Organic Chemistry. Viscosity of Ethyl Alcohol. L. GAILLARD (J. P h u ~ z . Chim. 1907 [vi] 26 482-487).-The relative viscosities (compared with that of water taken as unity) of absolute ethyl alcohol and of mixtures con- taining from 1 to 10 molecules of water per molecule of alcohol are 1.45 2.53 2.96 3.10 3.10 2-95 2.84 2-67 2.55 2.43 and 2.23 respectively whilst those of mixtures containing 95% 20% 15% 11% lo% and 5% of alcohol are 1.78 1.96 1.65 1.45 1.35 and 1.21 all the values having been obtained a t 15". Examination of these values shows that the viscosity of ethyl alcohol increases with dilution until a maximum value of 3.1 is reached for the two mixtures of the composition EtOH73H,0 and EtOH,4H,O and then diminishes and that absolute alcohol and a mixture containing 11% of alcohol have the same viscosity.This confirms the existence of the trihydrate the formation of which is accompanied by the maximum contraction and renders probable the existence of the tetrahydrate. Mixtures of the two alcohols EtOH,3H20 and EtOH,4H20 in any proportion what- ever all have the viscosity 3-1 indicating that intermediate hydrates are not formed. E. H. Action of Zinc Ally1 Iodide on the Anhydrides of Mono- basicAcids. ALEXANDER M. SAYTZEFF (J. BUSS. Phys. Chem. Xoc. 1907 39 Chem. 1232-1239).-Whenan anhydride of a monobasic acid reacts with ally1 iodide in the presence of zinc the following reactions most probably occur O(CO-R) + C,H5*ZnI = C,H,*CR(OZnI)*O*COR -+ CR(C,H,),*OH and as a side reaction CR(C,H,),*OZnI -+ C,H,* CR* 0- COR . The yield and purity of the alcohol are much superior to that obtained when the ester is employed instead of the anhydride.The following substances have been obtained. Methyldiallyl- carbinol yield 36.5% of the theoretical having b. p. 157-159" B 0,87747 Bio 0.86314 Bi 0.86258 (Sorokin gives B 0.8640 Bi3 0.8524). Ethyldiallylcarbinol yield 37-39% b. p. 175-1 76"/ 755.6 mm. Di 0.88603 0,86877 D: 0.87002 (Smirensky B 0.8776 0.8637). Propyldiallylcarbinol yield nearly 41% b. p. 192-194O DO 0.87939 L):* 0-86286 Di! 0.86412 (P. arid A. Saytzeff Ug 0.870'7 Bio 0.8564). isoPropyldiallylcarbino1 yield 3774 b. p. 18'7-188" 0; 0.88859 0.87133 0: 0,87259 (Rjabinin and Saytzeff 0 0.8647 B 0.8512). Alkylene Glycol-chlorohydrin E t h e r s and their Changes. JOSEF HOUBEN and KARL FUHRER (Ber.1 9 07,40,49 9 0-5 00 0)-Ethy lene glycol- chlorohydrin ether [a-chloro-/3-ethoxybutane] CH,Cl-CHEt *OEt7 origin- ally obtained by Lieben using zinc ethyl is more conveniently prepared by the interaction of dichloro-ether and magnesium ethyl bromide. It is not converted into methyl ethyl ketone or indeed changed by heating in boiling methyl alcohol with sodium hydroxide. a-Cldoro-P-ethoxyiso- hexicne,CH,Cl*CH(C,H,)*OEt is a colourless liquid b. p. 60-61"/8 mm. Z. K. Y vord. XCIV. i.74 ABSTRACTS OF CHEMICAL PAPERS. iso-a-Cldoro-P-ethoxy-isoheptane CH,Cl*CH(C,H,,)*OEt is a colourless liquid of unpleasant odour b. p. 77-'78"/9 mm. p-ChZoro-a-ethoxyethyl- benzene CH,Cl*CHPh*OEt is a colourless pleasant smelling liquid b. p. 107-108"/9 mm. ; when heated with sodium hydroxide it is converted almost quantitatively in to acetophenone and for the preparation of this from bromobenzene it is not necessary to first purify the hydrin ether.By the action of sodium iodide on the above chlorohydrin ether the chlorine is to a large extent replaced by iodine; the product obtained has b. p. 11O-11lo/9*5 mm. and distils as a dark red oil without much decomposition a t 226O/760 mm. y-Chloro - a - ethoxypropylbenxene CH,Cl*CH(CH,Ph)*OEt is a colourless liquid of agreeable odour b. p. 125-126O/9.5 mm. which like the aliphatic compounds is not altered on boiling with sodium hydroxide. 1-P- Chloro-a-ethoxyethyhaphthalene CH,C1*CH(C,,H7)*OEt has b. p. 178-179°/9 mm. and forms a yellow liquid of faint odour. Heated with sodium hydroxide it forms a-napht hy 1 me thy1 ketone.HENRY D. DAKIN (J. Biol. Chem. 1908 4 77-89).-Ammonium butyrate is readily oxidised by hydrogen peroxide a t 37" but the reaction is accelerated by warming. The products obtained mere acetoacetic acid acetone propaldehyde acetaldehyde acetic and formic acids and carbon dioxide; propionic acid was probably also present. It is probable that a- and P-hydroxybutyric acids are the initial products. All products except acetone are on further treatment converted eventually with carbon dioxide and water. Acetone is very resistant t o hydrogen peroxide. There is no need to assume that acetone is formed as an intermediate substance in the oxidation of all the butyric acid formed in the body. It is probable that P-hydroxybutyric acid may be decomposed so as to give acetic acid and its oxidation products.It is much less probable that the a-acid is an alternative initial product in tissue oxidation; this however may be further oxidised through propionic acid. W. D. H. J. TH. BORNWATER (12ec. trav. chim. 1907 28 413).-When yellow mercuric oxide is shaken with an aqueous solution of m-heptoic acid a t the end of some days the oxide is completely transformed into a white precipitate of mercuric heptoate (CH,Me*[CH,],*CO,),Hg. It crystallises from methyl alcohol in nacreous plates m. p. 106'5O. Solutions of the salt decompose after a time mercuric oxide being deposited ; they are rendered more stable by addition of heptoic acid. Mercuric heptoate does not form a double salt with mercuric chloride.E. F. A. Oxidation of Butyric Acid by Hydrogen Peroxide. Mercuric Heptoate. E H. Derivatives of Undecenoic Acid J. TH. BORNWATER (Rec. trau. chim. 1907 26 409-4 1 2).-Methyl undecenoate (Noerdlinger Abstr. 1890 1237) prepared according to Perkin's method for the ethyl ester (Trans. 1886 49 ZOS) has b. p. 249*5-250°/780 mm. m. p. - 27.5" D15 0.889. As the temperature rises from 11.2' to 2 5 O the ?2D falls from 1.44301 to 1.43727. Ethyl undecenoate has m. p. - 37*5* b. p. 263-263-5"/780 mm. D15 0.881. Undecenornethylamide CH,:CH*[CH-,],.CO.NHMe,ORGANIC CHEMISTRY 75 prepared by the action of an aqueous solution of methylamine on the crude chloride forms fine crystalline plates m. p. 46' (below that of the arnide Franchimont Abstr. 1897 ii 542).Undecenodimethyl- amidr CH,:CII*[CH2],*CO*NMe2 obtained by shaking an ethereal solution of the chloride with an aqueous solution of dimethylamine hydrochloride is a liquid b. p. 186.5'/20 mm. D;' 0.89278 which solidifies when cooled in ice and salt to a solid m. p. - 16.5'. E. H. Action of Ozone on Compounds containing Triple Linkings. CARL D. HARRIES (Bey. 1907 40 4905--4908).-The author disputes Molinari's statement (Abstr. 1907 i 1039) that ozone does not react with substances containing a triple linking or a benzene double linking. Stearolic acid and phenylpropiolic acid yield with ozone unstable gubstances which exhibit the typical reactions of ozonides. c. s. Oxidation of Ammonium Salts of Hydroxy-fatty Acide with Hydrogen Peroxide. HENRY D. DAKIN (J. Biol.Chem. 1908 4 9l-l00).-The ammonium salts of glycollic lactic a- and /3- hydroxybutyric a-hydroxyisobutyric and a-hydroxyisovaleric acids were oxidised with hydrogen peroxide. With the exception of glycollic and P-hydroxybutyric acids the primary products are an aldehyde carbon dioxide and water [R*CH(OH)*CO,H =R*CHO + CO +H,O]. In the Case of a-hydroxyisobutyric acid acetone is formed. More or less of the aldehyde is further oxidised to the corresponding acid and in some cases oxidation goes on still further ; thus lactic acid yields acetaldehyde acetic acid and carbon dioxide Leucic acid undergoes oxidation like other hydroxy-acids. Glycollic acid yields firat glyoxylic acid and formaldehyde then formic acid and finally carbon dioxide and water /3-Hydroxybutyric acid yields numerous products including acetoacetic acid acetone acetaldehyde acetic and formic acids and carbon dioxide.W. D. H. The Reduction of Ethyl Oxalate. WILHELM TRAUBE (Bey. 1907 40 4942-4956. Compare Lowig J. pr. Chem. 1861 [iJ0 83 129 and 84 1 ; Debus this Journ. 1872 25 365 ; Eghis ibid. 1871 24 820)-A solution of ethyl oxalate in absolute alcohol was reduced with sodium amalgam and in order to avoid hydrolysis of the esters tile product was mixed with an excess of alcoholic hydrogen chloride and fractionally distilled. I n the first fraction ethyl alcohol hydrogen chloride and a small amount of ethyl carbonate passed over and then a small amount of ethyl glyoxalnte alcoholate and ethyl glycollate. A fraction distilling between 170' and 220° consisted mainly of ethyl diethylglyoxylate CH(OEt),*CO,Et and ethyl oxomalonate CO(CO,Et) together with a little ethyl oxalate.The residue wheu distilled under reduced pressure gave a fraction 160-200"/20 mm consisting mainly of ethyl deoxalate (Klein Abstr 1880,36) (crystals) and ethyl tartrate (liquid). Tliu diethylglyoxylic ester which is formed in considerable amounts is not a primary reduction product 9 276 ABSTRAOTS OF CHEMICAL PAPERS. but is formed by the action of the alcohol and hydrogen chloride on the ethyl glyoxylate alcoholate. The formation of the acetal can he prevented by using just sufficient hydrogen chloride to neutralixe the alkali formed during the reduction or by using an alcoholic solution of oxalic acid. Under these conditions the chief product is the alcoholate (20-25 grams from 100 of ethyl oxalnte) which appears to be the first product of reduction EtO*CO*CO*OEt -+ EtO*CO-CH(OH)*OEt. Ethyl g2yoxubte alcoholate CO,Et*CH(OH)*OEf may be separated from the mixture of reduction products by fractional distillation and forms a colourless liquid b.p. 136-138O. When heated i t gives rise to an extremely strong odour and when mixed with the theoretical amount of phosphoric oxide decanted and distilled it yields ethyl glyoxalate b. p. 130° which readily polymerises. When warmed with barium hydroxide the alcoholate and also glyoxylic acid yield gaseous hydrogen. The alcoholate condenses with ethyl malonate in the presence of acetic anhydride yielding Perkin and Bishop's ethyl ethylenetricarboxylate (Proc. 1891 7 41) which is hydrolysed with 25% hydrochloric acid to fumaric and malic acids.The ethyl ethylene- tricarboxylate reacts with ethyl malonate and sodium ethoxide forming ethyl propanepentacarboxylate from which tricarballylic acid is produced on hydrolysis. Attention is drawn to the fact that many of the products formed by the reduction of ethyl oxalate occur in plant structures (compare Koenigs Ber. 1S92 25 800). J. J. S. Simple Ester Anhydrides of Saturated Dibasic Organic Acida. D. MOL (Rec. tiwv. cAim. 1907 26 373-408. Compare Abstr. 1906 i 4).-The ester anhydrides of the dibasic acids are obtained by (1) the action of the monoalkyl chloride on the mixed alkali alkyl salt; (2) the interaction of phosphoryl chloride and a slight excess of the alkali alkyl salt (compare Gerhardt Annalen 1853 8'7 237; Geuther ibid.1862 123 113) or (3) the action of acetyl chloride on the alkali alkyl salt (compare Bouveault Abstr. 1900 i Ethyl anhydro-oxalate O(CO*CO,Et) can be prepared by either of the three methods. It is a colourless liquid with a faint odour b. p. 139O/15 mm. 140°/16 mm. which in a freezing mixture solidifies t o crystals m. p. 8O. The liquid has D:"'" 1.2480 m2 1.42762 rt? 1.42592. Its ethereal solution reacts with dry ammonia gas form- ing ethyl oxaninte and ammonium ethyl oxalate. When very rapidly heated at 240° ethyl anhydro-oxalate decomposes evolving carbon dioxide and forming anhydrous ethyl rnesoxalate and a liquid having the same empirical formula as the latter but double its molecular weight.At 150° the ester anhydride forms carbon monoxide and dioxide and ethyl formate. Attempts to prepare ethyl anhydro- malonate by the second and third methods give no definite result pro- bably owing to the reactivity of the hydrogen atoms of the :CH group. The action of potassiiim ethyl malonate on ethyl malonic chloride has not been studied. Ethyl anhydrosuccinnte O(CO*CH,*CH,*CO,Et) is prepared either f;)S the interaction of sodium ethyl succinate (Blaise Abstr. 1899 i 474).ORGANIC CHEMISTRY. 77 793) and ethyl succinic chloride obtained by a modification of Michaelis and Hermens' method (Abstr. 1892 1494) or by the action of phosphoryl chloride on the former salt. It forms colourless crystals m. p. 28O. I n ethereal solution i t is attacked by dry ammonia forming ethyl succinamate C,H,,O,N as colourless needles m.p. 75" and an extremely deliquescent solid identified from its reactions as ammonium ethyl swcinate. When boiled under the ordinary pressure ethyl anhydrosuccinate carbonises and after four distillations a mixture of much succinic anhydride and a little ethyl succinate is obtained. By the action of phosphoryl chloride on sodium ethyl glutarate (obtained by Blaise's method) ethykanhydvoglutarate O(CO*CH,*CH,*CH,~CO,Et) is formed as a colouriess liquid which when strongly cooled solidifies to crystals m. p. 7-8". The liquid has b. p. 150°/15 mm. D:3'5 1.1245 rtg 1.44466 and rtg 1.44275. The author points out that the customary method of preparing acid chlorides by addition of phosphoryl chloride to the salt of the acid is contrary to the original directions of Gerhardt who added the powdered salt to the oxychloride. This would account for the poor yields obtained by some workers.A vacuum distillation apparatus based on Dewar's absorption of gases by charcoal cooled in liquid air is described. E. H. . Synthesis of Methylethylmalic Acid. M. L. SHDANOVITSCH (J. Buss. Php. Chem. SOC. 1907 39 Chem. 1411-1414).-Ethyl a-bromobutyrate reacts with pyruvic acid in the presence of zinc forming ethyl methylethylmalate CO,Et*CHEt*CMe(OH)*CO,Et the yield being 81-S4% of the theoretical ; when hydrolysed crystals are formed which could not be purified. The ammonium salt has m. p. 172.5-174"; at 1 7 9 O it resolidifies and then melts a t 180-18lo (Micha.el m. p. 179O) ; the silver salt has also been obtained.Z . K. Conversion of Methyl Alcohol into Formaldehyde and the Preparation of Formalin. E. I. ORLOFF (J. Buss. Yhys. Chern. Xoc. 1907 39 1414-1439. Compare Abstr. 1907 i S92 1008).-The conversion of methyl alcohol into formaldehyde is not a reversible reaction and is accompanied by secondary reactions such as CH20-+ CO+H and 2H2+O2=2H,O &c. The yield of formaldehyde is a maximum when the following relations are observed. The quantity of oxygen the total quantity of alcohol vapour = 0-4 1 ; oxygen total quantity of the gaseous mixture = 0-1375 1 ; total quantity of alcohol vapour total quantity of gaseous mixture = 0.342 1. When in these circumstances the action proceeds without the application of external energy C2C,/V2= 0*00103 (where C and C = concentration of the methyl alcohol and oxygen respectively and Y= the mean velocity of the gaseous mixture through the catalyst).The function of the catalyst is discussed at length the above rela- tions being true when the catalyst consists of a roll of copper gauze 12 cm. in length 16 mm. transverse section in which there are 15 x 15 threads in each cubic centimetre.’I8 ABSTRACTS OF CHEMICAL PAPERS. The ordinary thermodynamic equation for the energy of a reaction is not applicable here. An equation is deduced by which it is possible to calculate the total quantity of gas which should be obtained in any experiment but it was observed that the quantity actually obtained was always more than that required by this equation this being due to the absorption of the unknown gas (CH,),O by the palladium chloride contained in the palladium employed for the absorption of hydrogen.The mixture of gases in the various experiments contains 2% to 18% of this gas which has an odour resembling slowly oxidising phosphorus and is decomposed at a red-heat. The Ammonia Reaction for Distinguishing between Enolic and Ketonic Derivatives. 11. ARTHUR MICHAEL and HAROLD HIBBERT (Bey. 1907 40 4916-4918. Compare Abstr. 1907 i 1010).