos.o- a-3 4- trih ydroxgphen y Zethane C,H,( 0 H) ,* C H( 0 H) CH,CI is prepared from the methylene ether by prolonged heating with a large excess of phosphorus pentachloride and subsequent hydrolysis with a mixture of acetone and water.It forms needles which decompose about loo" gives an intense green coloration with ferric chloride and soon decomposes when kept exposed t o the action of light. The carbonic ester C0:O2:C6H,*CHCl*CH,C1 formed as an intermediate product in its preparation may be isolated as an oil b. p. 190°/13 mm. P-Bromo-a-3 4-trihydroxyphenyylethane is prepared from the corre- sponding methylene ether in an analogous manner.It crystallises in clusters of small needles m. p. 92-93O decomposing to a dark violet substance shows the same intense green coloration with ferric chloride and decomposes even more easily than the chloro-compound. Either compound when dissolved in alcohol and shaken with a large excess of aqueous methy lamine is converted into adrenaline. Although the compound prepared in this manner has not yet been obtained in the form of crystalline salts it is very active physiologically. Chloro- P- b~orno-a-hydroxy-3 4methyylenedioxyphen ylet hane C H , 0, C H,C1* CH( OH) CH,Br prepared by the action of sulphuryl chloride on bromohydroxy- methylenedioxyphenylethane crystallises in well-formed long needles m. p. 128-129O.The halogen cannot be removed by heating with aqueous acetone. The acetate forms crystals m. p. 89". C H, 0, C,H,C1*CH(OH)*CH2Cl obtained by the action of sulphuryl chloride on chlorohydroxy- methylenedioxyphenylethane separates in needles m. p. 126-137". A tetrabromo-compound prepared by the action of bromine vapour on a/3-dibromomethylenedioxyphenylethane forms tiny crystals m. p. $r-Safrole ciiloroh ydrin CH, O,:C,H,*CMe( 0 €3) CH,Cl prepared by the action of chlorine on $-safrole is a faintly yellow-coloured oil. It is converted by treatment with phosphorus pentachloride and subsequent hydrolysis with water into di?LydroxyphenyLJI-alZylchloro- hydrin C6H3(0H)2*CMe(OH)*CH2Cl a thin oil from which a-methyl adrenaline is obtained as a bright golden-brown powder.The corresponding dichloro-compound 14 1 - 1 43".154 ABSTRACTS OF CHEMICAL PAPERS. isoSafrole dichloride CH,:O,:C,H,*CHCl*CHMeCl (Hoering Abstr. 1905 i 903) is an oil b. p. 164-166’/11 mm. 270°/760 mm. with much decomposition. P- Ch Zoro - a-h yd~ox y -a-( 3 4-)dioxyphen y Zpropane C,H,(HO),*CH(OH)*CHMeCI forms needles m. p. 104-105’ (decomp.) and when shaken with methylamine gives rise to P-methyladrenaline a bright yellow powder. P-Bromo-a-hydroxy-3 4-dioxybromophenylethane m. p. 157-158O is conveniently prepared by the action of bromine on a solution of vinylcatechol methylene ether in carbon tetrachloride. The acetate has m. p. 1OO-10lo. Oxidation with permanganate forms mono- bromopiperonylic acid m. p. 201-202’. P-Brorno-a-hydroxy-3 4-cc~~6onatobromopht?nyZethane CO:0,:C,H,Br*CH(OH)*CH2Br forms glistening plates m.p. 107O and is converted when left in contact with acetone and water into /?-homo-a-3 4-tdydroxybromo- phenylethane C6H2Br(OH),*CH( OH)*CH2Br which crystallises i n lancet-like needles m. p. 121-123’ and gives a green coloration with ferric chloride in aqueous solution. a-3 4-Trihydroxy-/?-methyZamiraob~omophenyEethnne C,H,Br( OH),. CH(0H) C€€,*NHMe is obtained by the action of methylamine on the above as a light brown powder. E. F. A. New Syntheses of Adrenaline and Allied Compounds. HERMANN PAULY (Ber. 1909 42 484-4S5).-It is claimed that Bijttcher (preceding abstract) had not proved that the product obtained by him is adrenaline. K. W. CHARITSCHKOFF (J. Buss. Phys. Chern. Xoc. 1908 40 1757-1774).-Oxidation by means of air in presence of alkali serves as a means of characterising hydrocarbons and of estimating them in mixtures such as naphtha and its fractional distillates.Under the above conditions saturated hydrocarbons give a negligible quantity of liquid oxidation products whilst naphthenes give polynaphthenic or asphaltogenic acids which are syrupy liquids D 1.2 incapable of cryatallising and are not reduced to more highly hydrogenated compounds by means of sodium amalgam. These acids give the red coloration yielded by ketones with sodium nitroprusside reduce ammoniacal silver nitrate solution and Fehling’s solution and decompose on distillation even under greatly reduced pressure. They are soluble in alcohol benzene chloroform ether and carbon disulphide.Oxidation of the fraction of “Meteor” kerosine b. p. 169-171° consisting of one of [the isomeric decanaphthenes yielded a dibasic acid which on analysis and on determination of the molecular weight cryoscopically and ebullioscopicnlly mas found t o have the formula C2oH2504. T. H. P. 1-Acetyl-Al-cyctopentene as an Oxidation Product of A1-cyclo- Hexeneacetic Acid. WILLIAM H. PERKIN jun. and OTTO WALLACR (Bey. 1909 42 145-149. Compare Wallach Abstr. 1906 i 176; 1907 i 616; 1908 i 426).-The ketone C,H1,O (Harding Haworth J. J. S. Polynaphthenic Acids,ORGANIC CHEMISTRY. 155 and Perkin Trans. 1908 93 1946) has been definitely proved to be acety lcyclopentene. The fact that both Al-cyclohexeneacetic acid and methyl-Al-cyclo- hexene yield acetylcyclopentene when oxidised at 0" with perman- ganate proves that in this reaction a rupture of the six-membered ring occurs and is followed by a closing of the ring to give a cyclo- pentene derivative The possibility of such a reaction must be borne in mind when the constitution of a cyclic compound is based on an examination of the products of oxidation with permanganate. J.J. S. Isomeric Cinnamic Acids. EINAR BIILMANN (Ber. 1909 42 182-188. Compare Liebermann Abstr. 1903 i 255 ; Erlenmeyer jun. Abstr. 1906 i 429).-It is shown that allocinnamic acid m. p. 68O isocinnamic acid m. p. 57" (compare Liebermann Abstr. 1890 1417) and isocinnamic acid m. p. 38-46' (Erlenmeyer sen. Abstr. 1891 200) are chemically identical and are not chemical isomerides. The three substances are trimorphous and may be converted one into the other by simply melting the solid substance cooling the fused mass and inoculating with the acid required Thus the isocinnamic acid m.p. 41° may be obtained from allocinnamic acid by melting this acid in a tube closed with a cotton-wool plug and subsequently cooling the fused mass in a freezing mixture ; if this is heated to about 44' and inoculated with the isocinnamic acid m. p. 58" the whole mass solidifies and melts then at 58". rcZloCinnamic acid may be obtained from this in the same manner. Special precautions must be taken in crystallising isocinnamic acid m. p. 58' in order to prevent inoculation with allocinnamic acid. Thus in order to crystallise the former in a room "infected " with the latter it must be dissolved and the solution boiled after closing the vessel with a cotton-wool plug.This probably explains why Liebermann having once obtained o2locinnamic acid could not again obtain isocinnamic acid m. p. 58O. The isocinnamic acid m. p. 419 when treated with light petroleum appears at first to dissolve but in a few seconds the acid m. p. 58" crystallises out from the solution W. H. G. Remark on Biilmann's Discussion of the Isomeric Cinnarnic Acids. EMIL ERLENMEYER jun. (Ber. 1909 42 521-522. Compare Biilmann preceding abstract).-Polemical. Biilmann's observations are not wholly in accord with those of Liebermann and the author on the three acids from allocinnamic acid the fact that allocinnamic acid can be separated from the iso-acid is held to be against the idea of polymorphism.W. R.156 ABSTRACTS OF CHEMICAL PAPERS. Separation of Synthetic Cinnamic Acid into its Isomeric Components and their Re-combination into the Synthetic Acid. EMIL ERLENMEYER jun. [with 0. HERz] (Ber. 1909 42 502-513. Compare Abstr. 1906 i 21 176; 1907 i 318).-It has already been shown that the synthetic acid is a mixture of storax- cinnamic acid and another acid of m. p. 128'. It has now been demonstrated that this admixed acid is not benzoic thienylacrylic or an alkyl- or methoxy-cinnamic acid. Fractional crystallisation is not a suitable method for obtaining this acid but it may be obtained by fractional distillation of the ethyl esters. Ethyl storax-cinnamate has b. p. 148-151'/20 mm. whereas the ethyl ester of the synthesised acid has b.p. 152-165O/20 mm. and leaves in addition a considerable residue (10-20%). This distillate on careful refractionation gave a separation ; the fraction of lowest b. p. on hydrolysis yielded " storax " acid that of highest b. p. gave the acid m. p. 1289 heterocinnnarnic acid. Moreover this hetero-acid like the cinnamic acid from storax exists in two forms. The residue just mentioned distils at 269-271° and on hydrolysis with cold 20% alcoholic potassium hydroxide a salt separates which yields hetero-p-cinnnarnic acid as an amorphous pre- cipitate m. p. 128'. It exhibits all the chemical properties of a cinnamic acid and i t separates from ethereal solution in a characteristic chalky form. It dissolves in '7-7.30 parts of 75% alcohol whereas storax-a-cinnamic acid dissolves in 16.67 parts and storax-P-acid in 11.31.The hetero-/?-cinnamic acid on repeated dissolution in petroleum is converted into the a-modification which crystallises in glistening thin leaflets m. p. 130-131'. It dissolves in 9.40-9.54 parts of 75% alcohol and by re-solution in water or alcohol it is converted into the chalky isomeride. When storax-a- and hetero-a-acids are mixed in equal proportions and crystallised from ether the synthetic acid is reformed also the two a-acids form mixed crystals. The hetero-/?-cinnamic acid does not give a single substance ; on the bottom of theAvessel the &acid is seen and glistening leaflets on the sides. W. R. Salt Formation and Addition Reactions of the Isomeric Acids obtained from Synthetic Cinnamic Acid and Demonstra- tion of their Different Chemical Behaviour.EMIL ERLENMEYER jun. [with 0. HERZ and G. HILGEKDORFF]l (Ber. 1909 42 513-521. Compare preceding abstract).-The salts of storax-a- and hetero-P- cinnamic acid exhibit strong resemblancea yet the original acids are recovered from them unchanged; thus the diphenyloxyethylamine salt of storax-a-acid crystallises in slender needles m. p. 177'; the salt of the hetero-P-acid crystallises similarly m. p. 172'. Brucine forms an acid and a normal salt with the hetero-/?-acid which are very similar to those of the storax acid ; they are however somewhat more soluble and differ slightly in optical rotatory power (20'). A non-crystallisable syrup was obtained by mixing the two acids and attempting to prepare a solid brucine salt.A potassium hydrogen storax-a-cinnamate C18Hlb04K is obtained from 2 mols. acid and 4 mol. potassium carbonate whlch is acid t o testORGANIC CREMISTRY. 157 paper and stable ; it crystallises from alcohol (75%) in long crystals ; the potassium hydrogen salt from the synthetic acid forms leaflets and the similar salt from the hetero-@acid is amorphous. Benzoic acid also forms a potassium hydrogen snlt. The properties described hitherto as descriptive of the different isomerides have all been physical. However chemical differences also exist; the dibromide from storax-a-acid is formed more readily than that from hetero-@-acid; the ester of storax-a-acid is more rapidly hydrolysed than the hetero-/3-ester and these acids may be separated by taking advantage of the fact that hypochlorous acid forms an additive compound much more slowly with the hetero- than with the storax-acid.The storax acid dibromide crystallises in stout crystals m.. p. 205-206° ; the hetero-dibromide forms thin leaflets m. p. 204' whilst the dibromide from the synthetic acid is intermediate in crystalline character. By Liebermann's method' all these dibromides give the original acids. Synthetic cinnamic acid when fractionally precipitated from its aqueous sodium salt solution is separated into hetero-a- and -p- and storax-a-acids which shows that these acids differ in strength also. The nature of the isomerism is discussed shortly and the opinion expressed that these isomeric phenomena are due to differences in the benzene nucleus.W. R. Action of Ammonia and Amines on Tetrahydrosalicylic Esters. ARTHUR KOTZ and B. MERKEL (J. pr. Chern. 1909 [ii] 79 102-125).-Ethyl 3-amino-1-methylcycZohexane-4-carboxylate (Abstr. 1906 i 88) which does not react with aqueous or methyl alcoholic ammonia vields with boiling aniline alcohol and the v m. p. 261' (decomp.) and by heating ~ H M ~ ~ H $ - ~ H substance CH,-CH;C*CO ' alone at 28d' for&s alcohol and the bimolecular compound CIGH2,O2N2 m. p. above 300'. Ethyl l-methylcyclohexan-3-one-4-carboxylate when heated with aminocyclohexane yields a substance C,H,,0N2 m. p. 264' which appears to be identical with the preceding. With boiling aniline ?HMe*CH,-fi*N€€Ph (1 mol.) the ester yields the ccnilinoanilide CH,-CH,*C*CO NHPh' m. p. 130° whilst with benzylamine at the ordinary temperature with or without methyl alcohol it yields the substance yHMe*CH,-F:N*CH,Ph CH,-CH,*CH-CO,E t ' m.p. 61° into which the attempt to introduce a second N*CH,Ph group was unsuccessful. Ethyl l-methylcycZohexan-3-one-4-carb- oxylate reacts ( a ) with the calculated amount of piperidine at the b. p. t o form ethyl 3-piperidino- 1 methyl-A3-cyclohexene-4-carboxylate FHMe*CH,* fi*C,NH CH,-CH,*C* C0,Et ' m. p. 123O ; (b) with carbamide in warm dilute sodium ethoxide solution VOL. XCVI. i. m158 ABSTRACTS OF CHEMICAL PAPERS. . ( c ) with methyl- yHMe*CH,*fi*NH*y 0 CH,--CH,*C*CO*NH ' t o form the substance alcoholic benzenylamidine to form the quinazoline derivatiue yHMe*CH,*$!:N-gPh CH2-CH,* C:C(OH)* N ' m. p. 227' and (d) with piperazine at 150° to form the substance CH2<@!&3>C* C,N,H *c<gfoy;:E>cH m.p. 21 6'. Ethyl cyclohexan-2-one-1 -carboxylate when heated with aniline yields m. p. 7 H CH N HPh CH,*CH,*C*CO,Et ' ethyl- 2-anilino- A h y clohexene-l -carboxykate 2 9 O and reacts with piperazine in a sealed tub; at $50'' firming the CH,* CH,*C-N c. s. II A C H C H m. p. %O0. II v 4' subst ance I I CH,*CH,*C*CO*N Synthesis of P-Hydroxy-P-phenylpropionic Acid. W. N. ANDRIEWSKY (J. Russ. Phys. Chem. SOC. 1908 40 1635-1 638).-In presence of zinc benzaldehjde and ethyl bromoacetate react giving ethyl P-hydroxy-P-phenylpropionate (compare Dai'n J. Russ. Phys. Chem. SOC. 1890 22 44) the changes being represented by the following equations (1) CH,Br*CO,Et + Zn = ZnBr*CH,*CO,Et ; (2) ZnBr*CH,*CO,Et + Ph-CHO = ZnBr*O*CHPh*CH,*CO,Et ; (3) ZnBr*O*CHPh*CH,*CO,Et + H20 = OH*CHPh*CH,*CO,Et + ZnBr *OH.T. H. P. Condensation of Mesoxalic Esters with Aromatic Tertiary Amines. ALFRED GUYOT and EDMOND MICHEL (Compt. rend. 1909 148 229-232).-Ethyl mesoxalate readily undergoes condensation with aromatic tertiary amines. Ethyl dimethyl-p-amimophmyl- tartronate NMe,*C,H,*C(OH)(CO,Et) prepared by heating an acetic acid solution of dimethylaniline with ethyl mesoxalate for thirty minutes forms colourless leaflets m. p. 76.5'. The following corn- pounds have also been prepared Methyl p-dimethylaminophenyl- turtronute prisms m. p. 1 15" ; ethyl p-dz'ethylanzinophenyltartronate NEt,*C,H,*C(OH)(CO,Et) prisms m. p. 45' ; the methyl ester needles m. p. 103".On hydrolysis with aqueous potassium hydroxide these substances form the corresponding acids which are unstable and have been converted into aldehydes and also into glyoxylic acids of the type R*CO*CO,H and glycollic acids of the type R*CH(OH)*CO,H. Under the influence of phosphoryl chloride the foregoing esters undergo further condensation with aromatic tertiary amines. Thus ethyl p-dimethylaminophenyltartronate and dimethylaniline yield ethyl tetra~th?/ldianziizodiphen ylmnalonate C( C,H,*NMe,),( CO Et) white leaflets m. p. 93'. The following compounds have been pre- pared in the same way Etlu~l dii,zethyZantinodiet~~yZu~~inodipheny~-ORGANIC CHEMISTRY. 159 NMe2*c6H4>C(C0,Et)2 m. p. 83" ; NEt,*C H ethyl tetraethyl- nralonate d~minodiphsi~ylmalonute prisms m.p. 82.5" ; the methyl ester prisms m. p. 08O ; methyl tetrametf~ylc2iccmino~lilenylmatonale leaflets m. p. I 66" ; methyl dimeth ylaminodieth ylamin odiphenylma Zonate NNe2*c'3H4>C( NEt2*C,H4 C0,Me)2 needles rn. p. 121O. Alcoholic potassium hydroxide converts these esters into the corresponding tetra-alkyldiaminodiphenylacetic acids which are unstable and have no definite m. p. (compare Weil Abstr. 1894 i 419). w. 0. w. m-Toluic Acid. ERTCH M~LLER (Ber. 1909 42 423-434).-A continuation of the iuvestigations of Findeklee (Abstr. 1906 i 42) and Jurgens (Abstr. 1907 i 1036). The present communication deals principally with an improved method of converting m-toluic acid into 3-methylphthalic acid and OF various condensation products derived from the latter substance.Experiments have also been made with the object of definitely establishing the constitutions of the four possible nitro-nz-toluic acids. I. 3-kfethylphthalic Acid.-3-Methylphthalic anhydride when heated with phenylacetic acid in the presence of sodium acetate at 2 3 6 O y ields benxy liclene-3-methylphthalide gH*CMe:y*CO*Y CH-CH=C--C:C H Ph' which crystallises in small leaflets m. p. 151° and is converted by a 10% aqueous solution of potassium hydroxide i n to 3-methyldeoxy- benxoin-2-carboxylic acid flH CMe:?oCo2 crystallising with CH*CH=C*CO* CH,Ph' 1H,O in gypsum-like crystals m. p. 77-79'. The latter when reduced with sodium amalgam yields a salt of a y-hydroxy-acid which when treated with hydrochloric acid yields benxyl-Y-methylphthcclide L which crystsllises in groups OF needles m.p. 87-92'. If the salt of the y-hydroxy-acid is heated a t 21Z3 for four hours and then treated with dilute hydrochloric acid i t yields an oil which is undoubtedly J-met?~ylstilbenc9-2-carbo~y~~c acid for it is converted on red uc tion into 3 -met?& y Zdibanxy I - 2 - carboxy Zic acid H -CMe:?*CO,H CH*CH=C*CH,*CH,Ph' crystallising in nodular aggregates of rhombic prisms m. p. 125-126O. It was shown that the acid has the given formula and not gH*CMe $l*CH,* CH,Ph CH*CH=-C*CO,H 9 by V. Meyer's lam of esterification (Abstr. 1895 i 228; 1896 i Although 3-methylphthalylglycine ethyl ester cannot be converted by Gabriel and Colman's method into an isoquinoline derivative 547). n a 2160 ABSTRACTS OF CHEMICAL PAPERS. (compare Jiirgens Zoc.cit.) the latter may be obtained from 3-methyl- phthalic acid by the following method. Benzylidene-3-methylphthalide is converted by gaseous nitrous acid into nitro benz ylidem- 3met?~ylphthalide C,H,Me<-b CPh. 02 which crystallises in yellow leaflets m. p. 198-199' (decomp.) and is converted by hydriodic acid and red phosphorus into 3-phenyl-8-methyt- isocoumarin C,H3Me<cH:bPh long colourless needles m. p. 131'. The latter compound is converted by alcoholic ammonia into 3-phenyZ- co.0 co-0 "-TH which crystallises in small CH:CPh' 8-n~et?~y~isocc6?~bost?/ri~ C,H3Me< groups of needles m. p. 331' and is converted by boiling phosphoryl chloride into 1 -cl~loro-3-pheny?- 8-methyl isoquino line C C 1 3 C 6 H 3 " e < ~ ~ 6 ph' crystallising i n needles m.p. 64 -65'. 3-Pl~enyl-8-metAyZisoquinoline C16HlJS obtained by reducing the last-named compound with hydriodic acid and red phosphorus has m. p. 51'; the hydriodide pale yellow needles m. p. 2 16-218' (decomp.) ; Iydrochloride long slender needles m. p. 236-240' ; chromate granular crystals m. p. 164' ; platinichloride pale yellow needles m. p. 221' (decomp.) ; picrate granular crystals m. p. 232O and aurichloride Cl6H:,,N,HAuC1 H,O microscupic needles m. p. 2 1 1' (decomp.) were prepared. 11. Nitration of m-Tohic Acid.-wh-Toluic acid when nitrated is conveKted into 2-nitro-m-toluic acid 4-nitro-m-toluic acid and 6-nitro- m-toluic acid. It was shown that the compound ILI. p. 215-216O is 6-nitro-m-toluic acid by reducing i t to the amino-compound and distil- ling the latter with lime whereupon o-toluidine was obtained.5-Amino-m-toluic acid C,H,02N crystallises i n groups of small needles with a pink tint m. p. 183' and yields nz-toluidine when distilled with lime. Methyl 6-nitro-m-toluute has m. p. 8 1-83° ; methyl 5-nitro-m-toluate crgstallises in plates m. p. 84-85' ; methyl 4-nitro-rn-toluate forms needles m. p. 7r3-79°. W. H. G. Claisen's Acid Cyanide Synthesis. FERDINAND MAUTHNER (Bey. 1909 42 188-195).-1t has been shown previously (Abstr. 1908 i 348) that 3 4 5-trimethoxybenzoyl cyanide may be prepared from 3 4 5-trimethoxybenzoyl chloride by Claisen's synthesis. I n the present communication it is shown that the chlorides OF anisic ctcid veratric acid dimethylgentisic acid 2 3 4-trimethoxybenzoic acid and 3 4 5-trimethoxybenzoic acid may be converted by this method into the corresponding cyanides which when hydrolysed are first converted into amides and finally into a-ketocarboxylic acids.This method of preparation of the a-keto-acids of phenol ethers is better than t h a t devised by Bouveault (Abstr. 1897 i 530 ; 1898 i 585 ; 1899 i 286) because in this case the positions of the radicles in tho molecule are known. By employing Bouveault's method of converting an a-ketocarboxylic acid into the corresponding aldehydeORGANIC CHEMISTRY. 161 (Abstr. 1896 i 649) it is possible t o pass from phenol ether carboxylic acids to the corresponding aldehydes thus R*CO~Cl-+R*CO*CN-+R*CO*C02H-+R~C~N*R'-+R*CH0. p-Nethoxybenxoyl cyanide C,H,O,N prepared by the action of hydrogen cyanide on anisyl chloride in the presence of pyridine crystallises in colourless needles m. p.63-64'. It is converted by cold concentrated hydrochloric acid into p-methoxyphenylglyoxylamide C,H,O,N colourless needles m. p. 15 I -152O and p-methoxyphenyl- glyoxyhc acid. The following compounds are prepared by methods similar to those just described m-Methoxybenzopl cyanide C,H,O,N forms colourless crystals m. p. 111-112' ; it is not readily attacked by cold concentrated hydrochloric acid. 3 4-Dimethoxpbenzoyl cyanide C,,~,O,N crystal- lises in colourless needles m. p. 11 6-1 17'. 2 ; 5-DzmethoxybenxoyZ cht?oride C,H,O,Cl prepared by the action of phosphorus pentachloride on 2 5-dimethoxybenzoic acid is a colourless oil b. p. 163-164'/ 15 mm 2 5-Dimethoxybenzoyl cyanide C,,H,O,N forms pale yellow needles m.p. 97-98'. 2 5 -DimethoxyphenylgZyoxyZamide C,H,lO,N crystallises in needleq ID. p. 128 - 129'. The corresponding acid first obtained by Bonveaiilt as an oil crystallise8 in needles m. p. 75-76". 2 3 4-Trimethoxybenzoyl chloride C,,H,,O,CI has b. p. 175-176'11 1 mm. m. p. 42'. The corresponding cyanide C,!HllO,N crystallises in colourless needles m. p. 89-90'. 2 ; 3 4-Trzmethozy- poAenylgZyoxy?ic acid C,,H,,O crystallises in colourless needles m. p. 139-140' ; the amide CllH1305N forms needles m. p. 106-107'. 3 4 5-Trimethoxybenzoyl cyanide has b. p. 17S-179'/14 mm. W. H. G. Methyl-carbonato-derivatives of Phenolcarboxylic Acids and their Use for Synthetical Operations. 11. EMCL FISCHER (Bey.1909 42 2 15-228).-The method of preparntion of the chlorides of phenolcarboxylic acids described recently (Abstr. 1903 i 892) cannot be employed with advantage when the hydroxgl group occupies a position ortho to the carboxyl group. o-Ethyl carbonate- benzoic acid has been prepared however by Hofmarm (Arne?*. Patent 1639 174 of Dec. 12 1899) by the action of ethyl chlorocarbonate on n mixtnre of salicylic acid and dimethylaniline in benzene. This method has now been employed to convert the two hydroxyl groups in 2 5-dihydroxybenzoic acid and 2 4-dihydroxybenzoic acid into methyl- carbonato-groups and fram the compounds formed the Corresponding chlorides have been obtained. o-Coumaric acid unlike salicylic acid adds on the methyl-carbonato-group in an aqueous alkaline solution and yields finally the chloride CO,Me*O*C,H,*CH:CH*COCI. p- M ethy Z-carbontctobenxo yloxy benxoic acid CO2Me*O*C6H,*CO*O*C6H,*CO,H obtained by the action of p-methyl carbonatobenznyl chloride on p-hydroxy Genzoic acid crystallises in very small slender needles m.p. 216-217O (corr. decomp.) ; it is converted by dilute aqueous ammonia into p-hydroxybenzoyloxybenzoic acid m. p. about 270' (decomp.) Klepl gives m. p. 261' (Abstr. 1884 446).162 ABSTRACTS OF CHEMICAL PAPERS. o-Methyl-carbonatobenzoic acid C0,Me*O*C6.H4;C0,H forms long glistening plates m. p. 135' (corr. decomp.) ; it is converted by phos- phorus pentachloride into o-methyl-carbonatobenzoyl chloride C,H704Cl a colourless liquid b. p. 107-110'/0*1 mm. ; the latter compound reacts with glycine or glycine ester forming methyl-carbo~tosalicylzlric a d d a viscid oil which is hydrolysed by aqueous sodium hydroxide yielding salicyluric acid (compare Bondi Abstr.1907 i 766). A substance Cl,H70,N is obtained as an intermediate product in the condensation of the chloride with glycine; it crystallises in very thin glistening microscopic plates m. p. 228' (corr.). 5-Methyl-carbonato-2-hydroxybanxoic acid C0,Me-O*C,H,( OH) CO,H obtained by the action of methyl chlorocarbonate on gentisic acid dissolved in N-sodium hydroxide solution crystallises in long colour- less needles m. p. 171' (corr.); it is converted by methyl chloro- carbonate and dimethylaniline in benzene into 2 5-dimetiiyl-carbonato- benzoic acid (CO2Me*O),C,H3*CO2H crystallising in thin plates m.p. 144-145' (corr. decomp.) ; the chloride CllH,07C1 forms microscopic needles m. p. 119' (corr.). 4-Methyl-carlonato-2-hydroxybenzo~c acid CgR,06 crystallises in long needles m. p. 143' (corr.). 2 4-Din~thyl-carbonatobsnzoic acid CllH,,O forms long needles m. p. 159' (corr. decomp.) ; the corre- sponding chloride CllHg07CI crystallises in slender needles or thin leaflets m. p. 86-87' (corr.). o-Xethyl-carbonatocinnarnic acid CO,Me*O*C,H;CH:CH*CO2H crystallises in slender needles m. p. 185' (corr.) ; the cldoride CllH,04C1 forms slender pliable needles. Condensation of Aldehydes with Phenolcarboxylic Acids. 11. E. HOST MADSEN (Arch. Pharni. 1909 247 65-77).-An extension of the reaction described previously (Abstr. 1907 i 423) to other aromatic aldehydes and acids.4 4'- Dihydroxy 5 ; 5'-dintethp?t~iphenylmethane-3 3'-clicarboxylic mid m. p. 248' (approx. decornp.) obtained from benzaldehyde and o-cresotic acid by the general process (loc. cit.) crystallises with 1H,O from ether on addition of light petroleum in tufts of colourless needles and gives in alcoholic solution on addition of ferric chloride a bluiah-violet coloration. The diacetyl derivative m. p. 140-1 45" separates from dilute alcohol in colourless crystale with lI-f,O and gives no colour immediately with ferric chloride but yields a bluish- violet colour with this reagent after boiling with water for some minutes. 4 ; 4'-Dihydroxy-6 6'-dintetl~yltri~l~en?/Z~net~~une-3 3'-dicarboxylic acid m. p. 271' (approx. decomp.) obtained by condensing benzaldehyde with m-cresotic acid crystallises from dilute alcohol in colourless felted needles and is similar in solubility to the first isomeride described but gives a redder coloration with ferric chloride.The diacetyl derivative m. p. 240-245' (decornp.) crystallises in colourless needles or rhomboidal plates and gives a violet coloration with ferric chloride after boiling with water. 2 2'-Dihydroxy-5 5'-dimetl~yltri~l~en?/l,meth~clr,e-3 3'-Jicarboxylic acid m. p. 240' (approx decomp.) obtained from benzsldehyde and W. H. G.ORGANIC CHEMISTRY. 163 p-cresotic acid forms a colourless crystalline powder and generally resembles the two isomerides described above but is somewhat hygroscopic. The diacetyl derivative in. p. I 35-140° crystallises in thin plates and unlike the two isomerides described above is soluble in chloroform ether or hot water.When vanillin is heated with salicylic acid in presence of hydro- chloric acid by the general process no condensation to a triphenyl- methane derivative occurs but decomposition ensues and phenols are formed. Vanillin salicylate m. p. 1 1 0’ (approx.) is obtained when phosphoric oxide is added to salicylic acid and vanillin dissolved in ether and the mixture heated under a reflux apparatus during twenty-four hours. It is coloured green by ammonia gives a violet coloration with Millon’s reagent and yields the characteristic colour reaction of salicylic acid with ferric chloride after boiling in water during a few minutes. The oxime m. p. 164*5’ of the ester forms long colourless needles. No condensation products could be obtained by the general process with (1) paraldehyde and o-cresotic acid (2) acetone and o-cresotic acid or (3) benzaldehyde and o-resorcylic acid.Derivatives of Phenenyltribenzoic [ 1 3 5-Triphenyl- benzene-2’ 2’ 2’”-tricarboxylic] Acid. GIORGIO ERRERA and A. VACCARINO (Gnzxetta 1909 39 i 1-1 l).-The authors have investi- gated further the two isomeric acids obtained by the action of concentrated sulphuric acid on phenenyltri benzoic acid (compare Errera Abstr. 1908 i 185) which are found to have m. p. 362O (instead of 349-350’) and 335-336’ (instead of 32 1’) respectively. The quantities of the two acids obtained are always very nearly in the ratio 4 (m. p. 362’) 1 (m. p. 335-336’) no matter whether the phenenyltribenzoic acid is used in the crude form or after repeated crystallisation.Both are transformed slowly but completely into tribenzoylenebenzene under the prolonged action of concentrated sulphuric acid on the water-bath. Both acids are also esterified moderately readily by Fischer’s method the one with the lower m. p. ratber more slowly than the other probably owing to its less solubility. The observation that tribenzoylenebenzene is formed the more readily from the acid m. p. 335-336’ leads the authors to interchange the two structural formulae previously given (loc. cit.). ~O-~*C(C,H;CO2H):~*~O C,H,*C*CH C* C,H,’ has therefore m. p. 362’. ethyl ester (m. p. 260° instead of 253’) and methyl ester C,6H,302’C02Me m. p. 336-337O were prepared.is deposited from nitrobenzene in yellow needles or large brick-red crystals m. p. about 429’. T. A. H. 2 3 5 6-Dibenzoylene- l-phenylbenzene-3’-carboxylic acid I t s sodium salt C,7H,,0,Na,H,0 and its Its nitro-derivative C,,H,,O,!NO,) 3 CO2 H 3 4 5 6-Dibenzoylene-1-phenylbenzene-2-carboxylic acid 70 -:=C(C,H,* CO,H):CH-)T;’* y,K C,H,*C c*co164 ABSTRACTS OF CHEMICAL PAPERS. crystallises from alcohol in pale yellow silky needles m. p. 335-336O. Its ethyl eRter C,,H,,O,*CO,Et crystallises from light petroleum in elongated yellow lamin% m. Q. 226O and its methyl ester C,,H,,O,*CO,Me cryetallises from light petroleum in minute yellow laminae m. p. 248-249’ ; the sodium salt C27H,,0,Na,5H,0 was prepared. Triethyl phenenyltribenzoate (compare Abstr. 