-The untrustworthiness of this reaction is further borne out by the behaviour of enolic ethyl diacetosuccinate in solution. From a light petroleum solution the ketone is precipitated ; from ethyl bromide the ammonium salt of the enol and from chloroform a mixture of ketone and enolic salt.Where the enol reacts more readily than the ketone an almost quantitative separation of the tautomeric substances can be effected with aqueous ammonia. Ketonic dibenzoylacetyl- methane and enolic tribenzoylmethane with ammonia in organic Synthesis by Means of Mixed Organo-metallic Compounds of Zinc. Constitution of the P-Acetoxy-ketones. EDMOND E. BLAISE (Compt. rend. 1907 145 1285-1287).-The P-acetoxy- ketones prepared by the condensation of the chlorides of pacetoxy- aliphatic acids with mixed organo-metallic derivatives of zinc (Abstr. 1907 i 749) do not form crystalline derivatives with either phenyl- hydrazine p-nitrophenylhydrazine phenylbeneylhydraeine or semi- carbazide. The only reaction for ketones giving a positive result is obtained with sodium nitro-prusside which in the presence of a trace of potash produces the characteristic yellowish-red coloration stable in acetic acid.Z . K. solvents both give precipitates. w. K. I n order to decide between the alternative formuh I. OAc*CHR*CH,*COR’ and 11. CHR<z;:>CR*OAc for the /3-acetoxy-ketones the author has determined their molecular volumes and those of compounds in which a closed lactonic or oxide- chain is known to exist. Whilst in the latter case there are con- siderable differences between the calculated and observed values due to the closure of the chain in the former only the normal differences characteristic of open-chain compounds are found. The conclusion is drawn that the P-acetoxy-ketones have the ketonic constitution (I). E. H. 0. MILLER (Ber.1907 40 4903-4905. Compare Vieweg Abstr. 1907 i 893). -Gladstone’s formula for mercerised cellulose C,,H,,Olo~NaOH is not substantiated by the experiments of the author who fmds that the percentage of sodium hydroxide in mercerised cotton increases with the concentration of the alkaline solution. Behaviour of Cellulose with Sodium Hydroxide. c. 8. ’79 ORGANIC CHEMISTRY Stereochemistry of Chromium. 111. PAUL PFEIFFER (Zeitsch. anorg. Chern. 1907 56 261-278).-The paper contains a summary of the mutual relationships of the stereoisomeric chromium salts and the methods for determining their constitution Part of the experi- mental material has already been published (Abstr. 1905 i 33; 1906 i 71 ii 614; 1907 i 895) and the remainder will be published in detail later (compare next abstract).The more important methods used in determining the constitution of the compounds have Stereochemistry of Chromium. IV. The Isomeric Dibromo- salts. PAUL PFEIFFER (Zeitsch. anorg. Chem. 1907 56 279-295. Compare previous abstract).-It has been shown in earlier papers that the diacidodiethylenediaminechromium salts [ En,CrX,]X (where En = ethylenediamine and X =acid group) exist in two stereoisomeric already been dealt with (Zoc. cit.). G. s. modifications distinguished as the cis-form (violet L -J salts) and the trans-form [g>Cr<g]X (green salts) respectively. L J I n the present paper the dibromo-salts and certain of their derivatives are described. Their constitution has been established mainly from their relationship to the dioxalato-salts already described.cifi-DibromodiethyZened~aminechromiu~ bromide [En,CrBr,]Br,H,O and the corresponding iodide and dithionate described in a previous paper (Abstr. 1907 i 895) have been more fully investigated. t r a ~ s - ~ ~ b r o m o d i e € ~ ~ y l e n e d ~ a ~ ~ ~ ~ e c ~ ~ ~ o m i u n ~ bromide [En,Cr Br27Br,H20 (microscopic,.green plates) is prepared by evaporating a n aqueous solu- tion of the diaquo-salt [En2Cr(02H,)Br]Br2 with hydrobromic acid in the presence of mercuric bromide. A double salt [En2CrBr2] Br,HgBr separates as a green liistrous crystalline powder; on the removal of the mercury by means of hydrogen sulphide a green solution containing the trans-salt is obtained. The corresponding salts described below are obtained from the green solution by double decomposition with the alkali salt of the correspond- ing acid.All including the bromide itself are soluble in water but the solutions are very unstable the iritraradicle bromine is eliminated and the colour changes simultaneously from green t o yellowish-brown With concentrated hydrobromic acid the compound [En,CrBr,]Br gives a double salt [En2CrBr,]Br,HBr,2H20 which occurs in grass- green transparent plates and is very unstable. trans-Dibromodieti~ylened~a~inechro~i~~ dithionate [Eo,CrBr,]S,O occurs in hstrous flat green needles ; the corresponding iodide nitrate and thiocyanate also form lustrous green needles. The compound [ En,CrI,]T,HgT obtained by the action of hydriodic acid on a solution of the bromobisaquobromide and mercuric iodide occurs in lustrous deep green leaflets almost insoluble in water.tmns-Dichlorodiethylened~a~inechrornizc~ dithionate [ En2CrC1,1S,0 prepared by the general method occurs in lustrous red needles which turn green on rubbing. trans-DiciLlorodiethylenedia~~,nechromiz platinichloride [En2CrC1,]PtC16,12H,0,SO ABSTRACTS OF CfIEMTCRL PAPERS. obtained by the action of chloroplatinic acid on the corresponding chloride forms small yello wish-green needles. Optically Active Trimethyl-a-propiobetaine (a-Homobetaine). EMIL FISCKER (Ber. 1907 40 5000-5008. Compare Abstr. 1907 i 192).-l-Trimet?~yZp~opiobetaine CHMe<i!Fei>O (compare Brii hl this Journ. 1876 i 698) prepared by the interaction of d-bromo- propionic acid with trimethylamine in the cold forms colourless plates decomp.242' (corr,) [a] - 19.7". It forms two dimorphous auri- chlorides (compare the behaviour of betaine Eischer Abstr. 1902 i 428 and Willstatter Zoc. cit. 266) the one crystallising in lustrous gold-colourcd thin crystals m. p. 259' (decomp. corr.) from the acid solution and the other forming a yellow powder consisting of micro- scopic short needles aggregated in crosses or six-armed stars m. p. 226' (corr.) obtained on crystallisation from warm water. They give the unchanged active betaine when decomposed with hydrogen sulphide. An identical trimethylpropiobetaine is obtained by the action of methyl iodide on d-alanine. The action of ammonia and of trimethylamine on d-a-brornopropionic acid takes place accordingly in the same stereochemical sense whilst it has already been shown that no Walden rearrangement takes place in the case of ammonia.By the interaction of trimethylamine and ethyl d-a-bromopropionnte in alcoholic solution a t the room temperature the compound CH,*CH( NR!Ie,Br)-CO,Et is formed quantitatively in large colourless needles m. p. 150-151O (corr.) but is quite optically inactive and is identical with that formed from inactive ethyl a- bromopropionate. Tha aurichloride separates in very thin characteristic yellow plates m. p. 96-97' (corr.). The compound yields inactive trimethyl a-propiobetaine when treated with silver oxide. It is possible by interrupting the reaction a t an early stage to obtain a product having [a]= - S-l' which yields a propiobetaine [a] - 3*2' that is about five-sixths racemised.Excess of trimethylamine rapidly racemises salts of ethyl trimethylaminopro- pionate but is without action on salts of ethyl d-alanine ester. It would appear that the mere presence of a quaternary ammonium group is sufficient greatly to increase the tendency of the betaine to racemise autoracemisation at a low temperature being characteristic of optically active quinquevalent nitrogen derivatives. G. S. E. F. A. Oxidation of Leucine a-Aminoisovaleric Acid and a-Amino- n-valeric Acid with Hydrogen Peroxide. HENRY D. DAKIN (J. Biol. Cheni. 1908 4 63-76).-Leucine on oxidation with hydrogen peroxide yields isovaleraldehyde isovaleric acid ammonia and carbon dioxide. On further oxidation acetone is formed from the isovaleric acid. The reaction closely resembles several biochemical changes in which leucine takes part.Breinl and Baudisch's statement as t o the formation of isobutaldehyde is incorrect and the product Liebig described when lead peroxide is used is not butaldehyde but isovaleraldehyde. a- Aminoisovaleric acid under similar conditions yields imbutaldehyde isobutyric acid ammonia and carbon dioxide.ORGANIC CHEMISTRY 81 Payt of the isobutyric acid is further oxidised with acetone and carbon dioxide. With lead peroxide a-aminoisovaleric acid yields isobut- aldehyde. a-Amino-m-valeric acid on oxidation yields n-butaldehyde butyric acid ammonia and carbon dioxide. On further oxidation the butyric acid is in part decomposed with formation of acetone aldehydes lower fatty acids and carbon dioxide.The first steps in the oxidation of each of the above amino-acids are analogous t o those observed in other amino-acids and may be expressed as follows R*CH(NH,)*CO,H + 0 = R CHO + NH + CO,. R*CH(NN,)*CO,H + 0 = R*CO,H + NH + CO,. W. D. H. Action of Nitrous Acid on Allylamine. LOUIS HENRY (Compt. Tend. 1907 145 1247-1249).-When an aqueous solution of allylamine neutralised by hydrochloric acid is treated with sodium nitrite allyl alcohol is the sole product. This shows that at the moment of formation the allyl alcohol does not undergo the isomeric change CH, CH*CH,*OH -+ CH,:C(OH) CH which occurs in the saturated propyl alcohol since the unsaturated alcohol CH,:C(OH)*GK would be immediately transformed into acetone and this is not formed. Thus allylamine behaves differently from propylamine towards nitrous acid The action of nitrous acid on allylamine niny be compared with t h a t on trimethyleneamine which gives not isoallyl alcohol YH2>CH*OH but allyl alcohol (Kijner J. Russ.Phys. Chem. Xoc. 1901 33 377). The action of sodium nitrite on dibromopropylamino hydrocbloride CH,*Br*CHBr*CH,NH,,HCl (Henry Awn,. Xoc. Sci. BrusseZs 1880 4 317) appears to be more complicated than the reaction with allylamine. VICTOR AUGER (Compt. rend. 1907 145 1287-1 290).-Potassium cyanide in con- centrated aqueous solution acts on (1) methyl sulphate giving 92% of the theoretical yield of acetonitrile ; (2) ethyl sulphate 90% of propionitrile ; (3) sodium methyl sulphate (which contrary to Beilstein is not anhydrous but contains lH,O) 92% of acetonitrile and 0.2-0*8% of methylcarby lamine ; (4) potassium ethyl sulphate ‘15% propionitrile and 0.45% of ethylcarbylamine (using the dry salts only 55% of propionitrile is obtained) ; (5) methyl iodide 95% aceto- nitrile and (6) ethyl iodide in the presence of methyl alcohol 97% of propionitrile in the form of its constant boiling mixture with methjl alcohol.I n the last two cases the carbylamine if formed would be destroyed by the alkyl iodide. Thus whilst Guillemard’s results (Alnstr. 1907 i 300) lead to the conclusion that potassium cyanide has the isocyanide constitution when in the solid state those of the author assign to it a normal structure when in aqueous solution. CH2 E. H. Preparation of Methyl and Ethyl Cyanides. E. H.82 ABSTRACTS OF CHEMICAL PAPERS.Preparation of cycZoPropane. GABRIEL GUSTAVSON (J. pr. Chern. 1907 [ii] 76 512. Compare Willstatter and Bruce Abstr. 1907 i 1018).-In the author's method of preparing cyclopropane (Abstr. 1888 240 ; 1899 i 421) by the action of zinc dust on trimethylene dibromide the reaction is carried out in 75% alcohol and the tempern- ture is raised above 60° only towards the end. The first portions of the product are rejected as the trimethylene dibromide always contains propylene dibromide. G. Y. ALFRED KLIEGL (Be?.. 1907 40 4937-4942. Compare Baeyer and Lahr Abstr. 1900 1 141).-o-Nitrotriphenylmethane cannot be obtained by condensing o -nitrobenzaldehyde with benzene. The product is a colourless resin which is completely soluble in concentrated sulphuric acid. The desired compound may be prepared readily from o-nitrobenzylidene chloride and benzene by Friedel and CrLtfts' synthesis.o-Nitrobenzylidene chloride N02-C6H4* CHCI (70-75%) and a small amount of a-a-dichloro-2 2'-dinitrobenxyl ether (5%) are formed by the action of phosphorus pentachloride on a benzene solution of o-nitrobenzaldehyde. The benzylidene chloride is a lemon-yellow liquid b. p. 143-144'/12 mm. and solidifies in a freezing mixture. It decomposes on exposure t o light or when kept for some time in contact with the atmosphere. When warmed with concentrated sulphuric acid the aldehyde (40%) is regenerated. The benzyl ether is probably identical with the product obtained by Zimmermann and Miiller (Abstr. 1885 771). A better yield (29%) is obtained by the action of phosphorus pentachloride on a well-cooled chloroform solution of the aldehyde.It is very sparingly soluble in all the ordinary solvents but may be crystallised from pure ethyl acetate and decomposes a t about lSOo. When boiled with acetic acid it yields the aldehyde and with alcohol the diethylacetal of the aldehyde NO,*C,H,*CH(OEt) b. p. 154-156O/18 mm. o-Nitrotriphenylmethane CI,Hl,O,N is best obtained when the reaction mixture with an excess of benzene is kept at the ordinary temperature for several days and then decomposed with dilute hydro- chloric acid. It crystallises from alcohol in palo yellow glistening plates or from light petroleum (100-140') in compact prisms m. p. 93-94' and does not give a coloration with alcoholic potassium hydroxide.J. J. 5. Action of Dichloroacetic Acid on Aniline and its Homo- logues. I. IWAN VON OSTROMISSLENSKY (Bey. 1907 40 4972- 4979).-When o-toluidine is treated with dichloroacetic acid the author was unable to detect the formation of di-o-toluidinoacetic acid according to Meyer (Abstr. 1884 47) ; the main product of the action was o-methylaminop~enyl-o-toZ.uidinoacetic acid C,,H,,O,N which separates from alcohol in prismatic needles m. p. 239-240° (decomp.). o-l'olyl-o-methylimesatin C16H140N2 obtained as a by- product separates from alcohol in glistening golden-yellow leaflets m. p. about 225' (decomp.) ; when boiled with acids it forms o-methyl- isatin and the toluidine salt. Synthesis of o-Nitrotriphenylmethane. (NO,*C',H,*CHCl),OORGAXIC CHEMISTRY.83 The mechanism of the interaction of o-toluidine and dichloroacetic acid is discussed and the results obtained by Meyer from the action of p-toluidine on dichloroacetic acid are confirmed. The action of aniline on dichloroacetic acid was also studied. A. McK. Salts and Ethers of Hexanitrodiphenylamine. D. K. ALEX- ANDROFF ( J . Russ. Phys. Chenz. Soc. 1907 39 Chem. 1391-1395).- s-Hexanitrodiphenylamine CI,H,(N0,),*NH*C6H~(NO~)~ is a typica,l example of a pseudo-acid (compare Hantzsch Abstr. 1906 i 576 651 833 856); thus whilst it is itself a slightly-coloured non- electrolyte its salts which are either the qn- or anti-derivatives are all bi ightly coloured. The sodium lithium silver and ammonium salts are red; the potassium and rubidium salts dark violet; they all correspond with the formula C,,H,O,,N,M.The crystalline forms of the two series are different but they all form bright yellow solutions. From the silver salt red solutions of either the syn- or anti-methyl and propyl ethers were formed which could not be isolated. Z. K. Which Substances Contain a Readily Resolvable Single Carbon-Nitrogen Linking ? HEHMANN EMDE (J. pr. Chem. 1907 [ii] 76 509-511. Compare Mohr Abstr. 1907 i 72l).-It was shown previously that on reduction with sodium amalgam cinnamyl- trimethylammonium chloride CHPh:CH*CH,*NMe,U yields tri- methylamine hydrochloride and a-phen ylpropylene (Schmidt and Emde Abstr. 1906 i 945). On the other hand the corresponding chloro- hydrin formed by addition of hypochlorous acid to the ethylene linking when reduced with sodium amalgam yields an amino-alcohol hydrogen being substituted for the chlorine atom.Hence the C-N linking in the cinnamylamine is rendered unstable by the ethylene linking in the grouping C:C*C*N. G. Y. Action of the Chlorides of Phosphorus on Phenolsulphonio Acids. I. RICHARD ANSCHUTZ (AnnuZen 1907 358 92-97)- The action of phosphorus pentachloride on phenol-p-sulphonic acid if analogous to that of the pentachloride on p-hydroxybenzoic acid (Abstr. 