1908 i 185) separates from light petroleum in faintly yellow prismatic crystals m.p. 71° belonging to the monoclinic system [FRANCESCO RANFALDI ~1 b c = 0.48681 1 0.958’73 ; /3= 88’31’24”J. Trimethyl phenenyltribenzoate C,H,(C,H,*CO,~~e) separates from methyl alcohol as a mass of colourless crystals m. p. 94-95’. The great differences between these esters of phenenyltribenzoic acid and the corresponding ones of phenylnaphthalenedicarboxy lic acid (Lamer’s ‘L diphenyltetrenedicarboxylic acid ”) (compare Michael Abstr. 1906 i 518; Lanser Abstr. 1899 i 916) afford a further confirmation of Michael’s views that these two acids are distinct. T. H. P. Inosic Acid. PH(EBUS A. LEVENE and WALTER A. JACOBS (Ber. 1909 42 335-338).-The authors furnish additional evidence of the constitution previously suggested for inosic acid (Abstr.1908 i 93 1). By heating a 28% aqueous solution of the barium salt for six hours at 126-130’ in a sealed tube barium phosphate is eliminated and from the solution which does not contain a pentose or hypoxanthine Haiser and Wenzel’s inosine (Abstr. 1908 i 561) has been isolated ; by more prolonged heating of the barium salt carnine itself is formed. Haiser and Wenzel regard inosic acid and carnine as being derived from the same parent substance. The authors believe that carnine is c. 5. AUGUSTE B~HAL (Compt. rend. 1909 148 179-182. Compare this vol. i 145). -Benzaldehyde can be prepared by boiling for thirty-two hours a mixture of benzylidene chloride (1 rnol.) and acetic acid (2 mols.). Catalysts such as cobalt chloride facilitate the reaction which is probably expressed by the equation CHPhCI + 2HOAc = Ph*CHO + Ac,O + 2HC1.The formation of acetyl chloride which occurs when only 1 mol. of acetic acid is employed is probably due to the action of hydrogen chloride on the acetic anhydride. Curves are given showing the rate of evolution of hydrogen chloride when varying amounts of acetic acid are employed. This reaction is Asymmetric Synthesis PAUL FREUNDLER (Bey.. 1909 42 233-234. Compare Henle and Haakh this vol. i 6).-It was desired to carry out a reaction which requires the influence of light with a racemic compound in circularly polarised light. To this end the conversion of r-o-nitrobenzaldehydediamylacetal (b. p. 186-1 8 7 O / 11 mm.) dissolved in v-amyl alcohol into amyl o-nitrosobenzoate was studied.The Heraeus quartz mercury lamp was used as the source of light and screened so that the light was mainly X=398. Action a degradation product of inosic acid. Preparation of Aldehydes and Acid Anhydrides. stated to be general. w. 0. w.ORGANIC CHEMISTRY. 165 was continued for 400 hours but in a single experiment no evidence of optical activity could be detected. E. F. A. Constitution of Dichloropiperonal." HERMANN PAULY (Ber. 1909 42 417-422. Compare Abstr. 1907 i 709).-Dichloro- piperonal formed by the action of sulphur chloride or sulphur dichloride on piperonaldehyde could not be isolated in a pure state hitherto owing to the presence of colloidal sulphur (compare Schimmel & Co. Abstr. 1906 i 513). It is now found that the sulphur can be removed by passing a current of chlorine into the mixture and distilling off the sulphur dichloride under reduced pressure ; pure dichloropiperonal is obtained by crystallising the residue from chloroform.Since it is so readily prepared by this method i t seemed highly probable that dichloropiperonal had the formula originally given to it by Fittig and Remsen namely COH*C,H,<>CCI,; nevertheless it has been found that when this substance is reduced with zinc dust it does not regenerate piperonaldehyde but yields methylcatechol carbonate ; thus proving the correctness of Delange's view that dichloropiperonal is really dichloromethylcatechol carbonate (Abstr. 1907 i 700). Methylcatecho2 cadonate C8H603 has m. p. 34-35O b.p. 133-135*5O/26 mm. 238-241"/760 mm. It is converted by 50% aqueous pyridine into homocatechol (3 4-dihydroxytoluene) which has m. p. 65" (corr.) and b. p. 251' (corr.). Bdhal and Desvignes give m. p. 51' (Abstr. 1892 1312). W. H. G. Gryetalline Form of 3 4'-Dimethylbenzophenone. PAUL P. SCHORIGIN (BUZZ. Acad. Sci. Xt. Petersburg 1909 79-80. Compare Ber. 1903 36 2027).-This ketone crystallises readily from alcohol in the form of long monoclinic needles La b c = 1.0409 1 0.4154 p = 91°45'] m. p. 82' b. p. 328-330°/760mru. DY 1.134. Z . K. Completely Methylated Flavone Derivatives. JOSEF HERZIG and BR. HOFMANN (Ber. 1909,42 155-159. Compare Abstr. 1891 1386; 1893 i 413).-Morin reacts with methyl sulphate in the presence of a large excess of sodium hyclroxide solution yielding the pentamethyl ether C,,H502(OMe) which crystallises from alcohol in colourless needles m.p. 154-157'. Its alcoholic solution is colourless but turns yellow on the addition of potassium hydroxide solution. When boiled with alcoholic potash it yields 2 4-dimethoxybenzoic acid and the trimethyl ether of o-hydroxyfisetol @H*C,H,(@Me),*CO*CH,*OMe (6-hydroxp2 ; 4-dimethoxyphenyl rrhethoxymethyl ketone) which separates from alcohol in compact colourless crystals m. p. 102-104°. The oxime C,H,O,N(OMe) crystallises from dilute methyl alcohol in colourless needles m. p. 147-149' and the methyl ether has m. p. 49-52". A 25% yield of quercetin pentamethyl ether (Waliaschko Abstr. 1904 i 760) can be obtained by treating quercetin with methyl C6H2(0Me),*CO*CH,*OMe,166 ABSTRACTS OF CHEMICAL PAPERS sulphate and sodium hydroxide and keeping for several days.When warmed with alcoholic potash the ether yields 3 4-dimethoxy benzoic acid and the trimethyl ether of o-hydroxyfieetol. J. J. S. Bisdiketohydrindene. HUGO VOSWINCKEL (Ber. 1909 42 465-470).-Considernble amounts of Nathanson's bisdiketohydrindene (diphthalylethane) ( A bstr. 1894 i 38) are obtained in the prepara- tion of dihydrox naphthaceneqninone (Gab1 iel and Leupold Abstr. 1898 i 482). &hen treated with a mixture of glacial acetic and nitric acid (1.48) at O' the hydrindene derivative yields a mixture of two oxidation products. The one dissolves readily in cold benzene whereas the other is very sparingly soluble. This second conzpound C18H1208 crystallises from hot chloroform in short six-sided prisms m.p. 61l0 and the structural formula r - C,H4<co.o>CH*CH( co- OH)* CO*C6H4*CH0 is suggested. It yields an acetyl derivative C120H1407 m. p. 3 1 5 O a benzoyl derivative C25H,607 m. p. 268' and a methyl ether Cl9HI4O6 which turns brown at 240' and decompohes a t higher temperatures. With phenylhydrazine the oxidation product yields a complex con- densation product (Cl,H120 + 5C,H8N2- 5H,O) which crystallises from glacial acetic acid in red needles with a high metallic lustre and m. p. 209'. The oxidation product dissolves in cold normal sodium hydroxide solution and the immediate addition of hydrochloric acid yields an acid C,,H1,0,,2H,O which crystalliaes f com glacial acetic acid in clear prisms m.p. 240'. Its solutions in ammonia or alkali carbonates have a reddish-brown colour and those in alkali hydroxides a reddish- brown colour which changes rapidly t o blue. Hot sodium hydroxide transforms the oxidation product in to phthalonaldehydic acid CO H*C,H,*CO* CO,H which cry stallises f roni water in small prisms and plates m. p. 144'. Itsphenylhydrazone has m. p. 229'. J. J. S. The Naphthacene Series. 11. HUGO VOSWINCKEL (Ber. 1909 42 458-465. Compare Abstr. 1906 i 99).-Phenol and acetic acid react with naphthacenediquinone in the presence of sulphuric acid yielding a product C18H80,,C:,H60,C,H40 which crystallises from nitrobenzene in pale yellow prisms m. p. 283'. The formula C (OH) (C,H,*OH)$ CO C,J%<C (0 H 1 (O*c),-C C*>C,H49 dihY droxYacetoxY-hYdroxY - phe,~?/ldihydronaphthacenequinone is suggested.The phenolic group is firmly attached and cannot be removed by reduction or hydrolysis whereas the acetyl group is readily eliminated. Acetic anhydride and zinc chloride transform the condensation Droduct into the tetra-acetvl c(oA~)(c,H,=oA~).c.~o derivative C,H,<c(oAc) ,-j cO>C,H which forms pale yellow crystals m. 6. 28KORGANIC CHEMISTRY. 167 The condensation product dissolves in dilute alkalis yielding brownish-violet-coloured solutions and the addition of mineral acids yields the three products 1. ~riiLyd~ox?/-?LydroxypA~n yZdiA ydronaph thacenepuinone C( OH) ( CGH4-OH) * CO C"H,<C(OH),--C. C0>cGH4' -It is insoluble i u benzene but crystallises from dilute alcohol in yellow prisms m.p. 1 go" dissolves in alkalis giving characteristic colorations and dyes silk an orange colour. Its solution in concen- trated sulphuric acid has a reddish-violet colour which turns to a steel-blue .when warmed ; with acetic anhydride and zinc chloride i t yields a monoacetyl derivative C,,H,,O7 which Feparates from glacial acetic acid as a colourless cryhtalline powder m. 1'. 285'. . . - isolated as the calcium salt. The acid separates as a flocculent mass containing water of crystallisittion; wrieri heated a t 80" it loses 0*5H,O assumes a crystalline texture and then melts at 130". Treat- ment with acetic anhydride and zinc chloride leads to the elimination of water and the formation (jf an ucetyl derivative OAc*C,H,*~I'h-~H* CO which crystallises from glacial acetic acid in golden-yellow plates m.p. 2664 Treatment with inetbyl sulphate transforms the acid into a tetrametiLy1 derivative which forms colourless plates m. p. 124'. 0-c )*CH*CO ' >C,& OMe* CGH,*CPh( OMe)*C( C0,M.e) C( CO,Me)*COPh C( C,H,'OH)(OH)*~H* $!( OH) 3. A compound C,H,<CO C! H C(0H) >'GH4 (*) which crystallises from dilute alcohol in orange-coloured needles m. p. 174'. It dissolves in alkali hydroxides to a violet solntion and in sulphuric acid to a pure blue solution. Itl yields a monoacetyl deriv- ative C,,$,,O m. p. 1 7 2 O . Resorcinol orcinol and phloroglucinol condense with naphthacene- diquinone and glacial acetic acid in the absence of sulphuric acid. The product obtained from resorcinol has the composition C,,H,,O and forms a reddish-brown crystalline powder m.p. 234". Nupkdiacenepuinhydrone C18Hs04,C18HZ004 is obbained by the union of naphthacenediquinone with dihydroxynaphthacenequinone in nitrobenzene solution and is identical with the compound previously described as a desmot ropic modification of naphthacenediquinone. J. J. S. Reactions of 9 10-Dihydroanthracene and of Anthranol. ROBERT PADOVA (Compt. rend. 1909 148 290-292).-When 9 10- dihydroanthracene is heated at 250' for two and a-half hours with diphenyldichloromethane tetrccphen?/la~~t~LraxyliZene CP h 2 C<' '4>C CPh C6H4 is obtained. This has m. p. 305" and is identical with the substance168 ABSTRACTS OF CHEMICAL PAPERS. I I obtained by Staudinger (Abstr. 1908 i 410) by the action of anthraquinone on diphenylketenquinoline.On reduc- tion with sodium and benzyl alcohol it yields the /\/\/\ compound I (below) which has m. p. above 360" and I ' I I shows an intense violet fluoreFcence. formed by the action of amyl nitrite on a solution of A/\/\ dianthrone in pyridine. The action of chloroform I I I 1 and alcoholic potassium hydroxide onanthranol leads \/\/\/ to the formation of a substance crystallising in deep This is 10-oxanthryl-9- anthraquinonementhane (formula 11) The acetyl derivative has m. p. 201-202O. The bermoyl derivative forms canary-yellow prisms m. p. 2 1 6-2 1 8". 0 \/ Dianthraquinone (annexed formula) is said to be red prisms m p. above 310'. 0 230° but is not sharp. The name dianthranol is /\/\/\ assigned to this compound that previously described as I dianthrauol or dianthrone (Zoc.cit.) being regarded as IORGANIC CHEMISTRY. 169 the action of magnesium on a mixture of allyl bromide and a ketonic compound under the conditions previously laid down (Abstr. 1908 i 3-AZZyZmenthan-3-oZ C13H2*0 b. p. 1 30°/22 mm. prepared from 2-Allylborneol b. p. 130'/20 mm. from camphor and allyl bromide. A4-AZZyZ-3-p-rnenthen-3-oZ C13H,,0 b. p. 135'/27 mm. from pulegone and allyl bromide. These three alcohols which were obtained in about 90% yields are colourless mobile liquids. Treated under the above conditions with allyl bromide piperonal yields a thick yellow liquid b. p 169-1'70"/27 mm. ; furfur- aldehyde a thick yellow liquid b. p. 266-272'; menthyl oxide a colourless mobile liquid b. p. 168-170O (slight decomp.) with a smell like that of camphor ; benzylideneacetone an almost colourless liquid b.p. 165O a t which temperature water is given off ; benzil a thick brown liquid which decomposes when distilled under 22 mm. pressure. The reaction between allyl bromide and a ketonic compound in presence of magnesium sometimes fails without apparent reason. One condition necessary for success is a slow gentle action any strong heating always lowering the yield of alcohol. The Grignard Synthesis. Action of Magnesium Phenyl Bromide on Camphor. H. JERMAIN M. CREIGHTON (Trans. Nova Xcotha Inst. Sci. 1908 11 (4) 593-59i).-The interaction of ethereal magnesium phenyl bromide and camphor in equal molecular quantities at 60" leads to the formation of phenylborneol C,,H!,Ph*OH b. p. 258-260' or 143-145'/14 mm.D 0.977 [a]D 7'55 in alcoholic Attempts to Resolve Racemic Camphoric Acid and iso- Borneo1 into Active Components. ERNST BECKMANN (Ber. 1909 42 485-491. Compare Pickard and Littlebury Trans. 1907 91 1973).-The isoborneol obtained from camphene by Bertram and Walbaum's method (Abstr. 1894 i 204) has m. p. 212' and is slightly dextrorotatory in solution the value for [a]D varying from + 1.2' to + 3.9' according to the solvent used. When oxidised the isoborneol yields a camphor which is slightly Isevorotatory and on further oxidation a camphoric acid which is also slightly laevorotatory. No isocamphoric acid is formed as treatment with acetyl chloride completely transforms the acid into its anhydride. The acid obtained is mainly r-camphoric acid with a slight excess of the E-acid and can be resolved by repeatedly crystallising the acid cinchonidine salt from aqueous alcohol.The d-acid had m. p. 183' and [a]D + 44*4' and the Z-acid m. p. 186-187' and [a] - 50.7O. Attempts to resolve the isoborneol itself were made by conversion into the isobornyl hydrogen succinate and resolution of this by means of its cinchonidine salt. isoBornyl succinate C24H3804 has m. p. 37' and resembles camphor in appearance. isoBorny1 hydrogen succinate C,,H2204 is a clear oil with an acid taste and an odour of isoborneol. The cinchonidine salt 753). allyl bromide and rnenthone. These products are under investigation. T. H. P. solution (compare Zelinsky Abstr. 1901 i 660). c. s.170 ABS'CRACTS OF OHEMICAL PAPERS. C,,H,,0,N2 crystallises from dilute alcohol in slender needles m.p. 107". By crystallising from its 40% alcoholic solution nine fractions with [aID varying from + 11.3" to - 2.5" were obtained. The genetic relationship of the camphors and borneols is repre- Fented by the following scheme ,I-isoborneol >-+ I-camphor. / d-isoborneol +\ I-borneol d-camphor ' d-borneol J. J. S. Components of Ethereal Oils. Constitution of Camphene. Its Oxidation with Ozone. FRIEDRICII W. SEMMLER (Bey. 1909 42 246-252).-When ozonised camphene forms only one ozonide which is decomposed in two ways on the one hand (to the extent of about 30%) into camphenilone C,H,,O and this t o a hydroxy-acid 6-hydroxycamphenilonic acid which forms a beautifully crystalline &lactone CgHI,02 whilst on the other hancl acids C,H1402 are formed.Ccmphene oxonide annexed formula prepared / I \ CH CH (~<cH by leading a stream of ozone through camphene I AH dissolved in chloroform is a viscid oil which C'H C<yH2 decomposes when distilled in a V ~ C L I U I ~ . Cum- /CH,*CH phenilone CH-CH2*CH has m. p. \CMe2*CO/ CH 40° D3* 0-9705. The semicarbazone CgH14:N *NH*CO*NH has m. p. 223' ; the oxime has m. p. log" b. p. 128-129'/14 nim. The nitride C,H,,N prepared by boiling the oxirne with dilute sulphuric acid has b. p. 85-90°/12 mm. D20 0.9449 n 1.47348. Camphoceenic acid obtained by the action of alcoholic potassium hydroxide ou the citrile has b. p. 145-146"/11 mm. D20 1.020 n 1.4862. P I \ \ I / 0 3 \ I / H,*CH( CMe,-OH) )CH forms a CH; CH( C0,H) 8-Hyd~oxycamphenilonic acid thin syrup b.p. 125-175O/lO mm. ihich 'decomposes forming a solid distillate of thelactone. This has m. p. 95-96' b. p. 1 26-128"/10 mm. and forms large plates ; it dissolves slowlyin a slight excess of potassium hydroxide and this solution yields a colourless silver salt. The silver ,salt interacts with methyl iodide forming methyl 6-hydroxycampheni- Zonate b. p. 126-127"/10 mm. D20 1.0423 n 1.46797. Both the acid and lactone behave as saturated compouuds to permangnnate. The acid CgH1402 obtained also by the decomposition of camphene ozonide in a vacuum is regarded as a mixture of an unsaturated monocyclic and a saturated dicyclic acid. It has b. p. 136-140°/10 mm. D*O 1-028 m 1.475 ; the methyl ester has b. p. 94-96'/10 mm. D20 0,988 n 1.46261.In view of these results crude camphane consists t o the greater /CH,-CH \CMe2-C(-CH,)/ part of semi-cyclic-camphene CH- C H9- ,'CH. E. F. A.ORGANIC CHEMISTRY. 171 Constituents of Ethereal Oils. Inversion of Carvenene CloH (Terpinene ?) into isoGarvenene CIoH (isoTerpinene 3). FRIEDRICH W. SEMMLER (Ber. 1909 42 522-52'7. Compare this vol. i 1 lo).-Carvenene has the following constants D202 0.8443 ng'2 1.49065 which result confirms the conclusion previously arrived at that cyclic conjugated double linkings cause an exaltation in the molecular refraction (cal. 45.240 found 46.6 19). When carvenene is heated with alcoholic sulphuric acid for two hours isocarvenene CloH16 b. p. 59-62'/10 mm. D20 0.845 nD 1.480 (the exalta- tion in t h i s case is only 0*4) and a dicarvenene C20H32 b .. p. 170-173'/10 mm. D20 0*92S n D 1.5175 are obtained. The physical constants for isocarvenene are identical with those of terpinene obtained from sabinene mono- or di-hydrochloride and i t has been found that all terpinenes are converted into a terpene by alcoholic sulphuric acid the physical data of which agree with those of isocarvenene. This compound yields terpinene nitrosite identical with that obtained from carvenene. I n order to investigate further the conversion of carvenene into the iso-compound the action of bromine on '' terpinene " from sabinene dihydrochloride in amyl alcohol-ether sdution was studied ; crystals of terpinol tetrabromide were deposited thus proving that terpinol is present in the "terpinene," which has hitherto been regarded as pure when prepared from the dih y drochloride.Carvenene on repeated reduction with sodium and amyl alcohol gives dihydrocccrvenene ( A2-tetrahydrocymene) CloHls an oil b. p. 55-56'/12 mm. D20 0.824 nD 1,461. Oxidation of carvenene with ozone yields dimethylacetonylacetone (b. p. S2-86°/10 mm.). Carvenene is regarded as A' '3-dihydrocymene and isocarvenene A' ; '-dihydrocymene. W. R. Sesquiterpenes. ERNST DEUSSEN (Ber. 1909,42,376-383 ; 680). -The author is unable to say from which of the two and possibly three isomeric hydrocarbons present in caryophyllene (Abstr. 1908 i 353) the following substances are derived. The oxidation of caryophyllene (a - 14') by dilute aqueous potassium permanganate at 0' yields a glycol Cl>H2,0 m. p. 120.5" (Zoc.cit.); from the oily potassium salts remaining after the removal of the glycol two acids have been obtained. One is a liquid monobasic acid Cl0H1,O3 which forms a crystalline semi- carbuzone C,,H,,O,N m. . p. 186' (slight yellow coloration) and the other is a crystalline monobasic acid CsH804 m. p. 179*5-1S0.5' which sublimes without decomposition does not form a semicarbazone and is not identical with Baeyer's A2 4-dihydro- phthalic acid. When a solution of caryophyllene in acetone containing a little water is cooled in a freezing mixture and oxidised by the gradual addition OF powdered potassium permanganate (two atomic proportions of oxygen) a substance ClOHlsO,,. m. p. 145-146' is obtained which separates from hot benzene in white needles is unchanged by dilute sodium hydroxide at loo' has a bitter-sweet taste and172 ABSTRACTS OF CHEMICAL PAPERS.appears to be a glycol since it is changed by dilute sulphuric acid to an amorphous white substance C1,H1,O2. [With A. LOESCHE.]-T~~ residue remaining after the distillation in a vacuum of oil of clove stalks freed from eugenol yields by treatment with alcohol a voluminous white substance (C21H300) m. p. 146O which can be purified by repeated precipitation of its chloroform solution by alcohol. c. s. Ethereal Oil of the Root Bark of Cinnamomum zeylani- cum. A. A. L. P I L a R m (Plharm. Weekblad 1909 46 50-54).-The chief constituent of the oil of the root bark of Cinnamomum xeykanicurn is camphor. The other constituents are pinene cineol dipentene phellandrene eugenol safrole probably carophyllene and borneol and possibly cinnamaldehyde. The oil from the leaves contains 76% of eugenol along with pinene and cinnamaldehyde. The oil from an old sample of the stem bark contained 50% of cinnamaldehyde and that from a specimen of young bark 70-75%.In both pinene benz- aldehyde and eugenol were also present. A. J. W. Extracts containing Glucosides. LEOPOLD ROSENTRALER and R. MEYER (Arch. Pharm. 1909 247 28-49).-The object of this research was to determine whether in the preparation of extracts of drugs containing glucosides by exhaustion with water as recommended by various Pharmacopeias decomposition of the glucosides ensued and if so whather this could be prevented by (1) neutralising the natural acids of the drug by adding calcium carbonate and (2) by rendering the enzymes inactive by immersing the drug in boiling 95% alcohol.Experiments with gentian centaury alder bark cascara sagrada bark and rhubarb showed that the first question must be answered in the affirmative that although in none of these cases did the calcium carbonate exert any deleterious action its protective action with respect to the glucosides was slight and that extraction with hot alcohol is harmful in the case of centaury is of no advantage in the case of alder bark but is to be recommended in the cases of gentian cascara sagrada bark and rhubarb. The methods adopted in esti- mating the glucosides etc. in these various extracts are described in detail in the original. T. A. H. Cholesterol as an Antidote to the Saponine. ADOLF WINDAUS (Ber.1909 42 238-246).-The action of cholesterol as an antidote to the power of saponins to dissolve blood-corpuscles discovered by Ransom has been ascribed to a chemical reaction and to a physical change such as absorption. The poisons of bees snakes and bacterial poisons are similarly counteracted by cholesterol. Digitonin and cholesterol when mixed in alcoholic solution immedi- ately give rise to a colourless crystalline precipitate in fine needles of digitonin- cholesteride C,,H,,O + C,7H,,0 formed as a simple molecular compound of the two components without any elimination of water. The compound decomposes above 2 4 0 O ; it is quite impossible to obtain cholesterol from it by prolonged extraction with ether,ORGANIC CHEMISTRY.173 It slowly dissociates when boiled in methyl-alcoholic solution for some hours. It is entirely without any solvent action on the blood-corpuscles. Other alcohols behave similarly to cholesterol towards digitonin. Phytosterol forms a molecular compound crystallising in thin needles ; the compound with stigmasterol is even less soluble. Digitonin-P- cholestanol is more soluble than the cholesteride and crystallises in stellar aggregates of needles. a-Cholestanol (cyclocholesterol) forms no such molecular compound. Digitonin-amyl alcohol (C,,H,,O + C,H,,O + 6H20) (compare Houdas Abstr. 1892 222) is more soluble than the cholesterol derivative. The air-dried product loses amyl alcohol when boiled with water. Digitonin-octyl alcohol behaves similarly. 0 t her alcohols linalool geraniol and sabinol also combine with digitonin.Cholesterol esters do not unite with digitonin nor do these esters counteract the poisonous action of saponins. When digitonin- cholesteride is acetylated it is easy to remove the cholesterol acetate. The reaction can be used to detect small quantities of cholesterol and to separate it from mixtures particularly in cases when cholesterol esters are also present. It is also applicable to the purification of digitonin. Solanin-cholestwide is very sparingly soluble in alcohol but crystal- lises with difficulty. Cyclamia cholesteride crystallises in minute needles but the cholesterol can be extracted from this with ether. Cyclamin also gives an insoluble crystalline additive product with octyl alcohol.From the analysis of this cholesteride the formula C36H56018 for cyclamin is obtained E. F. A. Scopoline. ERNST SCHMIDT (Arch. Phacrn. 1909 247 79-80).- It mas shown previously (Abstr. 1906 i 104) that scopoline is reduced without difficulty to hydroscopoline which contains two -OH groups. Further on oxidation with chromic acid scopoline yields pyridine- methochloride and from these observations the deductions are drawn that the -OH group of scopoline does not lie in the pyridine nucleus and that the same applies to the second oxygen atom which must be present in an ether or morpholine group. In confirmation of this view it is now shown that hydroscopoline when carefully oxidised with chromic acid yields a n z e t h y l ~ p e r i d i n e d i ~ ~ ~ o x y z ~ acid m.p. 214-21 6' (decornp.) which crystallises in transparent tablets and yields a crystalline azure-blue copper salt. The hydrochloride m. p. 224-225' (decornp.) is crystalline and the aurichlorids forms large yellow leaflets. act'-Dimethylpyridine on oxidation with permanganate furnishes methylpyridinecarboxylic acid (m. p. 129') and Ladenburg's act'- pyridinedicarboxylic acid. The latter on electrolytic reduction furnishes two isomeric hydrogenised acids of which one m. p. 206-207O seadily passes into the other m. p 158' and it is hoped by methylating these acids to synthesise the acid obtained by oxidising hyd roscopoline. T. A. H. C8HI,o,N 9 H2° VOL. xcvx. i. I)IL174 ABSTRACTS OF CHEMICAL PAPERS. The Chlorophyll Group. 111. New Method of Decom- position in the Chemistry of Chlorophyll.LEON MARCRLEWSKI (Biochem. Zeitsch. 1909 16 3-8. Compare Abstr. 2908 i 439).- The zinc compound obtained by the action of zinc hydroxide aud carbon dioxide on an alcoholic solution of chlorophyllan is termed “ zinc chlorophyll.” It is a complex metallic derivative of chlorophyll which it closely resembles in properties. Treatment with acids con- verts the zinc compound into chlorophyllan whereas alkalis (alcoholic potassium hydroxide) transform it into a substance analogous to alkachlorophyll the chief difference being that the new compound contains zinc whereas nlkachlorophyll contains magnesium. The name ‘‘ zinc-prophyllotaonin ” is suggested. The compound dissolves in ether yielding a brilliant greenish-blue solution with a red fluorescence.The solution gives five characteristic absorption bands between h 677 and h 492. Treatment of the new compound with concentrated hydrochloric acid yields phyllotaonin or allophyllotaonin. J. J. 5. Rotation of Tannin MAXIMILIAN NIERENSTEIN (Chem. Zeit. 1909 33 126).-Feist’s view (7bid. 1308,32 918) that the rotatory power of tannin i s due to admixture of dextrose formed by the hydrolysis of a glycogallic acid is not accepted. Experiments show that specimens of tannin which are free from dextrose have a high rotatory power. J. J. S. Tannin MAXIMILIAN NIERENSTEIN (Ber. 1909 42 353-354. Compare Abstr. 190S i 40).-Since luteo-acid:(pentahydroxydiphenyl- methylolidecarboxylic acid) and ellagic acid are produced by the oxidation of tannin the author has suggested that the production of ellagic acid in plants may be due to oxidation (Abstr.1908 i 897). This suggestion is strengthened by the fact that the hot filtered pyridine extract of myrobalan after dilution with water boiling and keeping for thirty hours yields ellagic acid whilst the concentrated mother liquor deposits luteo-acid identical in all respects with that obtained synthetically from tannin. c. s. The So-called “Bloom” of Pyrogallol Tannins and Its Identity with Ellagic Acid. MAXIMILIAN NIERENSTEIN (Chem. Zeit 1909 33 87. Compare Abstr. 1905 i 365 805).-The “bloom ” of some samples of sole-leather and of various pyrogallol tannin materials has been examined and with but one exception was conclusively shown to be ellagic acid. The exception is ‘‘ white mangrove,” the bloom of which is laguncurin a yellow dye.W. H. G. Coumarandione the Analogue of Isatin in the Coumarone Series. RICHARD STOERMER (Ber. 1909 42 199-202. Compare Stoermer and Kahlert Abstr. 1902 i 457).-It has at last been found possible to prepare coumarandione the lactone of o-hydroxybenzoyl- formic acid which is the analogne of isatin in the coumarone series. 1-Nitro-2-diisobutylaminocoumarone when warmed with alcoholicORGANIC CHEMISTRY. 175 potassium hydroxide is decomposed with the formation of diisobntyl- amine and the potassium salt of aci-nitrocoumaranone obtained as lemon-yellow needles. acid it liberates nitric peroxide and yields " leuco-oxindigo," When this salt is treated with an obtained as a canary-yellow 'precipitate m.' p.276" (decomp.). The leueo-compound is oxidised by chromic acid in acetic acid into coumarandione C,H,O which crystallises with 1 H,O in small yellow needles m. p. 1 7 8 O (decomp.) and is converted by hot dilute hydro- chloric acid into o-hyclroxybenzoylformic acid Coumarandione when acted on by hydroxylamine yields diisonitrosocoumayone a colourless crystalline substance m.' p. 203-205'. o-Hydroxybenzoylformic Acids and Coumarandiones. KAXL FRIES (Be,.. 1909 42 234-236).-o-Hydroxybenzoylformic acid occurs in an anhydrous form and also as monohydrate. The hyd~ata of 2-hydroxy-4-methylbenzoylformic acid crystallises in plates m. ,p. 64'; it is faintly yellow and stable in the atmosphere. The anhydrous acid is more soluble in benzene than the hydrate; it crystallises in feather-like needles m.p. 1 0 2 O which are almost colourless except when viewed in mass. The hpdrate of 2-hydroxy-5- methylbenzoylformic acid forms yellow prisms m. p. 75'; the anhydrous acid crystallises in needles m. p. 107O. These acids lose carbon dioxide and water when heated forming methylcoumarandiones but the yield is small and the product di5cult to purify. They are conveniently prepared by heating the hydroxybeozoylformic acids in benzene or petroleum solution with an excess of phosphoric oxide for fifteen minutes. W. H. G. 5-MethyZcoz~marandione C6H,Ne<(o>C0 crystallises in well- formed yellow plates m. p. 112'. I n contact with water it is slowly converted into the hydroxy-acid and goes into solution. It dissolves in concentrated sulphuric acid with a yellowish-red coloration and on dilution the hydroxy-acid is formed. The ketone reacts immediately with o-phenylenediamine but 2-hydroxy-3-m-hydroxy-p- tolylquinoxaline and not methylcoumarophenazine is formed.4-Methylcoumarandione crystallises in long golden-yellow prisms m. p. 149'. These diketocoumarans and the hydroxy-acids give the indophenin reaction with benzene containing thiophen and concen- trated sulphuric acid. E. F. A. Method of Preparation of Ketothionaphthens. KARL AUWERS and F. ARNDT (Ber. 1909 42 537-545).