1906 i 500) must lead to the formation in the first place of phosphoryl chloride and phenol-p-sulphonyl chloride and there- after to that of chlorosulphopheuyl dichloro-orthophosphate S0,Cl C,H,* O*POCl whereas Kekulk obtained p-chlorophenylphosphoryl chloride (this Journ. 1873 1239). On re-investigation of the reaction it has been found that Kekulk's compound is formed only if the immediate product is distilled under the ordinary pressure.is obtained if the product of the action of phosphorus pentachloride on potassium phenol-p-sulphonate is extracted with light petroleum ; it crystallises in colourless needles m. p. 87-88" b. p. 203"/13.5 mm. The dichlorophosphate C6H404Cl,SP,84 AUSTBACTS OF CHEMICAL PAPERS. prepared in the same manner from potassium 2 6-dibromophenol-4- sul phonate separates from carbon tetrachloride as a hygroscopic white crystalline crust m. p. 76-78' (compare Zincke and Glahn Abstr. 1907 i 698). G. Y. Oxidation of Thymol by the Oxidising F e r m e n t of Mushrooms. H. CousiN and HENRI HERISSEY ( J . Pharrn. Chim. 1907 [vi] 26 487-491.Compare Bougault Abstr. 1902,i 638).-When an aqueous solution of thymol is treated with the oxidising ferment of mushrooms in the presence of air a white precipitate is formed (Bourquelot Abstr. 1897 ii 66). The authors have prepared this precipitate by means of the ferment obtained from Russula delica and from Lactarius controversus. It contains the dithymol C,,K,~U,,H,O m. p. 100-101' described by Dianine (Abstr. 1882 623) which after the first melting resolidifies and again melts a t 164.5' (corr.) (Dianine gives 165-5') the m. p. of the anhydrous substance. The dithymol so formed is very pure giving colourless solutions in alkalis instead of the orange solutions obtained by Dinnine. The ferment obtained from the second source gives a less pure product.The white precipitate contains other compounds which seem to be of a quinonoid nature and have not yet been obtained crystalline. The oxidation product of thymol has no antiseptic power and the authors conclude that in many circumstances thymol is a bad antiseptic agent. E. H. Sulphoxides and Sulphines. KARL A. HOFMANN and K. OTT (Ber. 1907 40 4930-4936).-A solution of ferric chloride in thionyl chloride reacts with heptane from petroleum yielding a blood- red oil which gradually solidifies to a black crystalline mass of ditolyl- sulphoxide ferrichloride SO( C7H,),,FeC13 m. p. 60.5'. It decomposes when heated with water yielding ditolylsulphoxide and ferric chloride and dissolves readily in chloroform to an intense reddish-violet solution which shows two absorption bands 660-680 pp and 520-618 pp in addition to complete absorption from 440 pp in the violet end.A molecular mixture of benzyl sulphide and benzyl chloride reacts with an ethereal solution of ferric chloride yielding tribenxylsulphine chloride ferrichloyide S( C7H7)3Cl,FeC13 which crystallises from alcohol in pale yellowish-green twinned plates m. p. 98.5'. Bistribenxyl- suZphine chloride ferrichloride 2S(C7H7),C1,FeC1 is formed when excess of benzyl chloride is used or by the action of thionyl chloride and benzyl chloride on ferric chloride at the ordinary temperature. It forms thick glistening crystalline plates m. p. 9'7-107' (decomp.). I'ribenxylsulphine plutinichloride [S( C7H7),1,PtCIG is imoluble in water and has rn. p. 186O. I'ribenxylsulphine iodide forms a pale yellow powder m.p. 75' and the ferrocyccnide s(C7H,),H,FeC,N a white precipitate which decomposes at 180'. Benzyl chloride and benzyl sulphide do not appear to react in the absence of ferric chloride. The following mixed sulphine chlorides have been prepared with the aid of ferric chloride and from the ferri- chlorides the ferrocyanides have been obtained by precipitating with Toluene yields tho same product.ORGANIC CHEMISTRY. 85 ammonia and adding potassium ferrocyanide solution to the filtrate dibenzyl-tert.-butylsulphine chloride dietb y 1-tert.- butylsulphine chloride benzyldiethylsulphine chloride dibenzyl ethylsulphine chloride and triethylsulphine chloride The ferrocyanides form white precipitates all of which with the exception of the last are insoluble in water.The accelerating effect of the ferric chloride appears to be due to the formation of an additive comDound of the chloride with the sulphide. I ' 5. J. S. Transformation of the Tetramethylene Ring into the Trimethylene Ring. NICOLAUS J. DEMJANOFF (Ber. 1907 40 4961-4963).-Perkin (Trans. 1894 65 950) found that when cyclo- butylamine NH,*CH<CH%>CH2 is acted on by nitrous acid an alcohol C,H,O is formed to which he assigned the formula OH*CH<CH2>CH2. The author concludes that in the action in question the tetramethylene ring is converted into the trimethylene ring. It was oxidised by means of a mixture of chromic and sulphuric acids in aqueous solution ; the oxidation product exhibited reactions typical of aldehydes and the semicarbazone prepared from it was by no means uniform since by treatment with ether it was resolved into cyclobutanonesemi- carbazone m.p. 202" and a semicarbazone m. p. 126-127' which has all the properties of cydopropaldehydesemicarbazone. The latter compound is decomposed by dilute acids t o form an aldehyde. It is concluded that the oxidation product of the alcohol obtained from the amine NH,*CH<:E:>CH is a mixture of cgclobuttt- none and cyclopropanealdehyde. A. McK. CycZoButylcarbinol and its Isomerisation to Pentamethylene Derivatives. NICOLAUS J. DEMJANOFF (Bey. 1907,40,4959-4961).- cycZoButylcarbino1 OH*C€12*CH<cH2>CH (compare Perkin Trans 1901,'79,329) may be conveniently prepared by the reduction of ethyl c~clobutanecarboxylate by means of sodium and alcohol according to Bouveault and Blanc's method.It is a transparent thick oil b. p. 142-142*5O/750 mm. Di 0,9199 Di 0.9129 T Z ~ 1.4449. When warmed with concentrated hydrobromic acid it is converted into the bromide C,H,Br a transparent liquid b. p. 137-139' Dii 1.400 ng 1.4875. When reduced a hydrocarbon C5HZ0 is formed with b. p. 49.5-50° ; the propertlies of t h i s hydrocarbon agree with those CH% CH2 The alcohol C,H,O has b. p. 123-121'. CH2 of 'cyclopentane; but differ from those of methylcyclobutane. A. McK. Aromatic Alcohols. New Reactions. ROBERT FOSSE (C071zpt. reidd. 1907 145 1290-1293).-33enzhydrol-p-diinetbylamine similarly to xsnthhydrol and dinaphthapyranol (Abstr. 1906 i 975SG ABSTRACTS OF CHEMICAL PAPERS and benzhydrol-p-p-tetramethyldiamine (Abstr. 1907 i 414) con- denses with methylenic derivatives with elimination of water thus NMe,*C,H,*CHPh*OH + H*CHXY = H,O + NMe,*C,H,*CHPh'CHXY.By this reaction p - d i m e t h y Z a r n i n o b e n ~ ~ ~ d r ~ l ~ e n ~ o y l a ; e NMe,* C,H,* CHPh* CH (COPh) *COMe small faintly sulphur-yellow crystals m. p. 157-1 5 8 O and p-dimethyl- arninobenxhydrylucetylacetone colourless needles ni. p. 13 lo are obtained. I n the same way benzhydrol itself reacts with /I-ketonic esters and P-diketones giving compounds hitherto only obtainable by the action of a halogen derivative of diphenylmethane on the sodium compound of the methylenic derivative. By this new reaction there were prepared ethyl benxhydrylbenxo ylacetnte CHP h,* CH( CO P h) -CO,E t needles rn.p. 135' (on mercury) ; benxhyd~ylbenxoylacetone CHPh,* CH(COPh)*COMe fine white needles in. p. 148-1 50' and benxhydrylacetylucetone CHPh,*CH(COMe) m. p. 116' (on mercury). The hydroxyl of different diary1 secondary alcohols will also combine with methylenic hydrogen forming the compounds ethyl phenyl-a-naphthylmethyl benxoylucetate,aCloH7* CH Ph* CH( COPh) *CO,Et m. p. 160' (varies with duration of heating) ; phenyl-a-n~~hlhylrnethyl- acetylacetone aCl,H7*CHPh*CH(COMe) m. p. 126' (on mercury) ; phenyl- a-Taaphthyl melhylbenzoy Zucetone aC,,H,* CHPh*CH( COPh)*COMe m. p. 185-185.5' ; p-methylbenxhydrylucetyZcccetone CH,*C,H,*CHPh*CH(COMe) m. p. 104-106O and p-methylbeizxhydrylbe~xoylacetone CH,*C,H,*CHPh* CH( COPh)*COMe m. p. 130° (on mercury). By the action of methyl malonate on triphenylcarbinol carbon dioxide methyl alcohol methyl acetate and methy2 triphenylmethyl- malonate m.p. 130-131' (on mercury) are formed thus CPh,*OH + ZCH,(CO,Me) 2 CO + MeOH + C€€,*CO,Me + CPh,-CH(CO,Me),. This reaction with ethyl malonate gives Henderson's ethyl triphenylmethylmalonate aud at the same time triphenylmethane according to the equation CPh,*OH + CH,(CO,Et) = CO + CH,*CHO + CH,*CO,Et + CHPh,. Hitherto it has been possible to replace the oxygen in aldehydes by the group :CXY but not the hydroxyl in alcohols by the group *CHXY. E. H. Catechin. STANISLAUS TON KOSTANECKI and VICTOR LABIPE (Be?.. Compare Abstr. 1902 i 553 637; 1907 i 1907 40 4910-4912. 73).-lodocotechin tetranzebhyt ether m. p. 192-193' decornp. at 205O is obtained after a few hours when alcoholic solutions of catechin tetramethy1 ether and of iodiueORGANIC CHEMISTRY. 87 and iodic acid are mixed ; it separates from alcohol in long white needles forms an acetate C2,H2,071 m.p. 189O and develops a yellow colour with concentrated sulphuric acid which after a time becomes violet. The halogen is readily eliminated by zinc dust and alkali catechin tetramethyl ether being regenerated. Other halogenated pliloroglucinol derivatives in alcoholic solution lose the halogen in a similar manner. Ciamician and Silber's bromo- maclurin pentamethyl ether (bromoveratroylphloroglucinol trimethyl ether) is converted into leucomaclurin pentamethyl ether (2 4 6 3' - 4'-pentamethoxybenzhydrol) whilst phloroglucinol tri- methyl ether is regenerated from ~ibromophloroglzccinot trimethyl ether C,HBr,(OMe) m.p. 132-133' which is obtained by the bromination of the trimethyl ether in glacial acetic acid. c. s. Ethyl Diazoacetate and m-Xylene. EDUARD BUCHNER and KONRAD DELBRUCK (Annalefi 1907 358 1-35).-Buchner and his co-workers in a series of investigations (Abstr. 1896 i 230 ; 1897 i 282; 1898 i 639 ; 1900 i 298 ; 1901 i 385) have shown t h a t the product of the action of ethyl diazoacetate on benzene is ethyl norcardienecarboxylate a derivative of a dicjclic system consisting of a three-atom and a six-atom ring making together a seven-atom ring. Buchner and Feldmann (Abstr. 1904 i 57) have found the action of ethyl diazoacetate on toluene to lead t o the formation of ethyl 3-methylnorcardiene-7-carboxylate or of the products of the conversion of this into derivatives of the methylated seven-atom ring.In the present paper the substances obtained from ethyl diazoacetate and m-xylene are described and their constitutions discussed. The almost colourless oil b. p. 129O/10 mm. obtained on fractionally distilling the product of the action of ethyl diazoacetate on m-xylene yields analytical figures corresponding with ethyl dimethylnor- cardienecarboxylate but is a mixture containing comparatively little of this ester. The oil b. p. 115-125°/10 mm. obtained in the same manner from rnethvl diazoacetate when shaken with aaueous ammonia at Oo yielis 3 5-dimethyZ-A2~4-norcardiene-7-car~oxy~~mide (?H:CMeo~H>CH*CO*NH which crgstallises in colourless needles CMe:CH*CH m.p. 14Z0 and reduces permanganate in sodium carbonate solution. When boiled with 30% sulphuric acid the amide is hydrolysed forming 1 3-dimethylphenyl-4-acetic acid but if boiled with 5% sodium hydroxide it forms 3 5-dimethylcy~lo-A~~~~~-heptutrielze-l -carboxylic F]H:CMe*CH2>C*C02H. This crystallises in leaflets m. p. 151° CMe:CH-CH acid decolorises permanganate in sodium carbonate solution gives with concentrated sulphuric acid a yellow coloration resembling picric acid and when boiled with aqueous sodium hydroxide yields an acid m. p. 1 1 3 O . . The hydr 1 ysis of the crude ethyl dimethylnorcardienecarboxylate with sodium hydroxide leads to the formation of 3 5-dimethyZ-88 ABSTRACTS OF CHEMICAL PAPERS. which crystallises in flat needles m.p. 148O decolorises permangan- ate in sodium carbonate solution but is stable in air and gives a J ellow coloration with concentrated sulphuric acid. The mag- nesium calcium and barium salts are readily but the salts of the heavy metals only sparingly soluble ; the silver salt C,,H,,O,Ag is hygroscopic and when heated evolves the free acid m. p. 148'. The amide C,,H,,ON crystallises in colourless needles m. p. 107' becomes yellow and resinous on exposure to air reduces permanganate in sodium carbonate solution gives the characteristic yellow coloration with concentrated sulphuric acid and on hydrolysis with alkalis yields the acid m. p. 148'. On .treatment with bromine in glacial acetic acid solution under cooling the acid forms a dibromide Cl0HI2O2Br2 which is obtained as a white crystalline powder becomes yellow on exposure to light or at loo" decornp.1 8 5 O and is only partly soluble in aqueous sodium carbonate. The action of hydrogen bromide on the acid m. p. 148" leads to the formation of 1 :. 3-dimethylphenyl-4-acetic acid m. p. 105' ; the amide C,,H,,ON crystallises in colourless needles m. p. 183O. In some cases the formation of an unstable pyoduct intermediate between the dimethyl- cyctoheptatrienecarboxylic acid and the dimethy lphenylacetic acid was observed. 3 5-Dimethylcy~lo-A~~~-heptudielze- 1 -carboxylic acid C7H7Me,*C0,H prepared by reduction of the heptatrienecarboxylic acid m. p. 148" with sodium amalgam in presence of carbon dioxide crystallises in colourless needles m. p. 123" decolorises permanganate in sodium carbonate solution is readily oxidised by air and does not give a coloration with concentrated sulphuric acid.The amide crystallises in colourless leaflets m. p. 101'. The dibromide decornp. 1 7 5 O decolorises permanganate. 3 ~-D~methy~cyclo-A5-?~eptene-~-carboxyl~c acid C7H,Me,*C0,H prepared by reduction of the cycloheptatriene- or cycloheptadiene- carboxylic acid with sodium amalgam in boiling sodium carbonate solution in presence of n current of carbon dioxide separates from dilute alcohol in crystals m. p. 80' decolorises permanganate in sodium carbonate and bromine in glacial acetic acid solution is not further reduced by sodium amalgam and does not undergo trans- formation when boiled with aqueous potassium hydroxide. The amide crystallises in leaflets m.p. 167-168O. The acid is converted by theaction of hydrogen bromide in glacial acetic acid solution at looo or of boiling 50% sulphuric acid into 3 5-dirnethylcycloheptune- y-carbolactone C7H,,Me,<~o which crystallises from light petroleum in stout prisms m p. 76' and when boiled with aqueous sodium hydroxide forms the sodium salt of the corresponding hydroxy-acid which is isolated in the form of its silver salt as a white precipitate. 3 5-Dimethylcyclol~eptanecnrboxylic cbcid C,,H,,O,N prepared by reduction of the three preceding unsaturated acids with sodium in amyl alcoholic solution is obtained as an oil with an odour resembling that of the fatty acids. The amide C,,H,,ON crystallises in whiteORGANIC CHEMISTRY. 89 needles m.p. 157"; the silver salt C,,,H,,O,Ag forms yellow leaflets. G. Y. A Case of the Inhibiting Action of the Carboxyl Group. MAXIMILIANNIERENSTEIN and T. A. WEBSTER (Ber. 1908,41 80-81). -The condensation of various phenols and phenolic acids with formaldehyde in the presence of hydrochloric acid to insoluble diphenyl- methane derivatives (compare Abstr. 1907 ii 192) has been studied. With all phenols the precipitate obtained is completely insoluble in hot water; with hydroxy-acids the amount of precipitate is often less and only a portion is insoluble in boiling water. The soluble portion consists of hydroxyaurincarboxylic acids. With protocate- chuic acid and vanillic acid precipitates were not obtained. J. J. 8. Constitution of Phenylnaphthalenedicarboxylic Acid.A Reply t o Stobbe. ARTHUR MICHAEL and JOHN E. BUCHER (Ber. 1908 41 70-73. Compare Stobbe Abstr. 1907 i 769).-The formation of o-benzoylbenzoic acid by the oxidation of l-phenyl- naphthalene-2 3-dicarboxylic anhydride has been already mentioned by the authors. Most of the differences between Stobbe's results and those obtained previously by the authors (Abstr. 1898 i 256) are due to the fact that Stobbe did not follow the authors' detailed instructions. J . J. S. Condensation Reactions of &Unsaturated Aldehydes ; Formation of Benzene Rings. HANS MEERWEIN (ArznaZen 1907 358 71-91).