-Starting with p-tolyl methyl thioether a method is described of obtaining thionaphthen derivatives by using chloroacetyl chloride. pToZyZ methyl thioethm C,H,,,S from the sodium salt and methyl n 2176 ABSTRACTS OF CHEMICAL PAPERS.sulphate is a colourlesa oil b. p. 209"/747 mm. 9 4 O / 3 1 mm. D1,6 1.0302 nz 1.57537 which when heated with chloroacetyl chloride and aluminium chloride in carbon disulphide solution for five hours and subsequently distilled with steam is converted into keto-4- rnethy2thionaphtAen C,H,Me<';>CH,. It crystallises from petroleum in colourless needles m. p. 103" which gradually change when moist to carmine-red. On oxidation with potassium ferri- cyanide in diln te alkali '' 4'-dimethylthioindiqotin," C,,H,,O,S is formed which crystallises from nitrobenzene in brownish-red needles m. p. over 300'. C,H,Me<yf> C CHPh is formed by the condensation of benznldehyde and ketomethylthio- naphthen in alcohol in the presence of hydrogen chloride and forms long yellow glistening needles m.p. 145 *5O. forms stout yellow prisms m. p. 116O and is re-converted into the parent substance by alkali or alcohol. hT'tobenxylidene-thionu~htkeiz C,,H,,OS crystallises from alcohol in yellow needles m. p. 131.5"; its dibronzide C1,HloOBr,S forms crystals m. p. 114-115°. 6-Met~~Zthiol-3-rnethyZa,ceto~~~~enone SMe*C,H,Me*COMe from tolyl methyl thioether acetyl chloride and aluminium chloride crystallises from light petroleum in white needles m. p. 51.5". It is not hydrolysed by known methods either being I ecovered unchanged or suffering decomposition. The 6-thiol-3-methylacetophenone could not be obtained from the thiocresol by a similar method to the methyl ether. p-Tolyl chlorothiotacetate C,K,Me*S*CO*CH,Cl from thiocresol and chloroacetyl chloride which forms snow-white crystals m.p. 38" could not be converted into the o-chloroacetyl isomeride (compare Fries and Pinck t h i s vol. i 42). The acet2l compouud of thiocresol J,H,,OS is an oil b. p. 121'/14 mm. Cinchonamine and Certain Other Rare Alkaloids. BERNARD F. HOWARD and 0. CHICK (J. Xoc. Chern. Ind. 1909 28 53)-The results of trials with cinchonamine hydrochloride as a test for nitric acid and for the estimation of nitrates by the formation of cinchon- amine nitrate which is nearly insoluble in water especially in presence of free acid (compare Absti.. 1905. i 102) are given. Certain data respecting cinchonamine quinicine cinchonicine cupreine and concus- conine are also recorded. Cinchonamine hydrochloride may be used for the estimation of nitrates in certain cases where other methods present difficulties and yield results but little inferior to those given by the nitrometer process but is unsuitable for use in presence of salts of bismuth or other metals which yield insoluble oxychlorides. In aqueous solution 1/100,000 OF nitric acid can be detected and in acetic acid 1/500.Cinchonamine C19H240N [aID + 120° in alcohol does not contain methoxyl. Quinicine U20H2402N8 [a] + 38'40' in chloroform yields a Keto benx y Zidene - rneth y 1 t?Lionapht?Len The dibromide c16H120Br2S9 W. R.ORGANIC CHEMISTRY. 177 crystalline tartrate B,H2C4H406 and oxalate 2B,H,C,0,,9H20 and contains one methoxyl group. Cinchonicine C1,H,,ON [a] + 47O13' like quinicine could not be obtained crystalline ; it does not contain methoxyl.are crystalline. Concusconine C,,H,,O,N [.ID + 19'34' was prepared from cinchonamine residues ; it contains two methoxyl groups. Cupreine U,,H,,O,N,,. [.ID - 163'45' in alcohol contains no methoxyl. The amorphous platzmchloride B,H,PtCI,,H,O was prepared but the salt B,,H,PtC1,,4H20 referred to by LBger could not be obtained. Cupreine sulphate B,,H,SO is stated to crystallise with 6H20 but this salt prepared under various conditions was found to be anhydroue. The acid sulphate B,H2S04,H,0 crystallises in short stout yellow prisms. The disulphate B,2H,S04,3H,0 forms short silky needles and is deliquescent. The hydrochloride B,HCl,H,O crystallises in small slightly brown needles and the dihydrochloride B,2HCl is also crystalline The formulae assigned to these' alkaloids were confirmed by determination of the platinum in the respective platinichlorides.T. A. H. The tartrate B,H,C4H,0,,H,0 and oxalate 2B,H2C204 7H20 Isomerism of Ephedrine and +-Ephedrine. HERMANN EHDE (Arch. Phwrm. 1909 247 54-55).-In a previous paper (hbstr. 1908 i 203) the author has shown that ephedrine is better represented by the formula NHMe-UHPh*CHMe*OH than by OH*CHPh*CHMe*NHMe and that +-ephedrine is an optical isomeride of ephedrine. Gadamer (this vol. i 49) accepted this but suggested that the conversion of the one isomeride into the other by the action of hydrochloric acid is probably due to racemisation in the asymmetric complex containing the hydroxyl group rather than in that con- taining the methylimino-grouping.The author now points out that this explanation is not excluded by his former paper and that he left this point as an open question. T. A. H. Crystallography of the Ephedrine Damascenine and Aconitine Groups. K. SCHWANTKE (Zeitsch. Kryst. Min. 1909 46 73-115).-$-Ephedrine rhombic [a b c = 0.84492 1 1.8598 . Ephedrine hydriodide rhombic [a b c=0*73703 1 0*28643]. +-Ephedrine hydriodide rhombic [a b c = 0 60282 1 1.37221. Methylephedribe methiodide rhombic [a b c = 0.97926 1 0.760881. Methyl-$-ephedrine methiodide rhoubic L0.64227 1 1 *2088]. Damascenine hydrochloride triclinic [a b c = 0-66527 1 0.453 18 ; a= 89'51'; /3= 103'30'; y=89'11']; hydrobromide monoclinic [ a b c = 2.7575 I 2.4825 ; fi = 100°6'] ; hydriodide monoclinic [a b c = Aconitine rhombic [a b c = 0.54492 1 0.389171 ; hydrobromide rhombic [a b c=O*86455 1 1.30951 ; hydrochloride rhombic [a b c= U.1174S8 1 1.30401.Piciaconitine could not be obtained crystalline. Methylpicraconitine rhombic [a b c = 0.995'72 1 :1*31416]. Ethylpicraconitine rhombic [a b c = 0.117952 1 1.2700]. Aconine hydrochloride monoclinic [a 6 c = 0.6346 1 1 1.0374 ; /3 = 90'1. 2.7519 1 2.43'72 ; p = 99'27'1. L. J. S."178 ABSTRACTS OF CHEMICAL PAPERS. Dicyclic Quaternary Bases. AUGUST ALBERT (Ber. 1909 42 545-556).-1t has been shown by Gabriel and Uolman (Abstr. 1906 i 881) that when evaporated with water y-chloropropyl- piperidine is transformed into the quaternary salt and that the reaction is a reversible one. This paper deals with the preparation of a dicyclic quaternary salt containing one more methylene group in one of the rings.1-&Phenoxybutylpiperidine OPh.[CH,],*C,NH1 obtained by heating 8-chlorophenoxybutane with piperidine for four hours at loo' distils at 316-320'. It is purified by means of the hydriodide CI,H,,ON,HI which forms white feathery needles m. p. 147'; the hydrochloride has m. p. 156O the hydrobromide m. p. 159O the picrate m. p. 120-121' the rnercurichloride m. p. 138O and the gold salt m. p. 121'. When the hydrochloride is heated with hydro- chloric acid in a sealed tube at 150' for five hours 1-6-chlorobutyl- piperidine hydrochloiGde CH2C1* [CH2],*C5NH,,,HCl is formed quanti- tatively; it crystallises in white plates from acetone m. p. 162'; the auricldoride CgHlgNC1,Au has m.p. 93' the picrccte m p. 132O. 6-Bronrobutylpiperid~~ hydrobromide C,H,,NBr prepared in a similar rdanner forms plates m. p. 162.5'. A cold ethereal solution of 8-chlorobutylpiperidine is quickly converted into tetramethylenepiperylium chiloride >CH2 FH,*CH CH,*CH CH2*CH >NC1<CH,*CZ32 which forms white hygroscopic leaflets ; the auriclbloride C H,,NCl,Au has m. p. 245' the picrate C15H2,07N4 m. p. 232' the mercuri- chloride CgH,NC1,6HgCl m. p. 2 2 9 O the platanic?doride m. p. 237". Alkali converts 8-bromobutylpiperidine hydrobromide at once into the quaternary salt. That it is not the diquaternary salt C ~ H ~ ~ C 1 < ~ ~ ~ 3 > N C l C ~ H ~ ~ is proved by its synthesis from e-chloropentylpyrrolidine whereas if diquaternary salts were obtained in such regctions the isomeric compound C,H,NCl<[C8215>NC1C,H would be the result.This was accomplished by heating echlorophcnoxypentane with pyrrolidine at 100' for four hours when r-phenoxypentylpyrrolidine which distils at 317-318'/760 turn. was obtained. OPh*[CE2]5*C4NHfi,HCI has m p. 139' the hydriodide m. p. log' the aurichloyide C1,H,,ON Cl,Au m. p. logo and the piwaate m. p. 99-100'. forms light yellow very hygroscopic crystals ; the picrate and pzbolonate have been prepared. The base undergoes in ethereal solution isomeric change into the tetramethylpiperylium chloride. This quaternary salt does not give 6-chlorobutylpiperidine on evapor- ation of its aqueous solution thus proving more stable than the trimethylene compound. W. R [CH215 The hydrochloride r-Chloropentylpyrrolidine c1py O,"p,ORGANIC CHEMISTRY.179 Synthesis of Inactive 6-Coniceine. KARL LOFFLER and HANS KAIN (Ber.. 1909. 42. 94-107L-The constitution suggested by Lellmann (kbstr. 1890 l i 2 8 ) for 8-coniceine has been confirmed by direct synthesis. Pyridylacrylic acid (Einhorn Abstr. 1892 77) when reduced by Ladenburg's method with sodium and alcohol yields piperidyl- propionic acid which was isola?ed in tho form of the hydrochloride of the ethyl ester. The free acid when distilled under reduced pressure yields the which on reduction yH,*CH,* $7 H*CH2 lact im 2 -piprolidone CH,*CH,-N-CO>CH2' with sodium and alcohol ;ieldi piperolidine 5!H2*CH2*$7 H*-CH c H,. CH2*N-CH2>CH2* This is identical with inactive 6-coniceine which was prepared from i-coniine by a process similar to that used by Lellmltnn in the preparation of active 8-coniceine.Ethyl pperidylpropionate hydrochloride C,H,,N*CH,-CH,*CO,Et HCl crystallises from acetone in glistening colourless needles m. p. 122O. The aurichloride CloH190,N,HAuC14 forms yellow needles m. p. 127-128'; the platinichloride has m. p. 127-130'. The free ester has b. p. 143-144'/21 mm. and Di6 1.0214 and is hydrolysed by hot hydrochloric acid to the hydrochloride of the acid C,H,,O,N,HCl which melts at 188'. The aurichloride C,H,,O,N,HAuCl has m. p. 151' and the platinichloride 197O. The acad crystnllises from water in large rectangular plates containing water of crystallisation. It begins to sinter at 70' and melts at 105' or when anhydrous at 2-Piperolidone has b.p. 126-127'/12 mm. or 263-264'/760 mm. and Di5 1.0715. The hydrochloride is hygrxcopic ; the platinichZoride (C,H1,0N),,H,PtC16,2H20 forms large hexagonal plates and has m. p. 138' ; the aurichloride is oily. Piperolidine has b. p. 161' and DY 0.904 and its aqueous solution is strongly alkaline. The picimte C,H,,N,C,H,O,~ has m. p. 226'; the hydrochloride is hygroscopic ; the aurachlorade crystallises in compact needles m. p. 192' after sintering at 189'; the platini- chloride melts and decomposes a t 213' ; the mercuric salt has m. p. 235-238'. The ethiodide is formed immediately on the addition of ethyl iodide to an ethereal solution of the base and the corresponding platinichloride (C,H1,NEt)2PtC16 begins to decompose at 21 8' and has m.p. 229-230'. 147-148'. C;H,*CH,*Q H*CH CH,*CH,*N-CO 3-Hydroxy-2-piperolidone 2>CH*OH is obtained when Einhorn's a-pyridyllactid acidi is reduced and the aqueous solution of the resulting acid evaporated. It separates from acetone in colourless crystals m. p. 129-130° b. p. 183-184'/18 mm. or180 ABSTRACTS OF CHEMICAL PAPERS. 304-305'/760 mm. The aurichloride C,H1,O,N,HAuC1 m. p. 89-90° and the pIatinichZoride (C,H1,0,N)2,H2PtC1 m. p. 92 -94" are both readily soluble in water. J. J. S . Synthesis of p-Coniceine (I-a- Allylpiperidine). KARL LOFFLER and GOTTHOLD FRIEDRICH (Ber. 1909 42 107-1 16).-2-/3-Hydroxy- propylpiperidine (Ladenburg Abqtr. 1890 68) wheu heated at 100' with phosphoric oxide yields a mixture of two isomeric secondary bases one of these i a solid m.p. 18'. This can be resolved into active components the I-form of which is identical with p-coniceine (Loffler Abstr. 1905 i 917) which is thus shown to be l-a-allyl- piperidine. The isomeric b<tse iso-a-allylpiperidine which can be isolated from the alcoholic mother liquors of the picrate of the solid base can also be resolved into active components by means of the hydrogen tartrates. 2-P-Hydroxypropylpiperidine forms a picrate m. p. 11 1 -1 12' a platinichloride m. p. 148-149' and an aurichloride m. p. a-Allylpiperidins forms a well-defined picrate C,Hl,N,C,H,O,N m. p. 113-1 14.5'. The hydrochloride C8H,,N,HC1 crystallises in glistening plates sparingly soluble in acetone m. p. 206-207'. The awrichloride has m. p 107-108' and the platinichloride m.p. 184'. The free base has m. p. 18' b. p. 168*5-17OC/753 mm. and Di5 0 8716. It readily reduces permanganate and yields a nitroso- amine with nitrous acid. It combines with hydrogen iodide and the additive compound when reduced yields a-propylpiperidine. The d-tartrate of the d-base is less soluble than t h a t of the I-base ; it has m. p. 39' and iso-a-AZAylpiperidine yields an oily picrate. The hydrochloride C,H,,N,HCl has m. p. 186-187' and is stable when exposed to the air ; the pkatinichloride has m. p. 138-139' and the base has b. p. 166*5-168*5' and DF 0.8695. has m. p. 70-71'. The base from the tartrate has [ a$ + 24.8'1' at 15O and the corresponding hydrochloride m. p. 189-190'. The liquid base obtained together with p-coniceine by the elimination of water from conhydrine has [a]= - 25.5' and its hydrochloride has m.p. 189-190'. This base can be partly transformed into p-coniceine by saturating with hydrogen chloride at - 16" heating in sealed tubes a t 100' for several hours and then eliminating hydrogen chloride. When reduced by Ladenburg's method solid p-coniceine yields I-coniine and this affords a simple method of passing from conhydrine to I-coniine. J. J. S. 136-137'. + 49.89. The d-hydrogen tartrate C,H'l,N C4H606 Constitution of J/-Conhydrine. KARL LOFFLER (Bep. 1909 42 116-124. Compare Ladenburg and Adam Abstr. 1891 1119).- +-Conhydrine and conhydrine are readily separated by means of their hydrochloiides ; the salt derived from conhydrine is extremely hygro- scopic whereas that from the $-base crystallises well from alcohol and has m.p. 212-213'. The +-base has m. p. 105-106' (not 100-lOZ") b. p. 236-236*5' and aD + 10.98' to + 11 *06'. It crystallises from anhy-ORGANIC CHEMISTRY. 181 drous ether in extremely slender needles but from-moist ether in hydrated plates m. p. about 80'. Engler and Bauer's statement (Abstr. 1894 i 471) that $-conhydrine can be transformed into coiihydrine by simply preparing the gold salt and decomposing this in the usual manner is not confirmed. $-Conhydrine aurichloride C8H170N,AuC1 has m. p. 133-1 34O and the platinichloride forms slender golden-yellow needles m. p. 185-1 86'. $-Conhydrine is an hydroxyconiine since when treated with hydriodic acid a $-iodoconiine is obtained which on reduction yields d-coniine whereas conhydrine under similar conditions yields l coniine.Con- hydrine and $-conhydrine are not stereoisomeric as the latter yields no trace of peonicehe or its oily isomerids (compare preceding abstract). Similarly when the $-base is transformed into the iodo-derivative and hydrogen iodide is eliminated from this no trace of the dicyclic 8-coniceine is formed. It is shown that the hydroxyl group of the $-base cannot be present in the side-chain and must thus be attached to a carbon atom of the nucleus probably in the y-position. The $-coniceine CSHl5N obtained by the action of phosphoric oxide on $-conhydrine at 100-120° has b. p. 171-172' Dt5 0.8776 and [aID + 122.6' at 15'. It does not dissolve readily in water decolorises permanganate and forms a nitrosoamine. Its hydrochloride crystal- lises from a mixture of alcohol and acetone. and has m.p. 205-206O. The platinichloride has m. p. 153-154' and the aurichloride is an oil. The iodoconhydrine obtained by the action of hydriodic acid on $-conhydrine yields a hydriodide C,HIGNI,HI m. p. 2 16-2 17" whereas the isomeric compound obtained by the addition of hydrogen iodide to $-coniceine has m. p. 182'. $-Conhydrine. CARL ENGLER (Ber. 1909,42,559. Compare Engler and Bauer Abstr. 1894 i 471.).-As Loffler (preceding abstract) has shown that Ladenburg and Adam's $-conhydrine (Abstr. 1891 i 11 19) is a solid solution of conhydrine and $-conhydrine there is no foundation for the supposed conversion of the pseudo-compound into conhydrine. J. 3. S. w. K. 4-Picolylalkine [ 4-p- Hydroxyethylpyridine] 4 - Pipecolyl - alkine [ 4-P-Hydroxyethylpiperidine and Quinuclidine.KARL LOFFLER and FRITZ STIETZEL (Ber. 1909 42 124-1 32l-4-Methyl- pyridine condenses readily with 40% formaldehyde solution yielding Eoenigs and Happe's trimethylol derivative (Abstr. 1903 1 S51) but with a 20% aldehyde solution at 135-140' it yields the mono- methylol derivative 4-/3-hydroxyethylpyridine C,NH,*CH2*CH,*OH as a colourless syrup Di5 1.1016 and b. p. 125-126'/15 mm. It is most readily purified by means of the picrate C1,Hl,O,N which forms compact dark yellow crystals m. p. 122-123'. The platinichloride forms crystalline plates m. p. 164' (decomp.) readily soluble in water. The aurichloride has m. p. 124-125'. When heated with hydriodic acid and red phosphorus 4-P-hydroxyethylpyridine yields the oily iodide C,NH,-CH,*CH,I.The corresponding picrate forms long refractive prisms m. p. 108-110' and the platinichloride forms pale yellow needles m. p. 147-1489 When warmed the iodide is readily182 ABSTRACTS OF CHEMICAL PAPERS. \\ HCH-CH \CH=CEi!/ transformed into the isomeric pyridoniuin iodide C-CH,*CH - NI (compare Abstr. 1905 i 265) which crystallises from dilute alcohol in minute colourless needles m. p. 216-218'. The corresponding chloride forms minute crystals and the plutinichloride ( C7H,hT),PtC16 an insoluble flesh-coloared precipitate decomposing at about 300". It has not been found possible to transform Happe's tri-iodohydrin from the trimethylol derivative into an isomeric pyridonium salt. _ _ 4-p-Hydrox yethylpiperidine NH<C CH2*CH2>CH*CH,-CH2*OH H,.CH ob- tained by reducing the corresponding iyridine derivative by Laden- burg's method has b. p. 120-125'/15 mm. or 227-228"/760 mm. and Di5 1.0059. The uurichloride C7HI,0N,HAuC14 forms large compact crystals m. p. 108-1 10" ; thepzcrate is oily. With hydriodic acid and phosphorus the base yields the hydriodide C7H14NI,HI which crystallises from hot water in needles m. p. 158-159". The iodo-base is readily transformed into the quinuclidine hydriodide CH-CH;CH -NHI when its etheieal solution is boiled. The hydriodide forms a colourless syrup retidily soliible in water. The picrate crystidlises in slender pale yellow needles. The base C7Hl8N has b. p. 140-141' and DT' 0.9139. It does riot decolorise permmganate and forms an ethiodicle which is hygroscopic.It. has an intense odour of semen. /CH**CH2\ \C H,. c H:/' The platinichloride (C9Hl,N)2PtC16 has m. p. 3 12'. J. J. S. Condensation of 2 6-Lutidine with Formaldehyde and Derivatives of %Methyl-6-methylolpyridine. KARL LOFFLER and FRITZ THIEL (Ber. 1909 42 132-140. Compare Koexiigs and Happe Abstr. 1903 i 850). 2-Methyl-6-d,hylolpyridine distils at 121-12Z0/15? mm. and has m. p. about 55". It does not decolorise permanganate and yields a picrate which crystallises in pale yellow needles m. p. 102-102s50. The platinichloride has m. p. 183-185' (decomp.). I n the preparation of the monohydroxy-derivative an appreciable amount of a dihydroxy-compound C,H,,O,N is formed. This crystal- lises from a mixture of chloroform and ether in colourless prisms m.p. 73-74-5' and b. p. 185.5-186°/15 mm. The picmte crystallises from alcohol in yellow needles m. p. 133.5-134.5'. The platini- cidoride (C,H,,~,N),,H2PtC1 has m. p. 1'71-1 73" (decomp.) and the ccu?*ic/doride m. p. 141-142'. When oxidised with nitric acid the base yields dipicolinic acid and hence is presumably 2 6-diethylol- yyridine. 2-Methyl-6-ethylolpyridine condenses with benzaldehyde at 125-130' yielding a brown oil the platinichloride of wbich de- composes at 200-806°. This condensation product is probably 6-phenylmbthylol-2-ethylolpyridine OH*CH,*CH,*C5NH,*CH,*CHPh*OH. When heated at 125-130" with hydrobromic acid which has been saturated at O' the methylethylol derivative yields 2-methyl-6-bromo-ORGANIC CHEMISTRY.183 ethylpyridine. The picrate CSHloNBr,C6H302N3 crystallises from benzene in slender prisms m. p. 111'; the plutinkhloride separates from water in compact pointed crystals m. p. 183-186" (decomp.) and the aurichloride forms reddish-yellow needles m. p. 159-162' (decomp.). The free base is slowly isomerised to the pyridonium - I - - CH:CH-E-yH ' CH:CMe-NBr-CH,' bromide I which crystallises from acetone in snow- white needles m. p. 155-156'. 2-Me thyl- 6-e thylpyridine is obtained when the met h yl-bromoe thy 1- pyridine is reduced with zinc dust and hydrochloric acid ; it is usually accompanied by a certain amount of methylvinylpyridine which can be removed by treatment with acidified N/100 permanganate. The pure metbylethyl derivative is a colourless liquid b.p. 160-161*5°/ 760 mm. and D15 0.9229. The picrate C,H,,N,C6H307N3 forms yellow plates m. p. 127-127.5O ; the platinicldoride small crystals m. p. 188-190' (decdmp.) and the aurichloride yellow needles m. p. 1 2 7.5-1 2 8.5'. When reduced by Ladenburg's method the base yields two stereo- isomeric 2-methyl-6-eth~Z~iperidines which can be separated by means of their hydrochlorides C,H,,N,HCl. Of these one is sparingly soluble in acetone and forms long snow-white needles m. p. 153-5-154O. The corresponding platinichloride ( C,H17N) H,PtCI forms well developed prisms m. p. 188-190° and is readily soluble in water. The aurichloride has m. p. 134O and the picrate forms long needles m.p. 135'. The free base has b. p. 151-151.5'/T55 mm. (corr.) and DI4O5 0.8306. The base can be resolved into its active components by crystallising the acid tartrates.The sparingly soluble tartrate m. p. 58-59' gives a base with 13-97'. The platinichloride of the active base decomposes at 204-206O ; the aurichloride has m. p. 133*5-134*5O and the hydrochloride m. p. 287-288'. The hydrochloride which is readily soluble in acetone forms needles m. p. 171*5-172.5°. The platinichloride has m. p. 196-197' and the bme iso-2-methyl-6-ethylpiperidine is a colourless liquid b. p. 157-15S0/760 mm. and D 0.845. The picrate has m. p. 101.5-102° and the aurichloride is an oil The base can be resolved by means of camphorsulphonic acid but the acid tartrates are syrups. J. J. S. N-Hydroxydioxindole Trioxindole. GUSTAV HELLER [ with JULIUS SOLLING] (Ber. 1909 42 470-479).-Reissert has already prepared N-hydroxyindole (hbstr.1896 i 389 ; this vol. i 51). N-liydroxy- dioxindole (trioxiradole) C,H4<N(OH)>C0 is obtained when ammonium o-nitromandelate is reduced with zinc dust and water in the presence of ammonium chloride and then acidified with hydro- chloric acid. It crystallises from water in colourlesa prisms sinters at 167" and melts and decomposes at 172'. The aqueous solution has an acid reaction gives a blue coloration with ferric chloride and reduces Fehling's solution in the cold. Alkalis decompose the com- pound and in the presence of atmospheric oxygen anthroxanic acid is formed; if an excess of alkali is present isatin is also formed. CH(0N)184 ABSTRACTS OF CHEMICAL PAPERS. Trioxindole is converted into N-hydroxyisatin when its acetone solution is oxidised with a dilute acetic acid solution of permanganate ; acetoxy- dioxindole under similar conditions yields isatin.Oxidation with a hot alkaline solution of permanganata converts trioxindole into azoxy- benzoic acid and reduction with zinc dust and acetic acid yields isatyd (Heller Abstr. 1904 i 516). Acetoxydioxindole CloH,O,N crystallises from benzene in prisms which turn red a t 100' and then melt a t 125'. Its alkaline solutions deposit salts of isatoic acid when kept and its aqueous solution yields isatin when boiled. The N-benzoyl derivative C,H,O?N*COPh obtained by the action of benzoyl chloride in the presence ot aqueous sodium acetate solution has m. p. 126'. A different benzoyl deriv- ative is obtained by benzoylating in pyridine solution ; it bas m.p. 152O. With hydraziue sulphate and sodium acetate solution the trioxindole yields a compound C,H,O,N m. p. 243' which is insoluble iu alkaiis ; the mother liquors from the compound yield isatinhydrazone. With phenylhydrazine a cornpound C20H17N6 is obtained. It crystallises from alcohol in large pliable plates m. p. 226". Isatinosaxone which is isomerlc with this compound crystallises from a mixture of chloroform and light petroleum in slender reddish-brown needles rn. p. 183' (decomp.). J. J. S. Asymmetric Nitrogen. XXXV. One-sided Addition of a Tertiary Base to a Dihalogenide. EDGAR WEDEKIND (Ber. 1909 42 300-303).-The author attempted to synthesise an optically active compound containing two asymmeti ic nitrogen atoms.A completely analogous compound to tartaric acid is scarcely possible but it was hoped to prepare one in which the nitrogen atoms were separated by one or more methylene groups. It was found however that interaction of ethylene bromide with isokairoline (N-methyltetra- hydroisoquinoline) does not lead to the formation of ethylenebis-iso- kairolinium bromide but t o bromoethylisokairolinium bromide 'GH4<C €3,. N Me Br C H ,*CH,Br' which crystallises from a mixture of alcohol and ether decomp. 1 8 3 O . This compound has no further action on isokairoline and this inability to form a further additive compound is ascribed to steric hindrance. The iodide C,,H!7NBrI readily obtained from potassium iodide and a n aqueous solution of the bromide crystallises from ether and if the iodide or bromide is shaken with moist silver oxide neutralised with hydrogen chloride and plittinic chloride added the platinichEoride ( C,NHloMe CH,*CH,*OH),PtCYl is precipitated.N-Ethyitetrahydroisoquinoline has no action on ethylene bromide and ethylene iodide gives with isokairoline an abnormal salt. CH2- 7 H ~~h~lenebis-isokairoliniunl iodide CH,*YH CH,* C,H,' FH2-cH2>N MeEr* CH,*CH X MeBr< C,H,*CH easily obhained from ethylenebistetrahydroisoquinoline (1 mol.) andORGANIC CHEMISTRY. 185 methyl iodide (2 mols.) separates from alcohol as a crystalline powder decomp. 232O and the free base forms the pZcctinicldoride C,,H,oN,C1,Pt. The dicamphorsulphonate from the iodide and silver d-ca,mphorsul- phonate in moist acetone could not be resolved into fractions of differing rotatory power and the regenerated iodide is inactive.W. R. 5-Methylisooxazole. LUDWIG CLAISEN (Ber. 1909,42 59-6S).- The substance b. p. 103-105c/20 mm. obtained by Schmidt and Widmann (Abstr. 1908 i 456) and designated 5-methylisooxazole cannot be such. The author has already prepared 5-methylisooxazole b. p. 12d0 or 29-30'/20 mm. (Abstr. 1892 1072). I n the isooxazoles as in other homologous series the b. p. of the methyl derivative must lie between those of the parent substance and of the dimethyl deriv- ative. isoOxazole has b. p. 95.5" and dimethylisooxazole 141-142". A substance of b. p. 103-105°/20 mm. would have b. p. above 200" under atmospheric pressure and consequently cannot be a methyliso- oxnzole.Moreover Schmidt and Widmann's substance does not possess the unpleasant odour of pyridine which is so characteristic of the lower isooxazoles. The author contributes the following new properties in cormexion with the methylisooxazoles. The sesquioxime C8HI3OaN3 obtained previously (Abstr. 1 S9 I 41 6) is decomposed by warm N/%hydro- chloric acid yielding pure 5-methylisooxazole whilst with concentrated hydrochloric acid a mixture is obtained of 80% of 3-methylisooxazole and 20% of 5-methylisooxazole from which the latter is easily removed by treatment with sodium ethoxide (Abstr. 1904 i 14). 5-Jrlethylisooxazole in aqueous-alcoholic solution forms with platinic chloride a yellow crystalline compound (C,H,ON),PtCl m. p. 21 0-21 2' and a white crystalline merczcrichlorzde C,H,ON,BgCI and cadmicldoride C,H,ON,CdCI with aqueous mercuric and cadmium chlorides respectively. I n dilute aqueous potassium hydroxide 5-metbylisooxazole forms a clear solution of potassium cyanoacetone from which phenylhy drazine hydrochloride precipitates cyanoacetone- phenylhydrazone.Sodium cyanoacetone is obtained quantitatively as a white crystalline precipitate by adding alcoholic sodium ethoxide to a dilute ethereal solution of 5 -methylisooxazole and in aqueous-alcoholic solution yields with diazobenzene chloride a yellow crystalline phenyl- azocyanoacetone and with aniline hydrochloride cyanoacetoneanilide. 5-Methylisooxazole yields /3-iminobutyronitrile by heating a t 100" with alcoholic ammonia ; 5-stmino-l-phenyl-3-methylljyrazole by prolonged heating with phenylhydrazine and with methyl iodide at 100' a methiodide C,H,ONMeI m.p. 125-126" which in cold aqueous solution is converted by silver oxide into acetoacetmethylamide the iV-benzoyl derivative of which CH,*CO*CH2*CO*NMeBz m. p. 107O is obtained by slowly warming 5-methyl.isooxazola and methyl sulphate a t TO" pouring the product into water and adding a solution of potassium benzoate. The preceding reactions are quoted by the author as additional evicleuce for the correctness of the constitution of his 5-methyl- isooxazole. c. s.186 ABSTRACTS OF CHEMICAL PAPERS. Asymmetric Nitrogen. XXXVI. Quaternary Amino- ammonium Salts a New Type of Asymmetric Nitrogen. EDGAR WEDEKIND and WOLDEMAR MEYER (Bey. 1909 42 303-309). -The result of the experiments on isokairoline (this vol. i 184) lead t o the examination of other ditertiary bases with regard t o their additional activity towards alkyl haloids.The type employed was Ph>N=[CH2],*N<F a ; when x = 2 and a is Et benzyl bromide gives no additive compound ; when x = 3 and a is Me then benzyl bromide is quickly taken up by both tertiary nitrogen atoms ; if x = 2 and a is Me then only one molecule of benzyl bromide is absorbed to form a monoquaternary salt. An analogous amino-ammonium salt is formed from diphenyldimethylothylenediamine and methyl iodide ; the diquater- nary salt can be obtained indirectly however by the action of methyl sulphate and subsequent conversion of the methyl sulphate salt into di-iodide. The diquaternary or the amino-ammonium salt can be obtained from ally1 iodide and diphenyldimethylpropylenediamine according to the conditions.The conclusion is drawn that the inability t o form diquaternary salts in the case of dimethylme compounds is due to steric hindrance (Zoc. cit.) and that the lengthening of the chain t o three methylene groups enables the latent additive activity of the other nitrogen atom to become operative. The high molecular rotatory power of the amino-ammonium salts examined is in accord- ance with their high degree of asymmetry. Phen~ZbenxyZmethyZ-(methyZalzilinoethyZ)-an~monium bromide C,H 7*NMePhBr*CH2-CH2*NMePh from diphenyldimethylethylenediamine and benzyl bi omide is obtained in 59% yield and IS crystallised from acetone containing a little alcohol decomp.119-139O. Once with excess of bromide a dibromide C,,H,,N2Br2 was formed decomp. 