-The formation of aromatic from aliphatic compounds takes place in some cases with great ease whilst analogously con- stituted substances may not undergo ring condensation. Thus whereas the condensation product of methylethylacraldehyde and acetone is readily transformed into +-cumene (Barbier and Eouveault Abstr.1895 i 643) Dautwitx (Abstr. 1906 i 803) was unable t o obtain p-xylene from the Condensation product of tiglic aldehyde and acetone. The present author who has undertaken a systematic investigation of the factors determining the formation or non-forma- tion of rings in such cases finds that o-hydroxyrnesitylenic acid (I) is Cxmed from the condensation product (11) of methylethylacraldehyde and methyl malonate but that the condensation products of crotonaldehyde (111) and tolualdehy de (IT) with methylmalonate do not form aromatic hydroxy-acids CH,Me CH CH3 /\/ p M e Me / / \-/ "OH EH 70,Me RH flO,Me CIT \/ CH CH (1.1 (11.) (111.) (IV.) The ring formation is bevidently determined by the presence of VOL.XCIV. i k90 ABSTRACTS OF CHEMICAL PAPERS. substituting groups and by their position. Attempts ~ to ppepara aromatic hydrocarbons from the condensation products of croton- aldehyde and o-tolualdehyde with acetone were unsuccessful. Condensation of ap-Unsaturcited Aldehydes with Methyl Malonate Xynthesis of Homologous A~cclicyclic A cids.-Methyl citralidenemalonate CMe,:CH*CH,*CH,*CMe C H*CH :C( CO,Me),. formed in a 6 3% yield by the action of citral on methyl malonate in presence of pipendine at - loo is obtained as a viscid oil b. p. 190-195'/20 mm. DI5 1.043 ng 1.5126 ; the mol refraction observed 76.60 is considerably greater than the calculated 73-73 as has been found by other authors in the case of compounds containing conjugated ethylene linkings.When boiled with sodium hydroxide in alcoholic solution the ester is con- verted into an acid which is either 4-methyl-3-isoanzenyls~Z~cyl~c acid CMe,:CH*CH,*G',H,Me(OH)*CO,H or $-isohexen ylsalic y lie acid CMe, CH*CH CH C,H,( OH) C0,H. This crystallises in needles m. p. 16G-167' sublimes when carefully heated distils with superheated steam gives an intense blue colora- tion with ferric chloride in highly dilute alcoholic or aqueous solution and forms a dibroniide Cl,H,,0,Br2 crystallising in prisms rn. p. 160-161°. Methyl crotonylidenemalorzate C9Hl2O4 obtained in a 39% yield by the action of crotonaldehyde on methyl malonate in presence of piperidine a t - 5 O forms a yellow oil with a faint oclour b.p. 130-135O/15 mm. 1.1105 I Y L ~ 1.48849 The condensation product of a-methyl-P-ethylacraldehyde and methyl malonate C1,HI,O b. p. 139-145'/16 mm. is obtained in a 30% yield When boiled with alcoholic sodium hydroxide it is converted into o-hydroxymesitylenic acid m. p. 180" (Fittig and Hoogewerff Annalem 1869 150 333). Methyl o-tolylidenemalonate C,,H,,O forms white crystals m. p. 69-60' b. p. 165-170°/11 mm. and on hydrolysis yields o-methyl- cinnamic acid. Condensation of Crotonaldehyde with A cetone ; Cyotonylideneacetone. -The action of crot(ona1dehyde on acetone in aqueous sodium hydroxide leads to the formation of crotonylideneacetone CHlKe:CH*CH:CH*COMe in a 23% yield ; it is obtained as a mobile strongly refracting oil with an aromatic odour b.p. 78-80°/16 mm. D15 0,8990 ng 151954 is readily oxidised on exposure to air and forms an additive compound with four atoms of bromine. The oxime C7Hl10N crystallises in white needles m. p. 90-92' b. p. 124-125'/14 mm.; the semicarb- axone C,H,,ON crystallises in nacreous leaflets m. p. 157-158O ; the phenylhydraxone forms yellow leaflets m. p. 70-71O. On oxidn- tion with sodium hypochlorite at 70° the ketone yields chloroform and sorbic acid. o-ToZylidenecccetone C,,H,,O solidifies when cooled with ice and melts about the ordinary temperature forming a colourless strongly refracting oil b. p. 136-138"/10 mm. Constitution of Tannin. 111. MAXIMILIAN NIERENSTEIN (Bey. 1908,41,77-SO. Compare Abstr. 1905 i 914 j 1907 i 331).-The G. Y.ORGANIC CHEMISTRY.91 penta-acetyl tannin M. p. 203' may be reduced to the acetyl derivative m. p. 166O by means of zinc dust and glacial acetic acid. The latter acetyl compound acetyl-Ieucotannin when further acetylated in the presence of pyridine yields a hexa-acetyl-Zeucotannin m. p. 159'. Penta-acetyl-lencotannin is not reduced and penta-acetyl tannin cannot be further acetylated. These observations support the view that tannin is a mixture of digallic acid (tannin) and the corre- sponding reduction product (leucotannin) C,H,(OH),*CO*O*C,H,( OH),* CO,H (tannin) C,H,(OH),-CH(OH)*O*C,H,(OH),*CO,H (leucotannin). which may account for the optical activity of ordinary tannin. rufigallic acid than does triacetylgallic acid. The formula for leucotannin contains an asymmetric carbon atom When oxidised penta-acetyl tannin gives more ellagic acid but less J.J. S. Glycidic Esters and Aldehydes in the Naphthalene Series. GEOHGES DARZENS (Compt. rend. 1907 145 1368-1343. Compare Abstr. 1905 i 1 1 6 ; 1906 i 62 137 430; 1907 i 178 182 627).- Ethyl p- l-naphthyZ-P-methylZ~~~~ate O< . I obtained by 'the CH*CO,Et ' condensatiqn of a-naphthyl methyl ketone with :thy1 chloroacetate in the presence of sodium ethoxide is a colourless viscous liquid b. p. 1 65-170'/4 mm. ; the corresponding acid on distillation decomposes into carbon dioxide and a-1 -naphthylpropaZdehy.le C,,H7*CHMe*CH0 an amber-coloured liquid with an odour similar to t h a t of hydratrop- aldehyde b. p. 131-132'/4 mm. ; the sernicnrbaxone has m. p. Ethy I p-2 -nrq&?~yl-/3-meth ylg Zycidate similar1 y prepared t o the above is an odourless liquid b.p. 175-1SOo/5 mm.; the corre- sponding acid is solid and yields on distillation a-Z-nuphtlzylprop- ddehyde m. p. 53'; the semicarbaxone has m. p. 134-135'. The semicarbaxones of a- and up-naphthyl methyl ketone have m. p. 232-233' and 235-237O respectively. 209-21 0'. M. A . W. Mentbazine. NICOLAI M. KIJNER (J. Rzcss. Phys. Chern. Xoc. 1907 39 Chem. 1246-1250. Compgre Abstr. 1900 i 277).- I-Menthone when treated with hydrazine hydrate a t the ordinary temperature forms chiefly I-menthazine m. p. 51" [a]. - 107.68O; at higher temperatures or when the mixture is distilled it forms d-menthazine m. p. 8 3 * 5 O [a]= + 64-89' t o + 85.27". The latter is also formed when d-menthone is employed. The liquid product formed in the action of hydrazine hydrate on I-menthone consists of a mixture of I- and d-menthazines.The production of the d-men- thazine is due t o the isomerisation of I-menthazine at higher temperatures. Z. K. Ketone Derived from P-Hexahydrocarvacrol. LBON BRUNBL (Compt. vend. 1907 145 1427-1429).-When the P-hexahydro- carvacrol (P-carvacrornenthol) obtained by the direct hydrogenation h.292 ABSTRACTS OF CHEMICAL PAPER& of carvacrol in the presence of reduced nickel (Abstr. 1906 i 81) is oxidised with chromic acid it yields the ketone carvacromenthone b. p. 221-221*5O DO 0.908. The oxime amine and two isomeric semicarbazidea were prepared and were found to bo identical with the corresponding derivatives of tetrahydrocarvone described by Baeyer (Abstr. 1893 i 359) and Wallach (Abstr.1894 i 44; 1896 i 101) ; it follows therefore that P-carvacromenthol (1-methyl-4-iso- propylcyclohexane-2-01) is identical with tetrahydrocarveol. M. A. W. Components of Ethereal Oils. Constitution of Umbellu- lone C,,H,,O. FRIEDRICH W. SEMMLER (Bev. 1907,40,5017-5023). -The physical data for dihydroumbellulone show that it is not a dicyclic derivative belonging to the pinene camphor or dicyclo- octanone series (compare Tutin Trans. 1906 89 1104; 1907 91 271). Umbellulone C,,H,,O has b. p. 93-98'/10 mm. D20 0.958 aD 1.4895 uD -31.5' (100 mm. tube) mol. ref. 45.19. Dihydro- umbellulol C,,H,,O has b. p 91-93'/10 mm. D20 0,931 fiD 1.47348 aD - 27.5' (100 mm. tube). /I-Dihydroumbellulone C,,H,,O has b. p. S3-8'7'/10 rnrn,;Dio 0.928 !uD 1.451168 uD - 30.5' (100 mm.tube). forms oxymethylene and benzylidene com- pounds showing that the keto-group is adjacent t o a CH group. The oxymethylene compound has b. p. 105-107'/10 mm. D" 1.001 TZ 1.49097 ; it yields homotanacetonedicarboxylic acid on oxidation and gives a violet-red coloration with ferric chloride. The benxyl- idene compound has b. p. 185-188'/9 mm. D20 1.03 mD 1.574 and aolidifies to minute needles m. p. 81-82'. The molecular refractions of these compounds are all considerably higher than the calculated values as is also the case in the tanacetone aeries. I-Benzylidene-P-dihydroumbellnlone yields on oxidation d-homotan- acetonedicarboxyEic acid m. p. 146-147' uD + 2.5' (20% solution in 100 mm. tube) which unites with the I-homotauacetonedicarboxylic acid from d-tanacetone (compare Semmler Abstr.1904 i 176) to form i-homotanacetonedicarboxylic acid m. p. 179" and crystallising in short needles. The d-acid forms a neutral ethyl ester b. p. 148-153'/ 10 mm.,and an oily acid ethyl ester. Dihydroumbellulone is regarded as a tanacetone of the methone series CH,< C(CHMe2'*Co>C I whereas umbellulone has a double Dihydroumbellulone CH-CHMe bond adjacent to the keto-group GB,<?(CHMe2)- GO." CH.CM~:CH' E. F. A . Oxygen Derivatives of Camphene. THADDEUS MILOBENDSKI (J. Buss. Phys. Chern. Soc. 1907 39 Chenz. 1395-1403).-'I1he camphene prepared from isoborneol has m. p. 47.5-48*5' b. p. 159.5'/755 mm. and is optically inactive ; that from pinene hydro- bromide has m. p. 44-45' b.p. 159*5"/755 mm. [.ID -41'46'. * Ste also Tntin Proe. 1908 24.ORGANIC CHEMISTRY. 03 The formar when oxidised with permanganate yielded only a very small quantity of neutral products containing a glycol m. p. 197.5-19S*5° and a trace of acid having the odour of acetic acid. The glycol obtained from the other camphene has m. p. 181-185' [a] +21@40'; after subliming a t l l O o m. 'p. 156-177' and when re-sublimed at 96" m. p. 169- 175'. The glycol obtained from diacetyl- camphene has m. p. 160-161'. The first glycol m. p. 197*5-198*5' when dehydrated yields camphenilonealdehyde m. p. 68-5-70" and a white resinous substance distilling above 300°/15 mm. When the glycol is oxidised with potassium permanganate it yields camphenilone m. p. 36-37" a small quantity of volatile acids camphenilic acid m.p. 170-1 71" (sodium salt C,oH,,0,Na,5B,0) and camphenecam- phoric acid m. p. 135-136". With nitric acid the glycol yields two acids CloH1602 m. p. 93*5-94' C,,H,,O m. p. 191*5-192*5O apocamphoric anhydride C,H,,O m. p. 1 77*5-17S0 a ketonic acid m. p. 235O the oxinze of which has m. p. 195-196.5' and some other crystalline products which could not be isolated. With chromic acid the glycol yields camphenilone and cemphenecampboric acid. Camphenecamphoric acid obtained from either of the two camphenes mentioned above is optically inactive and has m. p. 135*5-136' and distils a t 235-237'/10-11 mm. 250-251"/20 mm. but when it is obtained from camphene prepared from borneol chloride it has m. p. 145-1 46'. The chloroanhydride of camphenecamphoric acid has b.p. 153.5-154.5O/13 mm. but in estimating the chlorine in alcoholic solution the results are too low. It was not found possible to obtain the pure ethyl ester by Fischer's method. The chromate is also described. An attempt was made to determine the constitution of the acid by bromination then removing hydrogen bromide by means of potassium hydroxide and finally oxidising t h e unsaturated acids so obtained with potassium permanganate but without success. One crystalline unsaturated acid m. p. 147.5-149" was thus isolat'ed ; it is readily soluble in water alcohol and chloroform. Z. E. Investigations in the Terpene and Camphor Series. LEO A. TSCHUGAEFF (J. Russ. Yhys. Clierrz. Soc. 1907 39 Chem. 1324-1343. Compare Abstr. 1905 i 71 166).-Since pinene is very unstable most of its derivatives have a different constitution from the parent substances ; consequently to obtain true derivatives the xnnthogen reaction has been applied as in this case polymerisation does not occur.Pinocamyheol was prepared from pinene by a modifi- cation of Wallach's method and then converted into the xanthogen derivative C,,H,7*O*C*Y,Me m. p. 60.5-61' ; it forms rhombic cryoltals [a b c = 1.3747 1 0.978751. A t 180-190° it decomposes thus C,oH,7-O*CS,Me -+ C,(,H,6 + MeSH + cso yielding inactive pinene; from this it is evident that pinocamphone and pinocampheol are true derivatives of pinene (compare Wallach and Engelbrecht Abstr. 1906,ii 683). I-Dihydrocarveol was converted into the xanthate CloH,~*O*CS,Me which by the action of ammonia yielded the arnide C,,HI7*O*CSNH m.p. 62-63' [a12 -138+39°,; it forms rhombic crystals [ c c b c == 0.6548 I 0.705SI. The racemic modification of this amide has94 ABSTRACTS OF CHEMICAL PAPERS. m. p. 95*5-96O crystallises in small needles and is much less soluble in organic solvents than the active amides. Methyl dihydrocarveol xanthate decomposes at 180-190' in exactly the same manner as pinocampheol xanthate forming the terpene CloHl6 b. p. 172-1 74O n2g5 1.469'72 D:::; 0.8382 [a] + 131.93'. The Sachgeisa oil or resin which is used as a chewing gum by the natives of South Caucasia when subjected to steam distillation yields an oil consisting almost wholly of inactive pinene together with a small quantity of active terpene. The resin is analogous with that obtained from the bark of the tree Pistacia Zenticus and known as mastic.Z. K. New Method for the Hydration of Pinene. PHILIPPE BARBIER and VICTOR GRIGNARD (Compt. rend. 1907 145 1425-1427)- When pinene in acetic acid solution is treated with a solution of benzenesulphonic acid it is converted to the extent of 52.3% into terpineol. For this purpose freshly-distilled French pineae is dissolved in an equal weight of acetic acid one-tenth of its weight of a 50% aqueous solution of benzenesulphonic acid added and the mixture shaken until it becomes homogeneous. After twelve hours water is added and the insoluble layer washed dried and separated by distilla- tion into two fractions the first boiling below SSo/15 mm. consists of unchanged pinene with a small quantity of a terpadiene b.p. 175-178" and the second fraction boiling above 85"/15 mm. after saponifi- cation with alcoholic potassium hydroxide at 1 10-115° is composed of terpineol b. p. 100-105°/13 mm. m. p. 35" together with a small quantity of borneol fenchyl alcohol and a viscous substance not identified. When lasge quantities of purified pinene are submitted to the above reaction a hydrocarbon having a lower boiling point than the original pinene can be isolated from the product. M. A. W. Santene. OSSIAN ASCHAN (Bey. 1907 40 4918-4923).-1n addi- tion to I-pinene I-camphene phellandrene Miiller's santene has been isolated from Siberian turpentine and identified by conversion into the nitrosochloride nitrosite tribromide (m. p. 77-80°.Miiller gives 62-63"} and hydrochloride as well as by direct comparison with the santeno obtained from sandal wood oil (Abstr. 1900 i 678). It has b. p. 140° D15 0.8698 n2'2 1.4690 and the formula C,H is confirmed. flaantenol acetate C,H,;OAc prepared by using acetic and aulphuric acids is a clear liquid resembling isobornyl acetate in odour b. p. 215-219°/760 mm. and S8-89"/8 mm. D2\ 0.9S71 optically inactive rz 1.45929 thus showing the compound t o be saturated. The santenol obtained on hydrolysis is a solid mixture two- thirds of which bas b. p. 195-196' and the remainder b. p. 196-198" and the conjecture is made that it is similar t o the isoborneol-borneol mixture obtained from camphene. By recrystallisation from light petroleum large transparent plates a.p. 97-98" are obtained. TheORGANIC CHEMISTRY. 95 phenylurethane forms long needles m. p. 61 -62'. Oxidation of snntenol results in the formation in small quantity of a ketone (ssmkarbazone m. p. 225-226'). Santene is also a constituent of oils from Pinzls picea Abies exelsa and a Swedish turpentine. W. R. Rusrsian Turpentine Oil and Russian Pine Tar Oil. IWAN SCHINDELMEISER (Chern. Zeit. 1908 32 8).