124-1 25'. The amino-ammonium compound is very easily resolved into its optical antipodes as the solubility of the I-base-d-camphorsulphonate in methyl alcohol is very much less than the d-compound. The extreme [MI of the fractions for the ions were - 4 4 2 O and + 417'. The two camphorsulphonates form snow-white needles decomp. 125O. The d-base-d-bromocamphor- sulphonate is the less soluble salt when t h e bromo-compound is used. The I-amino ammonium iodide C,,H,7N2T forms rhombic plates decomp. 115O [MI -411.5' in alcohol and [MI -424.6' in chloro- form. The d-iodide has [MI +403-2' in alcohol and undergoes autoracemisation in solution ; the velocity constant in 50% alcohol- chloroform solution is K = 0 00024 and in 96% alcohol K = 0*000033. The rate is therefore much slower in alcohol than in chloroform but that it takes place in alcohol which has a high dielectric constant is surprising in the light of Wedekind and Paschke's work (Abstr.1908 i 722). As benzgl bromide can be detected in the inactive solution the conclusion drawn previously that racemisation is due to decomposition and not t o intramolecular change is supported. P~~nyImet~yZethyZ-(ethyZaniZinoethyZ)-c~mmonizcm iodide NEtPh* C2H,-NMeEtPhI obtained from diphenyldiethylethylenediamine and methyl iodide in a closed tube heated at 80' for six hours crystallises from ether decomp.ORGANIC CHEMISTRY. 187 18O*,and the symmetricalcompound C,H,(NPhMeEtT) from diphenyl- diethylethylenediamine and methyl sulphate at 120' and precipita- tion by potassium iodide is yellow decomp.119-120'. ~ ~ p ~ e n y Z d ~ b e n z y Z d i ~ e t ~ ~ Z t r ~ m e t ? ~ ~ t ~ ~ e d ~ a ~ ~ o n dibromide CH,(CH,*NPhMeBr*CH,Ph), forms coloiirless crystals decomp. 195-1 97". The dicamphor- sulphonate is well characterised. W. R. Migration and Reciprocal Displacement of Acid Groups in Acylated Dibromohydroxybenzylphenylhydr- wines. KARL AUWERS (Ber. 1909 42 267-277).-An extension of the inquiry (Abstr. 1908 i 458). It has been shown that treatment of the dibromo-a-N-acetyl-o-benzoxybenzylphenylhydrazine OBz*C,H2Br2*CH2*NAc*NHPh with alcoholic potash does not yield a 1 3 the gxpected a-N-acetate but the a-N-benzoate OH*CsH2Br2*CH,*NBz.NHPh whether the hydrolysis is carried out with excess of alkali or not or in the warm or in the cold. The 0-radicle is usually the first to be split off and this may then displace the acetyl group from its position or the rule is reversed in this case the N-acetyl being first hydrolysed with subsequent migration of the benzoyl group. It is however to be noted in this connexion that the N-acetates a and p are very stable towards alkalis (lo%) whereas the NN-diacetate and ONN-triacetate give the a-N-acetate with a 1% alcoholic solution of potassium hydroxide ; further one molecular equivalent of alkali with the triacetate does not give the NN-diacetyl compound-a portion of the compound is not attacked the remainder being hydrolysed to a- N-a ce t a t e.With other esters the behaviour is quite otherwise the O-propionyl- a-N-acetyl compound on partial hydrolysis with aniline gives a- N-acetate and propionanilide ; alcohol potassium hydroxide giving however a-N-propionate and acetanilide.The 0-acetyl-a-N-pro- pionyl derivative is hydrolysed to a-N-propionate in the normal manner. The question of whether i t is .the greater mass of the migratory group which displaces the other acyl radicle or whether it depends on the space occupied by the groups was also examined b u t the results so far obtained have been meagre. The reactivity of phenyl- hydrazine is largely decreased by the introduction of heavy acyl groups and 8-benzoyl or heptoylphenylhydrazide do not react with dibromo-o-hydroxybenzyl bromide or its esters under ordinary conditions. Indirect methods of preparing these a-N-derivatives from phenylhydrazine and the corresponding ester of the bromide whereby subsequent intramolecular change would be induced have led to mixtures which could not be separated.The crude product however obtained by benzoylation of the a-N-heptoate on hydrolysis gave the a-N-benzoate so that it would appear that the heptoyl radicle containing the same number of carbon atoms as the benzoyl group is nevertheless displaced by it. The formyl compounds are distinguished by the easy displacement188 ABSTRACTS OF CHEMICAL PAPERS. of the formyl group ; thus the actidn of s-formylphenylhydrazide and dibromobenzoxybenzyl bromide leads to the formation of the a-N-ben- zoate and an analogous result is obtained with the acetoxy-compound.[With HUGO DANNEHL and K. ISIULLER.] -8- Plwayldibromo-o- hydroxybenxyl-a-N-formylhydraxine C1,H12@,N2Br2 prepared by heating 2 mols. of s-formylphenylhydrazide with 1 mol. of dibromo- o-hydroxyben zyl bromide in benzene solution crystallises from alcohol in colourless crystals m. p. 164-165". The a-Nformyl- 0-P-N-diacetyl derivative Cl~H,,0,N2Br2 is a yellow amorphous powder which on hydrolysis yields the a-N-acetate. The 0-benaoyl- a-N-formyl derivative C21H1G0SN2Br2 crystallises from alcohol in very slender white needles ni. p. 154O (decomp.). The 0-acetyl- a-N-propionyl derivative Cl,H,803N2Br2 crystallises from alcohol i n glistening leaflets m. p. 173-1749 and is not dissolved by aqueous alkali showing that under these conditions migration of the acetyl group to the P-N does not occur.The a-N-propionyl-0-benzoate C22H?o03N2F2 forms colourless needles m. p. 176-177O and on hydolpis yields the a-N-benzoate. The heptoate of dibromo-o-hydroxybenzyl bromide Cl4HI7O2Br3 prepared by heating the bromide with heptoyl chloride for three hours at 160° crystallises from methyl alcohol in silken needles m. p. 41'. The a-N-heptoate forms slender needles m. p1 146-148" and is soluble in aqueous alkali. W. R. Transformation of Azines into Hydrazones. GUSTAV KNOPFER (Monatsh. 1909,30,29-38).-The results of the author's investigation of the behaviour of aldazines and ketazines towards phenylhydrazine show that all these azines are converted by this means into the corre- sponding hydrazones (compare Fulda Abstr. 1903 i 199 ; Ofner Abstr.1904 i 818; Ott Abstr. 1905 i 376; Fiirth Abstr. 1907 i 61). That the translormation which takes place according to the equation CHR:N*N:CHR + 2NHPh*NH = 2CHR:NoNHPh + N,H is not a consequence of the mass action of the reagent is shown by the fact that the reacting substances were taken in approximately theoretical proportions the conversion of the azine being practically complete. The azine suspended in alcohol (or acetic acid) was heated with phenylhydrazine in a reflux apparatus until complete solution occurred. The following azines .of aldehydes and ketones giving azines and hydrazbnes which are readily identified were employed. (1) Benzaldazine. (2) Salicylaldazine. (3) Anisaldazine. (4) Gin- namaldazine. (5) Cuminaldazine. (6) Furfuraldazine. (7) p-Hydroxy- benzaldazine.(8) Vanillddazine. (9) Piperonaldazine. (10) p- (1 1 ) 0- and (1 2) m-nitrobenzaldazines. (1 3) p-Dimethylaminobenzaldazine. (14) ProtocatechzLaldazinu Gl,H1204N2 decomp. about 245O which is readily soluble in alcohol. (1 5) Resorcylaldazine C14H1204N2 which does not melt at 310'. (16) Methylphenylketazine. (17) Methyl-m- nitrophenylhtaxine C1,H1,O,N4 m. p. 194-195'. (18) Methyl-p- aminophenylketaxine ClGH18N4 which forms heavy yellow crystals m. p. 16 6" and dissolves readily in alcohol. (1 9) BenxyZi~erLeacetaxine CIOH20N2 which forms yellow crystals m. p. 160" and with phenyl-~ ~ G A N I C CHEMISTRY'. 189 hydrazine yields benzylideneacetonephenylhydrazone m. p. 159' (Fischer Abstr. 1884 1150 found 157'). T. H. P. The Aeoxine Analogue of aposafranine.FRIEDRICH KEHRYANN and WERNER GRESLY (Ber. 1909 42 347-349).-The azoxine analogue of aposafranine and of apothionine has been prepared by eliminating an amino-group from diaminophenazoxonium chloride (Abstr. 1903 i 279) in the usual way and has been isolated as the dark red crystalline platinichloride (C,,H,ON,),PtCI,. The chloride and impure nitrate have been prepared. c. s. Experiments on the S y n t h e s i s of H i s t i d i n e . OTTO GERNGROSS (Ber. 1909 42 398-405).-The object of this investigation was the synthesis of histidine which it was proposed to eEect starting from 4-methyliminazole (4-methylglyoxaline) by the following series of changes THoCH>CMe + CCl,*CHO -+ CH=N SJH*OH CH=N -+ >C*CH,*CR(NH,)-CO,H. The condensation product of 4-methylglyoxaline with chloral when hydrolysed with an aqueous alcoholic solution of sodium hydroxide yields however a-methoxyglyoxaline-4-propionic acid which has not yet been converted into histidine. 2-Methylquinoline and chloral when mixed form an additive product C,,H1,0NC13,H,0 which crystallises in large glistening cubes and prisms sinters at 56' m.p. 63' and dissociates into its components when kept or when dissolved in water. 4-Methylglyoxaline and chloral form a similar additive product C,H,ON,CI which crystallises in rosettes of hexagonal plates sinters at 116' and has m. p. 123' (decomp. ). 4-yyy- Trichlor 0- p-h y droxyprop ylg l y omline C3H3N,*CH,*CH(OH)*CC13 is prepared by heating 4-methylglyoxaline with chloral for forty-two hours a t 78-80'; it crystallises in prisms m.p. 195' (decomp.9 ; the hydrochloride C,H,ON,C1 forms stellate groups of crystals and decom- poses between 230-2460' ; the nitrate forms large colourless glisten- ing prisms decomposing above 195'; the omlate forms rosettes of prisms. The base is converted by sodium hydroxide in aqueous methyl alcohol at 2 5 O into amthoxygZyoxaline-4-propionic acid which crystallises in rectangular plates turns yellow at 2 1 0' and decomposes at 221O ; the hydrochloride C7H,,0,N,,HCI forms small needles sinters at 170° and decomposes a t 172'. The methyl ester hydrochloride C,H,,O,N,,HCl prepared by the action of hydrogen chloride on a solution of the acid in methyl alcohol forms silky needles which become orange-yellow at 173' and have m.p. 185' (decomp.). a-Chloroglyoxaline-4-propionic acid prepared from histidine by the VOL. XCVI i. 0190 ABSTRACTS OF CHEMICAL PAPERS. method of Windaus and Vogt (Beitr. chern. Physiol. Path. 1907 9 406) has m. p. 191" and yields a methyl esder hydTochZoride crystallising in large thin glistening plates m. p. 140". W. H. G. ERNST MOHR (Verh. Ges. deut. Naturforsch. Aerxte. 1907 ii 96-97).-Isatoic anhydride dissolves in an excess of cold sodium or barium hydroxide ; the clear solution yields sodium or barium carbonate and anthranilate when boiled. Isatoic anhydride dissolves in water containing an C7qO,N,,HCl Isatoic Anhydride (Anthranilcarboxylic Acid). v equal molecular quantity of sodium hydroxide forming a solution which probably contains the sodium derivative C,H,<NNa.co or co-p C H precipitates a corresponding barium derivative on N=C*ONa the addition of barium chloride and regenerates isatoic anhydride when acidified After a short time the solution deposits isatoic anhydride and under certain conditions contains sodium anthranoyl- anthranilate due to the action of the anhydride or its sodium derivative on the sodium anthranilate produced. Similarly isatoic anhydride reacts with glycine to form o-aminohippuric acid. Action of Hydriodic Acid and of Iodine on Dimethylamino- antipyrine (Pyramidone). HENRI COUSIN (Bull. Xoc. chim. 1909 [vi] 5 121-124; J. Phccrm. Chim. 1909 [vi] 29 49-54).- Hydriodic acid acts on pyramidone forming the iodide C13HlfON3,HI colourless prisms m. p. indistinct above 200' (decomp.). When iodine is added to this salt or to the free base in alcoholic solution the periodide C13HlfON3,HI,12 is obtained as brown needles insoluble in water.G. B. 5Amino-1-phenyl-3-methylpyrazole. ERNST MOHR [and in part LUDWIG SCHMIDT] (J. p. Chem. 1909 [ii] 79 1-49),- A continuation of the researches of von Walthel (Abstr. 1897 i 297) Many of the compounds described in this paper have already been investigated (compare Michaelis Abstr. 1905 i 476 ; Michaelis and Klopstock Abstr. 1907 i 735). The cyanoacetonephenyl- hydrazone prepared by the interaction of p-aminocrotononitrile and phenylhydrazine in dilute acetic acid has m. p. 99-100" (compare Burns Abstr. 1893 i 314; von Walther loc. cit.). The product obtained when the two substances are heated together or in alcoholic solution has m.p. 88-94" and dissolves in cold concentrated sulphuric acid forming an intense blood-red solution ; the substance m. p. 99-100° does not give an intense coloration ; these differences cannot yet be explained. Both substances when warmed with dilute hydrochloric acid at about 55' yield 5-amino- 1-phenyl-3- methylpyrazole. The latter compound appears to react both and as an aminopyrazole as an iminopyrazolone C. S. CMwYH N e ~ ~ ~ o ~ ~ ~ 9 for when it is tqeated with sodium nitrite and N<N P h C N H,'ORUANIC CHEMISTRY. 191 dilute hydrochloric acid it yields 4-oximino-5-imino-l-phenyl-3- methylpyrazolone (compare von Walther loc. cit.) and 5-diazo-l- phenyl-3-methylpyrazole chloride ; the presence of the latter in the solution is shown by the formation of an azo-dye on the addition of an alkaline solution of &naphthol. 4-Oximino-5 -imino-1-phenyl-$-methylpyrazolone appears to behave as CMe*fi*NO NPh*C*NH a tautomeric substance represented by the formulse N< CMe*?:N*oH; thus it reacts both as an acid and as a base; and NqNl?h*C:NH the solid substance is bright red the molten substance is dark green; the dilute solutions in indifferent solvents are sky-blue the alcoholic solution is reddish-violet. 5 -Amino- 1 -phengZ-3-meth y lpyrazole hydrochloride when crystallised from hot dilute hydrochloric acid forms long white needles; it contains water and hydrogen chloride in a loose state of combination and does not give a sharp m.p. crystallises in slender reddish-yellow needles m. p. 169O which when kept in the mother liquor change into compact orange-red prisms m.p. 176-178" (decomp.). l-PhenyZ-3-methylpyraxole-5-axo-~-naphthol C,oH160N4 wystnllises in glistening bright red microscopic needles m. p. 209-2 loo. During the preparation of 4-oximino-5-imino-l-phenyl-3-methpl- pyrazolone a by-product was obtained which is possibly 5-imino-i- CMe*Co it crystallises in NPh*b:NH ' phenyl-3-methyl-4 5-pyraxoqzcinone N< aggregates of lemon-yellow needles m. p. 133-1 34O. 4 5-Diamino-1-phenyl-3-methylpyrazole condenses with benzil CMe*E=N:$JPh mhich yielding tr~phenylmethylpyraxopyrazine crystallises in very pale lemon-yellow needles m. p. 190°. 