-Russian turpentine and pine tar oils contain sylvestrene dipentene and in the pinene fraction nopinene identified by the formation of the sparingly soluble acid m. p. 1 2 6 O and sparingly soluble sodium salt on oxidation with perman- ganate. The pine tar oil contains also toluene cymene and a quinone- like substance which has a sharp odour is resinified becoming yellow on treatment with sodium hydroxide and metallic sodium and reacts with hydroxylamine and phenylhydrazine together with saturated acyclic hydrocarbons one of which b. p.98-99' is probably a heptane. A sesquiterpene present in Russian pine t a r oil is,. perhaps identical with the sesquiterpene occurring together with cadinene in cade oil. G. Y. Turmeric Oil. HANS RUPE (Bey. 1907,40 4909-4910. Corn- pare Jackson and Menke Abstr. 1883 482).-When turmeric oil is boiled with dilute sodium hydroxide the main product is a substance containing oxygen b. p. 156'/12 mm. which is probably not identical with Jackson and Menke's turmerol and does not exhibit the properties of an alcohol aldehyde acid or ketone. When boiled with stronger alkali it yields an optically active ketone C,,H,,O b. p.11 9-1 20°/S mm. which forms a sernicarbaxone m. p. 11 9.5-1 20.5O an oxime b. p. 159'111 mm. and well-crystallised condensation pro- ducts with aromatic aldehydes. The ketone is oxidised by potassium permanganate to terephthalic acid and p-methylacetophenone and yields by treatment with alkali hypobromite a hydroxy-acid C12Hlc03 m. p. 150° and an acid C12H1602 m. p. 33-34' ; the latter is oxidised by potassium permanganate to a dicarboxylic acid O,,H,,O m. p. 228'. c. 8. Action of Nitrous Acid on Caoutchoucs. OTTO GOTTLOB (Zeitsch. angew. Chew%. 1907 20 2213-2221. Compare Harries Abstr. 1005 i 223 ; this vol. i 39).-The products obtained by the action of nitrous fumes on crude or purified caoutchoucs vary in com- position with the proportion of nitrogen peroxide present in the mixture of nitrogen oxides but all are more or less impure forms of Harries' nitrosite C1,H,,O7N,.The latter substance can only be obtained in a pure state by strictly following the directions given by Harries (Abstr. 1903 i lS9). The existence of the nitrosate C9HlBOON2 described by Alexander (Abstr. 1905 i 223 ; 1907 i 433; Zeitsch. angew. Chem. 1905 18 164) is doubtful. The same author's statement that. carbon dioxide is liberated during the action of nitrous fumes on caoutchouc is correct but the quantity evolved only corresponds with roughly 0.3% of the total carbon present in the caoutchouc treated. W. H. G,96 ABSTRA7TS OF CHEMICAL PAPERS. f * West African Copals especially Angola and Cameroon Copals. ALEXANDER TSCHIRGH and H.RAGKWITZ (Arch. Pharrn. 1907 245 415-426. Compare Abstr. 1897 i 92).-The constants are given of samples of copal from Sierra Leone Accra Benin Loango Congo and Benguela. The Angola copal examined had m. p. 140-170° acid number 135 saponification number 155 and iodine number 66. The copal was extracted with ether. From the ethereal solution 1% aqueous ammonium carbonate did not extract anything but I % aqueous sodium carbonate extracted (1) amorphous angocopalolic acid C23HR6.03 m. p. 8 5 O acid number 157 corresponding with monobasicity (the szlvey salt was analysed) saponification number 155 and iodine number 7 1 corre- sponding with one double bond precipitated in alcoholic solution by lead acetate and (2) st resinous acid not so precipitated.By evaporating the ether and distilling with steam an essential oil b. p. 140-160" D 0.85 3 passed over whilst yellow amorphous a-angocopaloresen C30F540A or C,,H,,O rn. p. 63-65' remained behind. From the residue of the copal insoluble in ether alcohol-ether extracted in addition to traces of angocopalolic acid yellow P-angocopaloresen C25HaS04 m. p. 220-224'. There remained insoluble in alcohol- ether a substance resembling bassorin soluble in aqueous sodium hydroxide and insoluble inorganic silicates. I n 100 parts of the drug are contained angocopalolic and other acids soluble in ether 64 ; essential oil 2 ; a-angocopaloresen 3 ; acid soluble in ether (t) 5 ; P-angocopaloresen 20 ; substance resembling bassorin 0.3 ; ash 5.7. The Cameroon copal examined had m.p. 105-125' acid number 126 saponification number 157 and iodine number 68. After extraction with ether for three rnonthF aqueous ammonium car- bonate did not extract anything from the ethereal solution but 1% aqueous sodium carbonate Extracted (1) amorphous cameroo- copalolic acid C21H3603 m. p. 98-100° acid number 160 corre- sponding with monobascity (the silver salt was analysed also) saponi- fication number 188 and iodine number 76*5 corresponding with one double bond precipitated iu alcoholic solution by lead acetate ; and (2) a resinous acid not so precipitated. By evaporating the ethcr and dietilling with steam a yellow essential oil b. p. 145-155' D 0.830 was driven over whilst viscous a-carneroocopaloreselz remained behind. From the residue of the copal insoluble in ether alcohol-ether extracted p-cameroocopalovesen C25H3S04 m.p. 220-224O. There remained insoluble in alcohol-etlher a substance resembling bassorin soluble in aqueous sodium hydroxide and an insoluble residue largely inorganic in character. I n 100 parts of the drug are contained cameroocopalolic and other acids 70 ; essential oil 2 ; a-cameroo- copaloresen 3 ; /I-cameroocopaloresen 20 ; substance resembling bassorin 3 ; ash 2. C. F. B. Heerabol Myrrh OSCAR VON FRIEDRICHS ( A d . Pharm. 1907 245 427-457. Compare Kohler Abstr. 1890 1317 ; Tucholka Abstr. 1897 i 584; and especially Tschirch and Bergmann Abstr. 19Q6 i 197 ; Lewinsohn Abstr. 1906,i 972).-Commpial samples ofORGANIC CHEMISTRY. 97 Myrrh0 eZecta aere examined and consisted of yellowish-brown to reddish-brown pieces with a waxy translucent fracture.The following substances were isolated from it (1) a volatile essential oil (8*8%) viscid yellow t o yellowish-green DIP 1.0 11 12. 1.5359 [ u] - 73*9' acid number 6.15 and ester number 47.6. From this oil there were separated formic and acetic acids and a crystalline acid m. p. 1 5 9 O which was not volatile with steam m-cresol cuminsldehyde and cinnamaldebyde and the crystalline monobasic myrrholic acid C17H,,05 m. p. 236' (of which t h e amorphous silver lead and coppel. salts were analysed) and the sesquiterpene heerabolene C,,H, b. p. 130-136'/16 mm. D2* 0.943 T, 1.5125 u 14'10' in 100 mm. tube the molecular refraction indicating a tricyclic sesquiterpene; this yielded a crystalline &hydrochloride C,,I-T,,,ZHCt m.p. 98-93'. (2) That part of the resin which was soluble in light petroleum yielded some acetic acid when submitted t o dry distillation. From that part of the drug insoluble in light petroleum but soluble in ether the following constituents were separated a-commiphoric cccid C,,H,,O m. p. 201-203" is monobasic ; p-cornmiphoric acid m. p. 2 0 5 O has the same formula and basicity; y-commiphoric acid C,7H2,0 m. p. 169-172' is monobasic; all three acids are amor- phous yellow to brown cannot be ncetylated and do not contain methoxy-groups. a-Heerabo-myrrhol G18H2605 m p. 248-250° forms a diacetpl derivative of m. p. 228' (decornp.) and is precipitated from an alcoholic solution by lead acetate ; P-heerabo-inyrrihol C20H2,i06 m.p. 1 6B0 forms a diacetpl derivative. Commipphorinic acid C,,H 3608 m. p. 135" is brown amorphous and monobasic ; the barium salt is insoluble in water and alcohol. A yellow alcohol C,,H,,O b. p. 264" which forms a monoacetyl derivative of b. p. 243' and 1s volatile with steam ; and the non-volatile yellow amorphous heeraboresen C,,H,,O m. p. 100-102° which contains one methoxyl group. The part of the drug insoluble both in light petroleurn and in ether was soluble in aqueous sodium carbonate. It was separated into (1) brown amorphous monobasic a-i~eerccbo-nzy.1.r~ololic acid C1,H,,O7 m. p. 320-225' of which the amorphous silver and lead salts were analysed but no acetyl derivative could be prepared ; i t is pre- cipitated in alcoholic solution by lead acetate and ( 2 ) p-myrrhololic acid C,,H,,O rn.p. 187-190° not so precipitated brown amorphous and monobasic of which the silcer salt was annlysed. The gum had [.ID + 2 3 . 8 O in 2% aqueous solution and was mixed with an enzyme of the oxyciase group ; when oxidised with nitric acid it yielded mucic acid and when distilled with hydrochloric acid furfuraldehyde ; hence it probably contained galactose and arabinose. No bitter principle was detected but the volatile oil has a biting unpleasant taste. C. I?. B. Baptisia Glucosides. IV. +-Baptisin. K. GORTER (Arch. Pharm. 1907 245 561-572. Compare Abstr. 1897 i 627; 1898 j 39; 1906 i 973).-The presence of one hydroxyl group in $-baptigenin has been confirmed by the preparation of the benzoate Gl5H9O5B2 crystallising in small white needles m. p.216'.98 ABSTRACTS OF CHEMICAL PAPERS. The substance obtained by heating the sodium derivative of $-baptigenin with ethyl iodide and alcohol (compare Abstr. 1906 i 973) is now shown to have the composition C,,H,,O and is named +!&xptigin; it crysballises in small colourless plates m. p. 172’ (not 1 6 9 O as previously stated). It yields neither an acetyl nor a benzoyl derivative and consequently cannot contain a hydroxyl group. Since the formation of $-baptigin is accompanied by the production of formic acid it follows that $-loaptigenin must have the partially structural formula CIpHsO,:CH*OH. No $-baptigin results on heating sodium t,6-baptgenin with ethyl alcohol alone and in the presence of ethyl iodide only one-half of the $-baptigenin is converted into $-baptigin.What probably happens in the latter case is as follows part of the sodium q-baptigenin is converted into the ethyl ether which is then hydrolysed with the formation of +-baptigin and ethyl formate C,,H,O,:CH*OEt + H,O = C14H1,0 + H*CO,Et. The ethyl formate together with ethyl alcohol reacts with more sodium $-baptigenin forming ethyl ether sodium formate and $-baptigenin C,,H,O,:CH*ONa + H*CO,Et + EtOH = C,,H,O,:CH*OH -t H*CO,Na + OEt,. The substance CJi4,O4 previously described (Abstr. 1898 i 39) is now shown to be rnetlqlbaptigenetin and is formed together with formic acid on hydrolysing $-baptigin with alcoholic potassium hydr- oxide. It yields on acetylation two acetyl derivatives colourless rhomboidal crystals m. p. about 1 as0 and colourless rectangular crystals m.p 148’. These could not be isolated in a pure state but it is probable from an analysis of the mixture that the compounds formed are triucet ylmeth y lbaptigmetin and acety bunhydrometh ylbapti- genetile. From the above facts together with those previously published (Zoc. cit.) it follows that baptigenetin must have the partially structural formula (I) and $-baptigin the formula (11). Since +-baptigenin when heated with potassium hydroxide solution yields baptigenetin formic acid and methyl alcohol it is probable that i t has the formula (111) /OMe ,,/O*CH CH-OH C12H,(OH),<gg {i] C H -O*C‘HO C H -O*CHO l2 “ 0 [l 41 l2 “\0[1 41 (1.1 (11.1 (111.) When heated under pressure with 5% hydrochloric acid a t 200’ for two hours methylbsptigenerlin yields a small quantity of a substance which has the properties of catechol.It is possible therefore that baptigenetin is a derivative of diphenylene oxide W. H. G. Chitin. TIIEODOR n. OFPER (Biochenz. i%itsch 1907 7 11 7-1 27). -Chitin prepared from the carapace of the lobster by successive treatment with dilute hydrochloric acid boiling 10% potassium hydr- oxide potassium permauganate arid sodium hydrogen sulphite was hydrolysed by 70% sulphuric acid at the ordinary temperature and yielded two amorphous substances of the Composition C,,H2,0,,N2. OneORGANIC CHEMISTRY. 99 of these is acetyldiglucosamine m. p. 194' (decomp.) soluble in water and optically inactive. The other is insoluble in water gives a reddish- brown coloration with iodine and is regarded as a polymeride of the former substance.I n acetyldiglucosamine one amino-group is probably acetylated whilst the amino-group of the second glucosamine molecule is condensed with the aldehyde group of the first. Chitin itself is regarded as a highly polymerised acetyldiglucosamine. G. B. Solanin from the Seeds and Flowers of Solanum Tuberosum. AMEDEO COLOMBANO (Atti R. Accad. Lincei 1907,;[v] 18 ii 683-690 ; 755-762. Compare Odd0 and Colonibano hbstr. 1905 i 455).- From a study of the physical and chemical characters of various samples of solanin the author draws the conclusion that the latter exhibits properties varying wiih the source from which i t is obtained. Thus solanin extracted from Solanum tuberosum differs essentially from that isolated from 8.sodomwum the two products yielding different solanidins when treated with boiling dilute hydro- cLloric acid. T. H. P. Phylloxanthin. LEON MARCHLEWSKI (Biochem. Zeitsch. 1907 7 282-285. Compare Abstr. 1907 i 69 71 784 7S7 865 S66 867 948).-Polemical. The identity of certain chlorophyll derivatives described by Tsvett and Willstatter is discussed and the former's spectroscopic results with phylloxanthin are described as incorrect. W. D. H. Rottlerin. FRANZ HEREMANN (Arch. Pharm. 1907 245 572-585. Compare A. G. Perkin Trans. 1893 63 975; 1895 67 230; Telle Abstr. 1906 i 973; 1907 i 435; Thorns Abstr. 1907 i 545).- Perkin's isorottlerin is considered t o be impure rottlerin ; his formula C33H3009 for the latter compound is however confirmed.Rottlerin in alkaline solution yields on oxidation with hydrogen peroxide at 75O cinnamic and benzoic acids. 2 4 6-Trihydroxytoluene results on de- composing rottlerin with concentrated potassium hydroxide solution at 150"; the same compound is also formed together with 2 4 6- trihydroxy-nz-xylene acetic acid and a tarry substance by heating a solution of rottlerin in 15% aqueous sodium hydrexide a short time with zinc dust. The tarry substance is oxidised in alkaline solution by hydrogen peroxide with the formation of a dibasic acid C,7H,,04 crystallising in slender colourless needles m. p. 184"; the silver salt U17H,,0,Ag2 and ethyl ester crystallising in needles m. p. 1 1 5 O were prepared. The acid is converted by cold fuming nitric acid into a dinitro-derivative I I I 1 crystallising in small colourless rhombic plates \/ \/ 284O ; the corresponding ccrnine forms C02H rinEshaped crystals.The dibromo-derivative C17H,,0,Br resiilts on treating the acid with bromine in glacial Bfe Me /\-GH2- /\ C17H1404(N02)2,100 ABSTRACTS OF CHEMICAL PAPERS. acetic acid; it forms stellate crystals m. p. 172-173'. bable that the acid bas the formula given on p. 99. It is pro- W. H. G. Cinchona Alkaloids. VIII. Constitution of Cinchonine PAUL RABE [with OTTO BU~HHOLZ] (Ber. 19OS 41 62-70).-The base C,,H,,ON (Abstr. 1907 i 954) obtained by oxidising cinchonine with chromic acid is termed cinchoninone in order t o indicate its relation to tropinone and codeinone. It is amphoterio in character and exhibits keto-enolic tautomerism since it yields both an oxime and an 0-benzoyl derivative.It is readily reduced and under special conditions can be converted back into cinchonine ; under normal conditions however a rupture of the molecule occurs duriag the reduction. Nitrous acid (arnyl nitrite) decomposes the ketonic base yielding cinchonic acid and a n oxime C,NH,,:N.OH a reaction which is analogous to the formation of diacetylmonoxirne from ethyl methyl- acetoncetate. The presence of the grouping -CO*CH< is t h w established. The oxime when hydrolysed yields meroquinenine and assuming Koenig's formula for this compound the following con- stitutional formul,? are deduced for the oxime C,NH13*NOH and cinchoninone CH,-CH* CH*CH:CH CH,*CH* CH-CH :CIS j I. 1 $%I IJ. 6HZ HO*N:C-N- CH C911,N*CO*CH N-CH,.Cincho?zi?zoneoxinze C1,H,,ON obtained by the action of free bydroxylninine on the ketone in a strongly alkaline solution forms a pale yellow amorphous powder m. p. 105-110'. It yields a methiodide C,,H,,ON,,IIIeI which has no definite m. p. ; it begins t o soften at 135" arid decomposes a t 145-150'. The benzoyl derivative C26H2402N2 of the base crystallises from light petroleum in colourless needles m. p. 131'; i t is readily hydrolysed by alkalis and possesses very feeble basic properties. Cinchoninone methiodide also yields a benzoyl derivative C,6H2,02N2,il!teI which is hydrolysed when boiled with alcohol. A 75% yield of a'-ozimino-~-vinyZ-quinuclid~ns (formula I above) is obtained by the action of amyl nitrite and sodic ethoxide on the ketone; i t crystallises from ethyl acetate or a mixture of ether and light petroleum (b.p. 40') in colourless prisms or needles m p. 146-147" and yields a methiodide C9H,,0N,,MeT xn. p. 224O (decomp.). *J. J. 5. Alkaloids and Bitter Principles of Calumba Root. VIII. KARL FEIST (Arch. Pharm. 1507 245 586-637. Compare Gadamer A.bstr. 1903 i 5 0 ; 1906 i 976)-Three alkaloids have been ob- tained from calumba root namely columbamine jateorrhizine and palmatine. Gunzel's work on columbamine (Abstr. 1906 i 976) has been confirmed ; further investigation has shown t h a t columb-ORGANIC CHEMISTRY. 101 axnine contains a hydroxyl group in addition to the four -OM0 groups ; columbamine iodide consequently has the partly structural formula C,,H,NI( OMe),*OH. Jnteorrhizine iodide which has the empirical formula C,oH,,O,NI is found to contain three -0Me groups and two hydroxyl groups so that the formula may be written C,7.H,NI(OMe),(OH),; in fact columbamine is a monomethyl ether of jateorrhizine since the mono- methyl ether of columbamine is identical with the dimethyl ether of jateorrhizine. Both coluinbamine and jat,eorrhizine also their methyl ethsrs are very similar to berberine yielding colourless tetra- hydro-derivatives Ssc.The methyl ether of columbamine yields on oxidation with potassium permanganate corydaldine (Dobbie and Lauder Trans. 1902 81 145) together with a trimethoxy-o-phthalic acid. The acid which was not obtained in a pure state melted a t almost the same temperature as gallocarboxylic acid trimethyl ether (3 4 5-trimet,hoxy-o-phthalic acid) but crystallised in a different form.Should the two acids on further investigation be proved to be identical then salts of columbamine methyl ether must be represented by formula I. If not the only other trimethoxy-o-phthalic acid po?sible is 3 4 6-trimethoxy-o-phthalic acid and salts of columbamine methyl ether mould then have the formula I1 OMe OMe X X The third alkaloid palmatine only small quantities of which are present in caluniba root closely resembles berberine ; it contains four OMe groups but no hydroxyl group and the iodide has the formula C,7H,o0,NT(OMe) ; the relationship existing between this alkaloid and columbamine is not yet known. The discovery of a second bitter principle in cnlurnba root named provisionally ' $ bitter principle 11," led to an investigation of columbin.The value obtained for the mol. wt. of the latter compound by the boiling- and freezing-point methods varied considerably with the solvent employed; consequently the mol. wt. of this substance is still unknown (compare Ulrich Abstr. 1907 i 331). Owing to the similarity of the two substances it is possible that the columbin hitherto investigated has been contaminated with (' bitter principle 11." Colurrdmmine nitrate C2,H,,0,W,,2&H20 crystallises in lemon-yello w needles m p. 232' ; the platinichloride (C2,H,,05N)2,H2PtCl is a yellow powder m. p. 238' (decomp.) ; the aurzchloride forms slender needles m. p. 220" (decomp.). Concentrated solutions of columbamine sulphate or nitrate yield on treatment with strong aqueous potasaium hydroxide the inner anhydride of columbamine which crystaliises in violet-black prisms commences to melt at 190° and decomposes above this temperature.Tetrahydrocolumbamine is most readily prepared102 ABSTRACTS OF CHEMICAL PAPERS. by the reduction of columbamine nitrate ; the suZphacte crystallises i n white silky needles ; the chloride forms a colourless crystalline powder commences to melt a t 150° and is completely molten a t 215'. All attempts to separate tetrahydrocolumbamine into its optically active components mere unsuccessful. Columbamine chloride reacts with benzoyl chloride yielding a substance obtained as a light yellow crystalline powder m. p. 152'. In pyridine solution however a substance obtained as a light yellow powder m.p. 212-213' is formed. Acetyl chloride reacts with columbamine chloride in pyridine forming a substance (acetyl derivative 2) which crystallises in slender yellow needles Q. p. 220' (decomp.). None of these substances was obtained in a pure state. That columbamine contains a hydroxyl group is shown by the preparation of the methyl ether ; the iodide of columbamine methyl ether results on heating colnmbamine iodide with potassium hydroxide methyl alcohol and methyl iodide in a sealed tube a t 100'; it crystal- lises in prisms m. p. 238-240'; the sulphate results on treating columbamine iodide with methyl sulphate in the presence of alkali; the rzitmte crystallises in slender light yellow prisms m. p. 2 3 P (decomp.). A concentrated solution of the sulphate when treated with 50% aqueous potassium hydroxide yields the $-form of columbamine methyl ether; it crystallises in light yellow prisms m.p. 136'. Columbamine methyl ether yields with chloroform an additive corn- pound C,,H,,O,N,CHCI forming small light grey crystals m. p. 1 8 2 O and with acetone an additive compound obtained as a dirty yellow fine crystalline powder. T'etrahydrocolumbnmine methyl ether is obtained by reducing the nitrate of columbamine methyl ether ; it crystallises in colourless prisms m. p. 148'. Columbamine methyl ether yields on oxidation with aqueous potassium permanganate corydaldine a trimethoxyphthalic acid CY6H(OMe),(C0,H) crystnllising in colourless slender needles m. p. 200° and an acid containing nitrogen crystallising in colourless prisms m.p. 200-202°. The composition of the latter acid is not yet known; its hydrochloride forms colourless needles rn. p. 208' (decomp.) and ccurichloyide crystallises in slender light yellow needles m. p. 188' (decomp.). I n order to compare the above trimethoxy- phthalic acid with gallocarboxylic acid methyl ether (3 4 5-tri- methoxyphthalic acid) this compound was prepared by treating the acid with diazomethane in ethereal solution and hydrolysirig the dimethyl ester so formed with alcoholic potassium hydroxide ; it crystallises in small colourless rhornbic plates m. p. 195'. Gallo- carboxyiic acid yields on treatment with methyl sulphate,in the presence of alkali a substance probably a monomethyl ether C,H,O,(OMe) crystallising in colourless needles m.p. 251 '. Jateorrhixine iodide C20H200,NI,H20 crystallises in reddish-yellow needles m. p. 208-210' ; the corresponding chloride crystallises from water with +H,O in light yellow needles m. p. 2U6' and from alcohol with 1H20 in copper-coloured needles m. p. 206'; the sulphate forms brownish-yellow prisms ; the nitrate crystallises in glistening C,,H,N*(OMe)vORGANIC CHEMISTRY. 103 golden-yellow needles m. p. 225" (decomp.). The latter salt yields on reductioo tetrahydro~ateorrhixine C,,H,,O,N crystallising in colourless needles m. p. 206". Jateorrhizine iodide yields on methylation a dimethyl ether identical with columbamine methyl ether iodide Palmutine iodide C,7Hlo0,NI(OMe) remains undissolved on treating the mixture of iodides of the alkaloids obtained from calumba root with aqueous sodium hydroxide ; it crystallises in slender yellow needles m.p. 238-240' (decomp.). The corre- sponding mitrate C,,H2,0GN*N0,,1 $H,O forms slender lemon-yellow needles m. p. 238-240". Reduction of this salt leads to the formation of tetrahydropaZmatine C,,H,,O,N crystallising in colourless leaflets m. p. 145" ; the cuwrichZorzcZe C,,H,,O,N,HAuCl forms small cinna- mon-brown crystals. An alcoholic extract of calumba root yields on evaporation a mixture of orange-red prisms and nodular aggregates of yellow crystals. The orange-red substance was found on investigation t o be jateorrhizine chloride with 2H,O. The yellow substance was found to be a mixture of columbnmine nitrate with some '' bitter principle 11." The latter substance crystallises in prisms m.p. 246' (decomp.) and is a lactone. I n agreement with the statement of Ulrich (Zoc. cit.) columbic acid was not detected in the alcoholic extract. W. H. G. isosparteine an Isomeride of Sparteine. CHARLES MOUREU and AMAND VALEUR (Compt. read. 1907 145 1343-1345. Compare this vol. i 44).-isoSparteine CI5Hz6N2 obtained by treating the hydriodide (Zoc. cit.) with sodium hydroxide is a colourless almost odourless oil b. p. 177*5-1'77" (corr.)/16.5 mm. [.ID - 25.01O in 10% alcohol SOlUtiOn Di7 1*02793,n~1.53319 ; the dihydrochloride is a deliquescent crystalline solid ; the pkatinichloride Cl,H2,N,,H2PtCI,,l~5H,0 forms silky tufts of crystals blackens at 230° and decomposes at 257-260" ; the sulplmte forms a thick syrup soluble in water or the alcohols and insoluble in acetone o r ether; the hydriodide m.p. 202' (corr.) has al - 33.2" in 5*5%methyl-alcoholic solution ; the dihydriodide Cl,H2,N,,2HI,H,0 is a crystalline salt optically inactive and yields the hydriodide on treat- ment with sodium carbonate ; the picrate C,,H,,N,,ZC,H,07~ crystal- lises in needles and has m. p. 178" (corr,). isoSparteine methiodide (Zoc. c i t . ) cannot be obtained by the action of methyl iodide on the base ; it is a crystalline salt m. p. 232O (corr,) [.ID - 18-39" in 1.25% aqueous solu- tion o r - 1 6 ~ 7 9 ~ in 6.2% methyl-alcoholic solution ; the hydriodide loses its water of crystallisation at 145O decomposes with loss of Me1 at 220-225" and has uD - 11*80° in aqueous solution. isosparteine is a saturated ditertiary base; it does not reduce acid permanganate solution and on treatment with hydrogen iodide does not yield methyl iodide ; the compound therefore contains methyl groups associated with nitrogen (Herzig and Meyer Abstr.1896 i 68). C,,H2,N,,MeI,HI,H,O M. A. W. Synthesis of Pyrrole and Piperazine Derivatives from the Three Nitroanilines. WALTHER BORSCHE and J. CAMPHER TITSINGH (Ber 1907 40 5008-5017).-The three nitroanilines dis-104 ABSTRACTS OF CHEMIQAL PAPERS. solved in acetic acid react with ethyl phenacylacetate to give pyrrole derivatives of +he following constitution C*2Et*F=CMe>N.C,H*.N02 CH:CPh The yield in the case of the metn- and para-compounds is about 70% but is much less from the ortho-derivative. Paat (Habilitations- schrqt Wiirzburg 1690) found that o-nitroaniiine did not react with ethyl phenacylacetate.f oi'ms citron-yellow rhombic plates m. p. 146-147' ; zinc chloride and bydrogen chloride reduce it t o the corresponding base ethyl-5-phenyl- l-m-urninopT~enyl-2-met~~~~~rrole-3-ca~~boxyla~e crystallising in colour- less needles m. p. 1 4 5 O which when diazotised and combined with phenol forms an orange hydroxycmo-compound. The corresponding p-nitrophenyl~yrrole derivative forms yellowish- red thick plates a. p. 116-117' and the p-amiizophenylpyrrole compound colourless matted needles m. p. 16 1-1 62'. The o-nitro- phenylpyrrole compound gives yellow needles m. p. 96-97' and the o-amicnophenyZ derivative m. p. log" decomposes rapidly in the atmosphere becoming red. s-Bis-m-nitrophenylaminoethane C,H,(NH*C,H,*NO,) (compare Gattermann and 'Hager Abstr.1884 1142) prepared by the inter- action of nz-nitroaniline and ethylene dibromide in presence of sodium acetate a t 150° whereby contrary to the experience with aniline no cyclic compound is formed has m. p. 206-208O. The corresponding tetra-ccnline crystallises in colourless glistening plates or flat needles m. p. 107O and forms a tetra-acetate separating in colourless needles m. p. 272". Ethy I- 5 -p7ke?zyZ- 1 - m- nitropJLenyZ-2 -met JL y Zpyrrrole - 3 -car box y lu te prepared by further heating of niiroph~nylarninoethane with ethylene dibromide forms brownish-yellow needles m. p. 220". s-Bis-p-nitro- phenylaminoethane (compare Jedlicka Abstr. 1 S93 i 699) is obtained in small quantity only by this reaction.Still worse is the yield in the case of the o-compound (compare Jedlicka loc. cit.) due to the decrease in basicity and less tendency to form quaternary ammonium compounds. n2-Nitroaniline reacts with chloroacetic acid to form a mixture of m-nitrophenylglycine N0,*C,H,=NH*CH,*C02H a yellow compound m. p. 158-159' and m-nit7.ophenyZgTycine-m-nitroaniZ~~e N0,*C,H4*NH* CH,* CO*NH*C,H,*NO a brown crystalline powder m. p. 201-20Z0. p-Nitroaniline reacts similarly to give y-nitrophenylglycine m. p. 225' and p-nitrophenyl- glycine-p-nitronnilide m. p. 260'. o-Nitroaniline on the other hand gave only traces of o-nitrophenylglycine. E. F. A. Catalytic Action of Finely-divided Metals on Nitrogen Compounds. MAURICE PADOA and C. CHIAVES (Atti R. Accad. Lincei 1907 [v) 16 ii 762-766.Compare Abstr. 1907 i 722).- When carbazole is heated at 200-220' for twelve to eighteen hours inORGANIC CHEMISTRY. 105 hydrogen under 8-10 atmospheres pressure and in presence of reduced nickel the following products are obtained (1) a base which yields a platinichloride m. p. 21 3" (decomp.) ; and (2) 2 3-diethylindole (?) m. p. 9 5 O and forms a dark-red piwate m. p. 172-173O and a picryl chloride compound C12H15N,C6H2Cl(N0,) m. p. 117'. The Melting Point of Phenylhydrazine and of Certain Osazones. Enm FISCHER (Bey. 1908 41 73-77).-Phenylhydrazine was purified by fractional distillation at 15-20 mm. solidification and removal of the liquid portion (repeated four times) crystallisation from anhydrous ether at low temperatures and finally by distillation under 0.5 mm.pressure. The melting point of the product as determined by stirring with a normal thermometer was found to be + 1 9 * 6 O . For ordinary purposes i t is sufficient to crystallise the base once or twice from its own volume of pure ether and then to distil once under a pressure of 10-20 mm. The base should be coloured pale yellow and should dissolve in ten times its vol. of a mixture of 50% acetic acid (1 pzrtj and water (9 parts). I n the preparation of osazones it is an advan- tage to use the old method namely a mixture of 2 parts of phenyl- hydrazine hydrochloride and 3 of sodium acetate as the sodium chloride thus formed facilitates the formation of the osazone. The phenyl- hydrazine hydrochloride must be colourless and if coloured should be crystallised from alcohol. The melting points of osazones depend to a certain extent on the manner in which the substances are heated.The previous melting points are confirmed namely 205' or 208' (corr.) for phenylglucosazone when the osazone is heated fairly rapidly. 'rutin's value of 2 1 7 O (Proe. 1907 23 250) could not be obtained. Certain phenylhydrazones for example pyruvic acid phenylhy drazone which decompose when heated melt differently according t o the rate at which they are heated. Action of Phenylhydrazine on Dibrornopyrotartaric Acid. FRITZ FICHTER and MARKUS GUGGENHEIM [and in part LUDWIG BRASCH] (J. p r . Chem. 1907 [ii] 76 545-551).-The action of phenylhydrazine on di bromopyrotartaric acid in hot aqueous solution leads t o the formation of the phenylhydrazone of P-aldehydopropionyl- phenylhydrszide (Perkin and Sprankling Trans.1899 75 11 ; Ellinger Abstr. 1904 i 639). As Reitter and Bender have found t h i s substance to be formed also by the action of phenylhydrazine on aconic acid (Abstr. 