4-Oximino-5-imino-l-phenyl-3-methylpyrazolone is converted by an alkaline solution of potassium hypochlorite into 1-phenyl-3-methyl- >0 straw-yellow 4 5-pyraxopinonedioxime anhydride N< plates m.p. 94-95O and by potassium permanganate in dilute sulphuric acid into 4-nitro-5-amino-l-phenyl-3-methylpyra~ole NqN€'h*C*NH,' a yellowish-brown powder m. p. 167-168O. The platinichloride C,oH,,N3,H,PtCl,,H,O N%Ph*C*N:CPh' CMe*C]:N NPh*C:N CMe$*NO W. H. G. Pyrimidines XLI. Formation of Purine Derivatives from 4-Methylcytosine. CARL 0. JOHNS (Amev. Chem. J. 1909 41 58-65. Compare Abstr. 1908 i 917).-When 2-oxy-6-amino-4- methylpyrimidine (4-methylcytosine) is nitrated in presence of sulphuric acid an almost quantitative yield of 5-nitro-4-methylcyto8ine &O- NH>Cl\le is obtained; it crystallises from water in C (NH,) C( NO2)' 0 2192 ABSTRACTS OF CHEMICAL PAPERS.small yellow prisms decomp. 260-280'. The position of the nitro- group is shown by the formation of Behrend's 5-nitro-4-methyluracil when it is heated with 30% sulphuric acid in a sealed tube. When treated in a similar manner with 20% acid cytosine and nitrocytosine give respectively uracil and nitrouracil. Attempted reduction of 5-nitro-4-methylcytosine by means of ammonium sulphide regenerated 4-methylcytosine but aluminium amalgam reduces it to 5 6-dianzino- co NH 2-oxy-4 - methylpyimidine N<C(NH,) .C( NH2)>cMe crystallising from water in long prisms containing 1 mol. H,O which do not melt but decomp. at 280-285'; the HN/\\C/\CO picrate decomp. 240'. I I I 5 6-Diamino-2-oxy-4-methylpyrimidine con- oc\/c-NH denses with carbamide when the anhydrous sub- stances are heated together at 170-180° giving 2 8-dioxy-6-methyZpurine (annexed formula) forming small sparingly soluble crystals that do not melt below 345".This compound is the last of t'he three possible dioxypurines t o be prepared. In a similar manner by condensing with thiocarbamide 2-oxy-8-thio-6-methyZpurine is obtained ; it is an almost insoluble crystalline powder not melting below 345". 5 6-Diamino-2-oxy-4-methylpyrimidine when heated with formic acid yields the monoformyl ~ ~ / \ \ c / \ c H compoiind C,H70N,,CH0 which forms minute I I 1 1 crystals from hot water solutions not melting OC,//c-N below 345'. This substance gives a white crys- talline sodium salt which loses water vigorously at 200' leaving a porous mass 2-oxy-6-methyL purine (annexed formula) readily soluble in water crystallising therefrom in slender prisms not melting but decomp.at 300-345". J. V. E. CMe NH N CMe NH N Synthesis of 1-Methylxanthine. MAX ENGELMANN (Ber. 1909 42 177-182).-1-Methylxanthine was first isolated from human urine by Kriiger and Salomon (Abstr. 1898 i 699). Since it had not been synthesised hitherto the author has effected this starting from cyanamide and methyl alcohol. Methylisocarbamide (methyl imino- mrbimate) prepared from cyanamide and methyl alcohol (compare Stieglitz and McKee Abstr. 1900 i 340) condenses with ethyl cyanoacetate in the presence of sodium ethoxide forming 4-imino- 6-oxy-2-metl7Lox~/d~hydropy~~imidi~~e NH<co-cH,>C:NH C( OMe) N a crystal- line substance m. p. 214-216" which when treated with methyl sulphate and aqueous sodium hydroxide yields 4-imino-6 -oxy-2-methoxy- 1 - methyldihydropyrimidine C6H,0,N colourless crystals m.p. 206-208'. The latter substance is converted by sodium nitrite and acetic acid into 5-oximino-4-imino-6-oxy-2-metltoxy- 1 -mPthyldzhydro- pyrimidine small violet needles m. p. about 145" (decomp.) which when reduced with ammonium sulphide yields 4 5-diamino-6-oxy- 2-methoxy-l-methylpyrimidine cry stallising in needles m. p. 160". The latter substance is converted by hot concentrated hydrochloric acidORGANIC CHEMISTRY. 193 into 4 5-diamino-2 6-dioxy-1 -methylpyrimidine the hydrochloride of which when heated with sodium formate and formicBacid at looo yields 5-formylamino-4-amino-2 ; 6-dioxy-l-methylpyrimidine crystallisiag in needles which do not melt at 300O; the crystalline sodium salt when heated at 230-240° liberates 1H20 with the formation of 1-methyl- xanthine.W. H. G. Action of Unsymmetrical Benzoylphenylhydrazine on o-Benzoquinone. WILLIAM MCPHERSON and H. 5. LUCAS (J. Amer. Chm. Soc. 1909 31 281-284).-1t has been shown in earlier papers (Abstr. 1896 i 127 ; 1900 i 411 ; 1901 i 572) that unsymmetrical acylphenylhydrazines react with p-benzoquinone t o form hydrazones of the general formula 0:R N*NAcR. Willstatter and Veraguth (Abstr. 1907 i 453) have found that under certain conditions these hydrazones readily undergo a rearrangement into the isomeric hydr- oxyazo-compounds OAc*R*N:NR’ in which the acyl group is attached to the oxygen atom. By the action of U-benzoylphenylhydrazine on o-benzoquinone o-benzoxyazobenzene OBz*C6H4*N:NPh is produced.It is probable that in this reaction the hydrazone O:C6H,:N*NBzPh is formed first and instantly undergoes rearrangement. o-Benzoxyazobenzene m. p. 93O crystallises in orange needles or plates and on hydrolysis yields o-hydroxyazobenzene (Bamberger Abstr. 1900 i 531) which on benzoylation is re-converted in the original substance. a-Benzoylphenylhydrazine reacts with tetrachloro-o-quinone with formation of the compound C,C1302-NH*NBzPh. E. G. Mechanism of Coupling Reactions. HANS TH. BUCHERER (Ber. 1909 42 47-49. Compare Dimroth a d Hartmann this vol. i 66).-The author and Sonnenburg have found that 2-naphthol-1- sulphonic acid couples with diazotised p-nitroaniline in sodium acetate solution to form p-nitrobenzene-azo-P-naphthol whilst in sodium carbonate solution the product of coupling is an easily soluble substance which readily changes to the preceding compound and is regarded as an 0-azo-derivative SO,Na*C,,H6*O.N,*C,H;NO,.0-Azocompounds have also been obtained from a-naphthol-6 8- disulphonic acid or salicylic acid and diazotised naphthionic acid or diazotised aniline ; these compounds readily change to ordinary 0- or p-hydroxyazo-compounds. c. s. Decomposition of Diazo-solutions. CARL G. SCHWALBE (Ber. 1909 42 196-199. Compare Abstr. 1905 i 618 843).-Polemical. Mainly a reply to Cain (this vol. i 70). Emphasis is laid on the fact that the author studied the rates of decomposition of diazo-solutions as prepared technically.The quantity of nitrous acid present in such solutions is sufficient to produce an increase in the velocity of decomposition. W. H. G. Gain’s Theory of Diazonium and Ammonium Salts. ARTHUR Compare Abstr. 1908 i 1021). The chief HANTZSCH (Ber. 1909 42,394-398. -Polemical. A further reply to Cain (this vol. i 70).194 ABSTRACTS OF CHEMICAL PAPERS. points raised are as follows (1) Comparison of the instability of the C,-ring in benzoquinone towards halogens hydrogen chloride mild oxidising agents etc. with the stability of the benzene nucleus in diazonium salts towards these reagents shows that these two classes of compounds do not contain the same C,-ring as represented by Cain’s formula ; (2) contrary to Cain’s statement the double linking in the group -N:N- is readily resolved by mild reducing agents as in the conversion of azobenzene into hydrazo- H benzene A compound having the annexed for- \/=\ - N.X mula would yield OR reduction a diamine and not /\=/- I I phenylhydrazine since the nitrogen atom in the I N group z>C<g would not be separated from the carbon atom by mild reducing agents; (3) it does not necessarily follow from the non-existence of aliphatic diazonium salts that the presence of the benzene nucleus is essential for the formation of diazonium salts.The stability of the latter is greatly influenced by substitution in the benzene ring and it is not remarkable that the compound resulting Irom the total replacement of the benzene nucleus by an alkyl group decomposes spontaneously ; (4) the process of ionisa- tion of ammonium salts in the manner represented by Gain is very improbable since in the case of trimethylethylammonium hydroxide and the corresponding nitrate dissociated ethyl alcohol and ethyl nitrate would be formed intermediately ; ethyl nitrate does not how- ever form ions.Further if the addition of alkyl halides to amines takes place thus R,N+ClR -+ R,N:Cl*R then the compound formed from methylamine and hydrogen chloride namely should be isomeric with that derived from ammonia and methyl chloride namely NH,:Cl*Me. W. H. G. NH,Me:Cl*H Change of Colour in Additive Reactions. DANIEL VORLANDER (Verh. Ges. deut. Nnturforsch. Aevxte. 1907 ii 91).-The salts of aminoazo-compounds and acids may be regarded as additive com- pounds or as ammonium salts.I f the latter is correct azobenzene- trimethylammonium chloride should be red; this is not the case the azo-ammonium ion being orange-yellow like azobenzene and aminoazobenzene. Solutions of hydrogen chloride or bromide in benzene carbon tetra- chloride or chloroform immediately colour dimethylaminoazobenzene. Moreover dimethylaminoazobenzene and p-methoxydimethylaminoazo- benzene form dark red conducting solutions in dry liquid sulphur dioxide whereas the solution of aminoazobenzene is yellow and non- conducting. An additive compound with sulphur dioxide is probably formed in the former but not in the latter case. The author draws the conclusion that the colour of the compounds of aminoazobenzenes and acids is conditioned by an additive relation between the amine and the acid.The cause of the different colour of the acid derivatives and of the quaternary ammonium salts is attribnted to the fact that in the former the union of the constituents is loose and of the natureORGANIC CHEMISTRY. 195 of that of a double salt whilst in the case of the ammonium deriv- atives the constituents are more intimately united as in complex salts. c. s. Study of the Constitution of Proteins by the Hydrolytic Action of Hydrogen Fluoride. Preparation of Definite Natural Peptides. LOUIS HUGOUNENQ and ALBERT MOREL (Compt. rend. 1909 148 236-238. Compare Abstr. 1908 i 706).-The author has extended his experiments on the use of hydrogen fluoride in the hydrolysis of proteins. The 60% acid diluted with twice its volume of water effects the complete hydrolysis of gelatin with production of free amino-acids.More dilute acid however is incapable of bringing about such profound decomposition ; the products in this case consist of diamines and certain uncrystallisable polypeptides which have been isolated in the form of well-defined picrates and are analogous to some synthetic polypeptides described by Fischer (Abstr. 1906 i 73). They appear to exist in proteins in definite combination and not to have arisen through the synthetic action of the hydrogen fluoride. The following compounds have been isolated from the products of hydrolysis of pepsin extract. A~gimyl-arginine dipicrate - m. p. 207' (corr'). GZutamzn-Zysi.lze pacrate C,,H2,0,N2,C,H3N,01,H,0 prisms m. p. 2 16". Lysyt-Zysine dipicrate C12H,,03N4,(C6 E1307N,) small tablets m.D. 238-242". C18H3804N12)(C6H307N3)2*2H20~ From gelatin &ginyt-o.r.ginine picrate C,2H,,03N8,C,H,07N,,2H,0 has been prepared. It forms needles m. p. 313'. w. 0. w. Combining Power of Egg-white for Hydrochloric and Sulphuric Acids. HEBBERT E. ROAF (Proc. physiol. Xoc. 1908 iv ; J. Physiol. 38).-Diluted egg-white was placed in a series of dialysing tubes immersed in various strengths of acid. After some days the amount of acid in the outer vessel was estimated and it was found that with two acids (sulphuric and hydrochloric) and varying concen- trations equivalent amounts are taken up by the same quantity of protein. It was to be expected that proteins as complex amino- acids should show a definite combining power for acids and alkalis. W. D. H. Osmotic Pressure of Haemoglobin. HERBERT E. ROAF (PTOC. phpiot. SOC. 1908 i-ii ; J. Physiol. 38).-The experiments were made by laking red corpuscles of the cow freed from serum with water The haemoglobin was reckoned as 90% of the dry organic matter. Their object was t o determine the effect of altered conditions on the '' solution aggregate " of the haemoglobin. Three determina- tions of osmotic pressure were made (1) with distilled water (2) with 0.34% sodium hydrogen carbonate and (3) with 0.2% of sodium carbonate; the results for 1% of haemoglobin were 5.7 5.3 and 11.6 mm. of mercury respectively which correspond with '' aggregates " of 29787 32035 and 14636 respectively. The osmotic pressure of protein solutions is altered by electrolytes and non-196 ABSTRACTS OF CHEMICAL PAPERS. electrolytes. Substances which prevent laking lower the osmotic pressure of hsmoglobin ; hsmoglobin is more affected by electrolytes than are serum-proteins. It is possible that the osmotic changes which occur in muscular contraction may be due t o alterations in the aggregation of proteins and not to liberation of inorganic salts. W. D. H. Nucleo-protein of the Pig’s Liver VITTORIO SCAFFIDI (Zeitsch. physiol. Chem. 1909 58 272-281).-By boiling and precipitation with acetic or tartaric acid a nucleo-protein was obtained from pig’s liver which contains 3-48-3.73% of purine nitrogen 2.67% of phosphorus and a pentose. It also contains iron in quantities varying from 0.5 to 3.6%. Schmiedeberg’s ferratin which was prepared in much the same way contained 6% of iron. W. D. H. Action of Rennet at Various Temperatures. C. GERBER (Compt. rend. 1908 147 1320-1322).-There are many causes which produce deviations from the law that the times taken to curdle a given quantity of milk are inversely proportional to the amount of ferment added. The present paper is concerned with such deviations as are due to a too speedy curdling so that the product of time and quantity of ferment is lowered. These deviations increase with the temperature and at the same temperature they increase with the quantity of ferment added. For the same quantity of rennet they are largest with specimens of rennet containing a high proportion of saline constituents. Calcium chloride however (and t o some extent hydrochloric acid) has an accelerating effect which is greatest when the enzyme concentration is greatest so that the above- mentioned negative deviation due to the large quantity of ferment present is annulled; the process thus becomes regular and the law is followed. G. B. A New Artificial Peroxydase. E. DE STOEKLIN (Compt. rend. 1908 147 1489-1491. Compare Abstr. 1908 i 490 746; ii 573). -Iron tannate can act as a peroxydase and in conjunction with hydrogen peroxide oxidises a number of substances which are resistant t o all peroxydases hitherto known. I n particular it attacks substances containing a single phenolic hydroxyl for instance guaiacol. I t acts like a true enzyme oxidising many times it own weight of ethyl alcohol to acetaldehyde and it produces a black substance from tyrosine in the same way as tyrosinase. LEONOR MICHAELIS and PETER RONA (Biochem. Zeztsch. 1908 15 217-219).-1n refer- ence to Resenscheck‘s work (this vol. i 74) the authors state that they also find that the presence of negative adsorbents diminishes the fermentative capacity of yeast juice to a small extent. Positive adsorbents have a somewhat greater inhibitory influence. G. B. [Effect of Adsorbents on Yeast Juice.] S. B. S.