1905 i 669) the interaction of phenylhydrazine and dibromopyrotartaric acid takes place probably in two stages the first consisting of the formation of phenylhydrazine hydrobromide and aconic acid. When boiled with mercuric oxide in alcoholic solution the phenylhy drazone-hydrazide is oxidised forming the diphenyldi- hydrotetrazone of P-aldehydopropionylphenylhydrazide N,Ph,(N:CH* CH2*CH2*CO-N,H2Ph)2 which separates in yellowish- or reddish-brown crystals m. p. 1229 gives with concentrated sulphuric acid a brown coloration becoming blue and finally violet and when heated with phenylhydrazine on the c6H,<NH>CEt CEt which crystallises from light petroleum in scales T.H. P. J. J. S. VOL. xciv. i. e'106 ABSTRACTS OF CHEMICAL PAPERS. water-bath is reduced to the phenylhydrazone-hydrazide ; the diphenyldihydrotetrazone is formed also but in smaller yields if a current of air is passed through a hot alcoholic solution of the phenylhydrazone-hydrazide. When treated with concentrated hydro- chloric acid in the cold the diphenyldihydrotetrazone is hydrolysed forming the diphenyldihydrotetrazone of P-aldehydopropionic acid which crystallises in colourless leaflets m. p. 160'. As this substance has not an acid reaction and does not react with barium carbonate but forms a readily soluble yellowish-white satt when boiled with aaueous barvta.it is considered to have the constitution The p-brorno~~enylhy~rccxone of P-aldegydopropionyl-p-bromopheny l- hydrazide C6H4Br*NH*N C H CH,*CH,- CO *N,H C6H4Br prepared by the action of p-bromopheny lhydrazine on dibromopyrotartaric acid crystallises in white needles m. p. 206'. The p - tolylhydraxone of /3 - aldehydopropionyl - p - tolylhydrazide C,,H,,.ON crystallises in glistening leaflets m. p. 2 1 7 O and on oxidation bv means of a current of air in alcoholk solution yields the di-p-tolytdi~~di*otetraxone C,,H,,O,N cry stallising in yello fv needles m. p. 153'. G. Y. Hofmann's Reaction with Amides and Hydrazine Derivatives of Carbonic Acid. AUGUST DARAPSKY (J. pr. Chem.1907 [ii] 76 433-466. Compare Schestakoff Abstr. 1905 i 332).-A detailed account of work previously published (Abstr. 1907 i 729). The following facts are new. Benzoylsemicarbazide is best prepared by the action of potassium cyanate on benzoylhydrazide in glacial acetic acid solution ; it is not oxidised to the azocarbonamide by chromic acid and when treated with sodium hypochlorite yields nitrogen carbon dioxide and benzoic acid. p-Bromophenylazocarbonamide sinters at 160' m. p. 17'7" (m. p. 165O Hantzsch and Glogauer Abstr. 1898 i 78). The action of sodium hypochlorite on p-methyl- p-bromo- and p-nitro-phenylazocarbonamide leads to the formation of the corresponding azoimides together with small amounts of the s-azo-compounds. P-Naphthylazoimide (Culmann and Gasiorowski Abstr.1889,1156) crystallises in white prisms m. p. 31-32'. as-Dibenzyl- and as-diethyl-carbarnides do not yield the as-disubsti- tuted hydrazines when treated with sodium hypochlorite. Benzoylhydrazide is converted by the hypochlorite into benzylidene- benzoylhydrazone or dibenzoylhydrazide and azodibenzoyl depending on the conditions of the reaction. G Y. Conversion of the Azine of 1 -MethylcycZohexone-3-one in to l-MethylcycZohexyl-3-hydr~~ine NICOLAI M. KIJNER ( J . &uss. Phys. Chem. Xoc 1907,39 Chem. 1240-1245. Compare Abstr. 1900 i 277 333)-The mine is prepared by the action of hgdrazine hydrate on methylcyclohexanone b. p. 170-172°/770 mm. aD + 1.52' (100 mrn.) but when the mine is decomposed with hpdruehloric acid itORGANIC CHEMISTRY 109 yields methylcyclohexanone b.p. 169*5'/750 mm. and uD + 12.20'. The alcoholic solution of the azine is reduced readily by sodium forming methylcyclohexylamine b. p. 154-155' aD - 1.70" (100 mm.) and rnethylcyclohexahydrrnzone methylcyclohexanone CHMed:2:eCH*NH*N Cd:2:!>CHMe b. p. 214'/90 mm. a' thick pale greenish-yellow liquid uD - 2 6 ~ 5 4 ~ (100 mm.). When treated with dilute acids it decomposes forming methylcycloliexanone and a salt of methylcyclohexylhydrazine which with alkalis forms the free methylayclohexylhydrazine b. p. 2095-210*5'/760 mm. Di0 0.9274 nz 1.4786 [.ID - 9.66'. It is a colourless liquid becoming thick but not crystallising at - 20'. It combines with hydrochloric and sulphuric acids and also with benzaldehyde and menthone.The com~oulzd,NHPh*CdoNH*NH*C7H13 crystallises in long needles m. p. 135" [a]D - 17.66'. Methylcyclo- hexane has n 1.42128. K. GEORGE FALK and JOHN M. NELSON (J. Amer. Chern. Xoc. 1907 29 1739-1744).-From the consideration of a number of compounds containing a double bond and existing in two stereoisomeric modifications it is inferred that if one of the isomerides is coloured the other will either be colourless or of a different colour from the first. Z . K. Stereochemistry of Indigotin. Indigotin has the constitution C,H,<:g>C:C<gE>C,H the carbonyl groups being in the 'cis-position since the compound yields only a mono-oxime (Thiele and Pickard Abstr. 1898 i 493). There is a Dossibilitv of the existence of a trans-isomeride which would be expected to have a different colour from that of ordinary indigo.Liebermann and Dickhuth (Abstr. 1892 480) have described a red diacetylindigotin. Ilt is suggested that a stereoisomeric change takes place during the formation of this compound and that it has the 8rc-cm-configuration. Similarly the tmns-structure is proposed for other red indigotin derivatives. Liebermann and Dickhuth's work has been repeated and their results confirmed. A general scheme is given of the relations between the acetyl derivatives of indigo and the bast methods of passing from one compound t o another. Liebermann and Dickhuth regarded a-diacetylindigo-white as containing the group *CO*bH*hH*CO* and the @compound as containing the group *C(OH):U*C:C(OH)*. It is considered more likely however that the a-form is internally compensated and that the /?-form is a racemic mixture capable of resolution into its optically active components.I 1 E. G. Electrolytic Reduction of Indigotin. HENRI CHAUMAT (Compt. rend. 1907 145 1419-142l).-lndigotin can be readily reduced by electrolytic hydrogen when it is intimately associated with the cathode of a cell in which sodium carbonate solution is undergoing elwtrolysie i 2108 ABSTRACTS OF CHEMICAL PAPERS. For this purpose the indigotin in a fine state of division mixed with a slightly coarser powder of graphite is piled round a stick of carbon in a linen bag and forms the cathode of an electrolytic cell charged with sodium carbonate solution and provided with a porous diaphragm to separate the two electrodes. The hydrogen liberated a t the cathode during the electrolysis reduces the indigotin to indigo-white which is dissolved by the equivalent of sodium hydroxide simultaneously formed.The introduction of the porous diaphragm to protect the reduced indigotin from the action of electrolytic oxygen liberated at the anode greatly increases the resistance of the cell and can be dispensed with if a solution of alkali or alkaline earth sulphite hydrogen sulphite or sulphide is added to the bath these salts being more readily oxidised than the indigo-white. HEINRICH WIELAND and LEOPOLD SEMPER (Annalert 1‘307 358 36-70. Compare Wieland Abstr. 1903 i 764; 1904 i 54).-The results of the investigation described in this paper have led the authors to suggest CH-YH for the so-called glyoxime peroxide the structural formula MeOaN- which is an oxide of furazan and is termed furoxan.The nomen- clature of the derivatives of glyoxime peroxide is altered accordingly ; thus diphenylglyoxime peroxide I I ,becomes diphenylfuroxan M. A. W. Constitution of the Glgoxime Peroxides. >o C Ph-8 Ph N*O*O*N The furoxans are readily converted into the corresponding furazans when heated with phosphorus pentachloride. In this manner phenyl- furazan ig prepared from phenylfuroxan. Diphenylfuraxan C,,H1,ON obtained from diphenylf uroxan crystallises in colourless prisms m. p. 94* yields an odour of benzonitrile and phenyIcarbimide when heated and remains unchanged on treatment with Caro’s acid. the action of phosphorus pentachloride on anisylmethylfuroxan ; it crystallises in white plates m.p. 79-41’. Phenylfuroxan (Scholl Abstr. 1891 317) cryst allises in colourless plates m. p. about 95O (slight decomp.) is stable in a desiccator yields benzonitrile but contrary to Scholl’s statement not benzaldehyde on prolonged boiling with alcohol dissolves unchanged in concentrated sulphuric acid or boiling concentrated hydrochloric acid and does not give Liebermann’s reaction or a coloration with ferric chloride. When treated with dilute sodium hydroxide phenylfuroxan rapidly dissolves evolving an odour of benzonitrile arid phenylcarbylamine and forming a yellow solution which must contain oxirninobenzoylformhydroxamic acid NOH:CPh*C(NOH)*OH as it gives with ferric chloride an intense brownish-red coloration stable towards mineral acids and with copper acetate a dirty green slimy precipitate which after solution in an acid gives the coloration with ferric chloride. When treated with ice- cold alcoholic potassium hydroxide or aqueous sodium carbonate and' ORGANIC CHEMISTRY.109 ether phenylfuroxan undergoes isomerisation which is explained with CPh*$lH*OH and the aid of the hypothetical intermediate product I I N*O*N*OH fi 'OH ; this K*O*N leads to the formation of hydroxyphenylfurazar crystallises in colourless needles m. p. 110-1 11' (decomp.) dissolves in aqueous alkalis and can for the greater part be regained by immediate acidification but is gradually decomposed by the alkali forming the preceding hydroxamic acid and benzonitrile. The hydroxyfurazan gives a brown coloration with alcoholic ferric chloride forms a crystalline acetate and reacts with phosphorus pentachloride with explosive violence yielding a crystalline product. OxirninobenxoyZamidoxime NOH CPh C(NOH) *NH prepared by treating phenylf uroxan in ethereal solution with ice-cold aqueous ammonia or in small amount by prolonged boiling of oximinobenzoyl cyanide with hydroxylamine crystallises in colourless leaflets m.p. 154O is soluble in alkalis or mineral acids and gives a n olive- brown coloratiou with ferric chloride. The dibenxoyl derivat rve C22H1704N3 forms leaflets m. p. 175-1 76'. Crystalline substituted amidoximes are formed from phenylfuroxan by the action of phenylhydrazine NOH:CPh*C(NO H )*NH*NHPh m. p. 173O (decomp.) or aniline NOH:CPh*C(NOH)*NHPh m. p. about 180' (decomp.).When boiled with water phenylf uroxan yields benzonitrile oxide which polymerises forming diphenylfuroxan formhydroxamic acid and an odour of benzonitrile. The transformation of furoxans into isonitrosoisooxalines has been described by Tonnies (Abstr. 1881 167) and by Angeli (Abstr. 1892 1 198). ifioNitrosoalzisy2iHooxaxoliiae OMe C,H4* CGN C(NuH'*xH2 formed by boiling anisylmethylfuroxan with methyl-alcoholic potassium hydroxide crystallises in colourless needles m. p. 172' (decomp.) is soluble in aqueous sodium carbonate and is decomposed when treated with alkalis. The benzoyl derivative Cl7Hl4O,N2 crystallises in white needles m. p. 143'. The action of methyl sulphate on the solution obtained on heating anisylmethyl- furoxan with methyl-alcoholic potassium hydroxide leads to the formation of a methyl derivative of isonitrosoanisylisooxazoline C1?H1203N2 crystallising in needles m.p. 107-1 08'. The dieubstituted furoxans are less reactive than the mono- substituted and are not attacked by ammonia aniline or phenyl- hydrazine even at high temperatures under pressure. Diphenyl- furoxan remains almost unchanged on prolonged boiling with alcoholic potassium hydroxide With magnesium organic compounds the furoxans form labile additive products from which they separate unchanged on treatment with water. The additive compound of magnesium ethyl iodide and anisylmethylfuroxan is an insoluble yellow substance. The $-nitrosite (N20?)[CH(CBH4*OMe)*CH2*NO,I formed from p-methoxgstyrene is obtained as a white crystalline powder decomp.110 ABSTRACTS OF CHEMICAL PAPERS.1 0 7 O gives the reactions for +-nitrosites and on distillation in a current of steam yields nitroanisylethylene and the nitro-oxime of p-met hoxystyrene OMe*C,H,*C(NOH)*CH,*N02. This crystsllises in colourless needles m. p. 112O decomp. 135O dissolves in aqueous alkalis and is precipitated by acids. This +-nitrosite and nitro-oxime differ from the homologous compounds derived from anethole in that they do not yield the Eorresponding furoxan. G. Y. Reduction of Diethylthiobarbituric Acid ALFRED EINHORN and HEINRICH VON DIESBACH (Ber. 1907 40 4902-4903).-The reduction of diethylthiobarbituric acid by sodium amalgam leads to the formation mainly of diethylmalonamide ; the by-products are 4 6-dihydroxy-5 5-diethyl-2 5-dihydropyrimidine (compare Tafel and Thompson this vol.i 58) which is isolated in the form of the double salt with mercuric chloride C,,HI,02N,,HgC12 m. p. 2 15-2 18O and bisdiethulmalonuZtetl.cl-aminoethane m. p. 340° which separates from dilute alcohol in white prisms containing 2H,O. 0. s. Thiazinee. 11. Derivatives of Tetraethylthionine. ROBERT GNEHM and ALFRED SCHINDLER (J. p r . Chem. 1907 [ii] 76,471-488. Compare Gnehm and Walder this vol. i 63).-Tetraethylthionine (ethylene-blue) is more reactive thaa methylene-blue as whilst the actmion of the theoretical amount of nitric acid in glacial acetic acid solution leads t o the formation of nitroethglene-blue NE t2* C,H,<:> C,H2 (NO,) NEt2X the nitration readily proceeds further to the formation of the nitrate of a dinitronitroso-base OH*N:C,H,< N s>C,H(NO,),*NEt,,HNO ; the position of the nitro-groups i n this base has not been determined.The paper contains an account of these substances and their reduction products. Tetraethylthionine is prepared by the action of sodium thio- sulphate and hydrochloric acid on nitrosodiethylaniline hydrochloride and treatment of the product with diethylaniline hydrochloride zinc chloride and sodium dichromate in boiling aqueous solution. The zincochloride is salted out as a blackish-blue powder and when gently heated with nitric acid in acetic acid solution yields dinitroisonitroso- diethylaminothiazine nitvate C,,H,,0,N5S HN0,,&H20 which separates from alcohol in green crystals ; the hydrobromide prepared by the action of hydrobromic acid and methyl alcohol on the nitrate is obtained in green crystals or as a brown powder forms bluish-red dichroic solutions which wibh the exception of the aqueous solution are fluorescent and with concentrated sulphuric acid gives a malachite-green coloration becoming bliie and finally rose-red on dilution. The free base formed by the action of sodium hydroxide on the hydrobromide is obtained as a brown flocculent precipitate ,H,505N!jS,HBr,$H20,ORGANIC CHEMISTRY.111 detonates when heated on platinum is insoluble in alkalis and again forms the dye on solution in hydrochloric acid. It gives with phenyl- hydrazine in acetic acid solution a brownish-yellow precipitate with ferric chloride a blood-red coloration with potassium ferricyanide a flesh-red solut’ion with phenol and concentrated sulphuric acid a green solution becoming bluish-red when poured into dilute sodium hydr- oxide and with aniline in methyl-alcoholic solution a violet coloration.The hydrochloride is crystalline. I n Formanek’s spectroscope the aqueous solution of the dye shows a line a t X=573 the alcoholic solution shows a line at X=573*4 and an absorption band in the blue; on addition of ammonia the lines disappear but the band persists Reduction of the dye with stannous chloride and hydrochloric acid leads to the formation of the hydrochloride of the leuco-base C,,H2,N,S,3HCI which separates from aqueous hydrogen chloride in crystals containing 5H20 or from methyl-alcoholic hydrogen chloride in white crystals Cl,H2,N,S,3HC1,3CH,0.The light brown base m. p. above 300° is readily oxidised by air. The dye prepared by oxidation of the leuco-base with ferric chloride is isolated as the xincochloride C16Hl,N,S,2HC1,ZnCI fcH40. It forms green to brown solutions in water alcohols or acids; the spectrum of the alcoholic solution has strong absorption in the red or after addition of ammonia a broad band in the green. Ethylene-green (Izitroethylerte-blue nitrotetraethylthionine) is isolated as the xincobrornide C20H240,N,SBr,~ZnBr,,2H20 ; it dissolves in water alcohols or acetic acid forming a bluish-green solution gives with concentrated sulphuric acid a dirty blue coloration becoming reddish- brown violet and finally bluish-green on addition of water and with fuming nitric acid a reddish-violet becoming deep blue on dilution. Addition of sodium hydroxide to the aqueous solution leads to the formation of a reddish-violet coloration and a precipitate which yields the original dye on treatment with hydrochloric acid ; potassium ferrocyanide in aqueous solution gives a light green coloration.The spectrum of the aqueous solution has a broad line at X = 639.7 and that of the alcoholic solution a broad line at A = 672. The hydr- iodide crystallises in green needles. ArninoethyZene-blue prepared by reduction of ethylene-green with stannous chloride and oxidation of the product with ferric chloride is isolated as the xincobromide C20H2eN4SBr,&ZnBr2,1 iH20. It forms deep blue solutions gives with concentrated sulphuric acid a reddish- brown with concentrated hydrochloric acid a yellow or with fuming nitric acid a reddish-violet coloration becoming violet to bluish-violet on dilution and yields a brown precipitate with sodium hydroxide.The spectrum of the alcoholic solution has a line about X = 623.8 and strong absorption in the red. Bvomoethylene-blue is formed by the action of bromine on ethylene- blue nitrate in glacial acetic acid solution ; the xincobromide C20H,6N,SBr,HBr,$ZnBr2,H20 was analysed. The dye forms deep blue solutions and gives with concentrated sulphuric acid an apple- green with concentrated hydrochloric acid a bluish-green and with fuming nitric acid a dark brown coloration becoming blue to violet-11.2 ABSTRACTS OF CHEMICAL PAPERS. blue on dilution On addition of so ium bydroxide the aqueous solution becomes violet and when d t e d turbid ; .on addition of ammonia the solution becomes reddigh-violet and fluorescent but blue when heated.With sodium hydroxide the alcoholic solution gives a cherry-red precipitate. The spectriim of the aqueous solution has a broad line at X=670 and a minor line at X=624; after addition of potassium hydroxide the broad line has X=676 and the minor line A - 614.8. The action of alcoholic ammonia on ethylene-blue nitrate at 145-150' leads t o the formation of as-diethylthionine which on oxidation and treatment with zinc bromide yields the xincobwmide NH,*C6H,<~>C6H,:NEt2Br,ZnBr*OH,H20 ; this loses H,O at 80-90'/35 mm. The dye is readily soluble forming deep blue solutions gives a reddish-brown product with fuming nitric acid and a reddish-violet precipitate with sodium hydroxide becoming blue on addition of hydrochloric acid and is readily reduced to the leuco-base by stannous chloride.Ammonia deepens the shade of the dye but on heating precipitates the base ; potassium ferrocyanide in acetone solution gives a light green precipitate. The aqueous solution gives a spectrum with a line at h=676 the alcoholic solution a line at X = 662 and strong absorption on the right. G. Y. Thiazines. 111. Derivatives of Alkylated Benzylanilines. ROBERT GNEHM and ALBERT SCHijNHOLZEH. (.I. pr. Chem. 1907 [ii] '76 489-508. Compare preceding abstract ; Scholtz Rohde and Bosch Abstr. 1904 i 992).-Attempts to prepare simple thionines from benzylmethyl- and benzylethyl-aniline were unsuccessful but on the other hand thiazines have been prepared from the sulphonic acids of these bases.The thiazines so obtained and a number of derivatives of benzylmethpl- and benzylethyl-aniline are described. The suZphate of as-benzylethyl-p-phen ylenediamine CH,Ph*NEt *C,H,*N H2,H2S04 has m. p. 146-148O (decomp.). BenzyZrnethyZ-p-nitrosoa?tiline NO*C,H,-NMe*CH,Ph separates from benzene in steel-blue crystals m. p. 52-53'; the hydrochloride forms n yellow crystalline precipitate m. p. 138'. The diarnine prepared by reduction of benzylmethyl-p-nitrosoaniline is obtained as a black oil and forms a sulphate crystallising in long white needles. Benz?lZethyZanilines~p~onic acid NEtPh*CH2*C,H,-S0,H,H,0 pre- pared by heating benzylethylaniline with sulphuric acid at 1 10-l2Oo crystallises in prisms sinters at 160-170' m.p. about 1909 The crystalline barium (C1,Hl6O,NS),Ba,4H20 and potassium salts were analysed. The oxidation of the sulphonic acid with chromic @cid leads to the formation of only small amounts of azobenzene and traces of benzoic acid. When heated with potassium hydroxide at 240-300° the potassium sulphonate yields p-~~ydroxybenxybthyk~nzZi.rze NEtPh*CH,*C,H,*OH m. p. 62-63' which does not form a rhodamine with phenol. The nitroso-derivative prepared from the sulphonic acid or its potassium salt is very soluble forms a green or in presence of C,,H160,NSK,ORGANIC CBEMISTR~ 113 mineral acids an orange-red solution and yields a green amorphous pracipitate with lead acetate. On reduction with zinc dust and sulphuric acid ?t forms an amino-sulphonic acid which is formed also by reduction of the dark red amorphous axo-sulphonic acid prepared by coupling diazobenzene chloride and benzylethylanilinesulphonic acid in alkaline solution ; the amino-sulphonic acid cannot be isolated either in the free state or as a salt.Dibenz yldiethylthioninedis~lphonic acid (?3H4'CH2>NEt C,H3<~>C,€€,oNE t * CH,-C,H,* S03H so,-o prepared &from benzylethylnitrosoanilinesulphonic acid by reduction with zinc dust and hydrochloric acid and successive treatment of the product with sodium thiosulphate and dichromate is identical with commercial thiocarmine. It is obtained as a bluish-black amorphous powder is readily soluble in water or alcohol is precipitated by sulphuric acid and gives with concentrated hydrochloric acid a green coloration becoming blue on dilution. Theleuco-compound C,0H3,0,N,S3 formed by reduction of the dye with zinc dust separates as a yellow flocculent precipitate on addition of sulphuric acid.The derivatives of benzylmethylaniline are prepared in the same manner as those of benzylethylaniline. Benx~lmethylanilin~~ulp~~onic acid C,,H,,03NS is obtained as a crystalline powder readily soluble in water ; the barium and potass&n C,,HI,03NSK salts are described. p-Hydroxybenaytmeth~baniline C,,H,,ON is obtained as a crystalline mass m. p. 40-41'. The nitroso-derivative of benzylmethylanilinesulphonic acid prepared by the action of amyl nitrite on the sulphonic acid in glacial acetic acid solution is obtained as a reddish-brown crystalline powder ; the product formed on reduction of this with zinc dust and sulphuric acid is not the p-amino-sulphonic acid Dibenzyldimethylthion~n~d~s~lp~onic acid and its salts are readily soluble and separate only as resins.The Zeuco-compound forms a yellow flocculent precipitate which decomposes becoming black when dried in a vacuum. rn-Nitrobe~xylnaethylsniline C R 402N2 prepared by nitration of benzylmethylaniline by Groll's method (Abstr. 1886 347) crystallises from alcohol in yellow leaflets m. p. 51-52'; the picrote m. p. 112-113O. Oxidation of the nitro-base leads to the formation of m-nitrobenzoic acid whilst reduction with seannous chloride and hydrochloric acid leads to the formation of m-aminobenxylmethyl- annitine which is isolated in the form of its acetyl derivative NMePh*CH2*C,H,*NHAc crystallising in coloiirless leaflets m.p. 88". Reduction of m-nitrobenzylethylaniline and treatment of the product with acetic anhydride leads t o the formation of the acetyl derivative NEtPh*CH2*C,H,*NHAc crystallising in leaflets m. p. 96'. Reduction of Azo-compounds by Means of Sodium Hypo- sulphite. HARTWIU FRANZEN and P. STIELDORF (J. pr. Chenz. 1907 [ii] 76 467-471. (C,,H,,O,NS),Ba,2T-IzO G. Y. Compare Grandmougin Abatr. 1907 i 850).-.114 ABSTRACTS OF CHEMICAL PAPERS. The reduction of an azo-compound such as helianthin to two primary amine molecules by means of sodium hyposulphite might take place according to the equation (I) NMe,*C,H,*N,*C,H,*SO,Na + 2Na2S,0 + 4H20 = NMe2-C,H4*NH2 + NH,*C,H,*SO,Ka + 4NaHS03 or (11) NMe,.C,H,*N,.C,H,*SO,Na + Na,S,O + 3H20 = NMe2*C,H,*NH + NH,*C,H,*SO,Na + NaHSOs + NaHSO,.The authors have employed two methods to determine by which reaction the reduction takes place. As 1 mol. of sodium hyposulphite requires 6 atoms but 1 mol. of sodium sulphite only 2 atoms of iodine when titrated the product of reaction (I) must reduce two-thirds but that of (11) only one-third of the iodine required for the titration of the same amount of the original sodium hyposulphite solution. The results obtained with helianthin and p-sulphobenzeneazo-a-naphthol show that the reaction takes place according to equation (I) The same result is obtained by determining the amount of sulphuric acid in the hyposulphite solution before and after the reduction ; only a very slight increase is found whereas according to equation (11) each mol.of hyposulphite must yield 1 mol. of sulphuric acid. G . Y. Action of Diazobenzene on Blutaconic Acid and Ethyl Glutaconate. FERDINAND HENRICH and W. THOMAS (Ber. 1907 40 4924-4930).-When glutaconic acid is treated with diazobenzene chloride (2 mols.) formccxylacrglic acid NHPh*N:C(N:NPh)*CH:CH*G02H is obtained accompanied by the evolution of carbon dioxide crystal- lising from alcohol in reddish-brown felted needles m. p. 1 9 9 O (decornp.). The sodium and potassium salts are sparingly soluble ; the silver salt is dark coloured. The ethyl ester C,,H,O,N crystallises in long slender dark red needles m. p. 1 2 3 O and is not identical with the formazyl compound previously obtained from ethyl glutaconate and diazobenzene chloride (Abstr.1902 i 422). This is now shown t o be ethyl r-p~enylaxogluta,co7zonate-phe~ylhydraxonQ CO,Et*C(N*NHPh)-CH:C(N:NPh)*CO,Et as it readily loses alcohol on boiling its alcoholic solution forming ethyl l-piLenyld-~enxeneaxo-6-pyridnxone-3-carboxylate Nph<N:C(c02Et )>C CO*C(N,Ph) Hs which crystallises in small brownish-yellow crystals m. p. 163-1 640. The conclusion that the azohydrazone has the constitution ascribed to it is supported by the fact that etbyl a-methylglutaconate does not give a corresponding derivative with diazobenzene chloride. With ethyl glutaconate the diazo-salts From 0- and p-toluidine and chloro- and bromo-anilines give similar derivatives to diazobenzene ; the tolyl compounds are deep dark red in colour and the others are yellow- ish-red.W. R. Action of Nitrous Acid on Proteins. ZACCARIA TREYES and GIOVANNI SALOMONE (Biochem. Zeitsch. 1907 '7 I1 -23).-Nitrous acid acting on proteins a t 0' produces ill-defined substances which the authors regard as diazo-compounds. The group of the proteinORGANIC CHEMISTRY. 115 molecule concerned in diazotisation is not the same as that which is concerned in the fixation of labile sulphur or in the combination with formaldehyde. The diazo-compounds show all the characteristic protein reactions although somewhat slowly and less clearly. After precipitation of the diazo-compounds no proteins remain in solution. On boiling with water and alkali the diazo-compounds form proteinq which give a violet biuret reaction.The biuret reaction can scarcely depend on the presence of the complex CO*NH since this group would be destroyed by the action of nitrous acid. G. 13. Studies on Enzymes. I. Quantitative Measurement of Pro- tein Hydrolysis by “Formaldehyde Titration.” S. P. L. SORENSEN (Biochem. Zeitsch. 1907 7 45-101).-The existing methods for estimating the extent of protein hydrolysis are arbitrary and unsatis- factory. A rational method must at4tempt the measurement of the quantity of carboxyl- and amino-groups formed during the hydrolysis. This is best done by titrating the carboxyl group with alkali after the aminic function has been abolished by formaldehyde according to Schiff’s method (Abstr. 1903 i 232). The reversibility of t h i s reaction and other circumstances render the employment of certain precautions necessary to ensure accuracy.The indicator must show an end point with as high a concentration of hydroxyl ions as possible; hence phenolphthalein or thymolphthalein (preferable in many cases) must be employed. The end point is not indicated by the appearance of a faint pink coloration but the titration must be continued until the solution has the same strong red colour as a test solution which is prepared for comparison by adding a few drops of 1V/6 baryta to a dilute formaldehyde solution. The latter has been neutralised previously so as t o give only a faint pink colour with phenolphthalein and by the addition of the baryta acquires the pronounced red colour which is desired. Under these conditions the amount of amino-acid found (in R pure N/10 solution) amounts on the average to 98% of the actual amount present.This applies to a large number of mono- di- and oxy-amino- acids ; only in the case of phenylalanine and tyrosine is a considerably smaller amount found than that actually present. The ratio between the extents of protein hydrolysis as measured by this method and by precipitation with tannic acid is generally greater than 1 ; at least in the early stages formaldehyde titration indicates a greater degree of hydrolysis than tannic acid precipitation. After the addition of formaldehyde uric acid can be titrated sharply as a monobasic acid. G. B. Hydrolysis of the Globulin from the Almond (Amandin). Hydrolysis of the Proteins of Maize. Hydrolysis of Gliadin from Rye.THOMAS B. OSBORNE and SAMUEL E. CLAPP (Amer. J. Phy~+ioZ. 1908 20 470-476 477-493 493-499)- The following table gives the main results in percentages :116 ABSTRACTS OF CHEMICAL PAPERS Amandin. Gliadin Gliadin Hordein Zein Alkali-soluble (rye). (wheat). (barley). (maize). protein of maize. Glycine ............ 0.51 0.13 0.02 absent absent 0'25 Alanine ... ........ 1.40 1-33 2-00 0'43 2.23 not isolated Veline ............... 0*16 not isolated 0.21 0'13 0.29 not isolated Leucine ............ 4.45 6.30 5-61 5.67 18-60 6 *22 Proline ............... 2'44 9.82 7.06 13.73 6.53 4-99 Phenylalanine ... 2.53 2.70 2.35 5.03 4.87 1'74 Aspartic acid ...... 5.42 0.25 0 5 8 not isolated 1'41 0.65 Glutamic acid ...... 23'14 33*81 37.33 36.33 18-28 12'72 Serine ...............( 2 ) 0.06 0.13 not isolated 0.57 not isolated Tyrosine ............ 1.12 1.19 1.20 1.67 3.55 3.78 Arginine ............ 11.85 2.22 3.16 2.16 1'16 7 -06 Lysine ............... 0.70 absent absent absent absent 2'93 . Histidine ............ 1.58 0'39 0.61 1.28 0.43 3.00 Ammonia ......... 3.70 5'11 5.11 4.87 3.61 2.12 Tryptophan ...... present present present present absent present - Cystine ............ - not deter- 0.45 not deter- not deter- mined mined mined Total ...... 59.00 64.31 65-81 71'32 61.53 45'44 The amino-acids absent in zein are present in the alkali-soluble protein of maize so thab the mixture yields all the amino-acids usually obtained from proteins. The gliadin of wheat and rye are probably identical but the differ- ences between it and hordein and zein are noteworthy. These three proteins are all soluble in alcohol and form a group characterised by their high content of glutamic acid protein and ammonia their low content of arginine and histidine and absence of lysine. Zein also lacks tryptophan and glycine. Fatty Acids of Protein Putrefaction and Optically Active Valerie and Hexoic Acids. CARL NEUBERU and E. ROSENBERU (Bio- chem. Zeitsch. 1907,7,178-190. Compare Abstr. 1906 i 923).-One kilo. of casein yielded on putrefaction 117 grams of fatty acids. More than one-third of these consisted of butyric acid which is considered to be derived from glutamic acid since this acid occurs abundantly among the amino-acids formed in the hydrolysis of casein. Somewhat smaller quantities of formic valeric and hexoic acids were obtained and still smaller yields of acetic propionic and a decoic acid. The valeric acid fraction had a rotation indicating the presence of 18% of d-u-methylbutyric acid and the hexoic acid fraction probably contained 46% of P-methylvaleric acid (derived from isoleucine). Similar results were obtained with putrefied gelatin. Conversion of Optically Inactive Triolein into an Optically Active Glyceride and an Optically Active Acid. CARL NEUBERG and E. ROSEHBERU (Biochem. Zsitsch. 1907 '7 191-198).- The authors have repeated and confirmed Neuberg's work on the diglyceride of dibromostearic acid (Abstr. 19U6 i 923). JULIUS LEWHOWITSCH (Chem. Zeit. 1908 32 54-55) ascribes the optical activity of Neuberg and Rosenberg's products to the intro- duction of optically active ricinus oil with the lipase employed in the hydrolysis of the glyceride. W. D. H. G. B. G. Y.