733 Organic Chemistry. Composition of Petroleum. Hydrocarbons in Pennsylvania Petroleum with Boiling Points above 216'. By CHARLES F. MABERY (Ante?.. Chem. J. 1902 28 165 - 198).-The following hydro- carbons have been isolated from the fractions of Pennsylvania petrol- eum boiling above 216'; they were purified by treatment with f uniing sulphuric acid. Tridecane C13H28 boils at 221-222' and has a sp. gr. 0.7834 and nD 1,4354 a t 20' ; its chloyo-derivative C,,H,,Cl boils at 135-140' under 12 mm. pressure and has a sp. gr. 0,8973 and n 1.451 a t 20'. Tetradecane C14H3, boils at 142-143' under 50 mm. and a t 236-23s' under 760 mm. pressure and has a sp. gr. 03'814 and n 1.4360 a t 20' ; its chloro-derivative C,,H,,Cl boils at 150-153' under 20 mm. pressure and has a sp. gr.09185 ; the dichloro-deriv- ative C,,H,,CI boils at 175-180' under 12 mm. pressure and has a sp. gr. 1,032 a t 20'. Pentadecane C15H32 boils at 158-159' under 50 mm. and a t 256-257' under 760 mm. pressure and has a sp. gr. 0,7896 and n 1.4413 a t 20' ; the dichlwo-derivative C,,H,,Cl boils at 175-180' under 13 mm. pressure and has a sp. gr. 1.0045 at 20'. Hexadecane C16H3 boils at 174-175' under 50 mm. and a t 275-276" under 760 mm. pressure and has a sp. gr. 0.7911 and n 1,4413 at 20' ; the dichloro-derivative C16H$12 boils at 205-2 10' under 16 mm. pressure and hss a sp. gr. 1,0314 at 20'. Heptadecane C17H36 boils a t 188-190' under 50 mm. and at 288-289' under 760 mm. pressure and has a sp. gr. 0.8000 a t 20'; the chZoro-derivative C17H,,CI boils at 175-177' under 15 mm.pressure and has a sp. gr. 0.8962 at 20'. The fraction which boiled a.t 199-200' under 50 mm. and a t 300-301'under 760 mm. pressure had a sp. gr. 0.8017 at 20' and fur- nished a chloro-derivative C,,H,,Cl which boiled a t 185-1 90" under 15 mm. pressure and had a sp. gr. 0.9041 a t 20'. When this fraction was cooled to -lo' a white solid octodecane Cl8HS8 separated which melts a t 20' and has a sp. gr. 0,7830 a t 20°/200 and 0.7816 at 40°/200 and nD 1.440. After the solid hydrocarbon had been removed by filtration the liquid portion had asp. gr. 0.81 10 a t 20' nD 1.4435 and a composition indicating that it mas a mixture of the two hydrocarbons The fraction boiling at 210-212' under 50 mm. pressure had a sp. gr. 0.8122 and n 1.4522 a t 20'. On cooling this fraction t o - lo' solid nonodecane C19H40 separated which melts at 33-31" and has a sp.gr. 0.7725 a t 3O0/5O0 and 0.7781 a t 40'/30' ; the filtered oil had the composition ClgHs8 a sp. gr. 0.8208 and nD 1.4515 a t 20'. The distillate collected a t 230-232O under 50 mm. pressure had a sp. gr. 0.8230 and n 1.4608 a t 21)'; it consisted of a solid heneicosane '1pH38 and C18H36' VOL. LXXXIT. i. 3 f734 ABSTRACTS OF CHEMICAL PAPERS. C21K44 melting at 40-41° and a liquid hydrocarbon C21H42 which has a sp. gr. 0.8424 at 20'. The fraction boiling at 240-242' under 50 mm. pressure had a sp. gr 0.8230 and n 1.454 a t 20'. On cooling it deposited a solid docosane C2,H4 which melts a t 44' and has a sp. gr. 0.7796 at 60'; the liquid portion C22H44 had a sp.gr. 0-8296 a t 20'. The portion collected a t 258-260' under 50 mm. pressure had a sp. gr. 0.8341 a t 60° 0.8320 a t TO" and 0.8310 at 80". It furnished a small proportion of a solid tricosane C23H48 which melts at 45' and has a sp. gr. 0-7894-0.7900 a t 60'; the filtered liquid C23H46 had a SP. gr. 0,8569 and nD 1.4714 a t 20'. The distillate at 272-274' under 50 mm. pressure consisted of a solid tetracosane C24H50 which melts a t 4 8 O and has a sp. gr. 0'7302 a t 60° 0.7893 a t TO' and 0.7875 at SOo and a liquid hydrocarbon C24H4SY which has a sp. gr. 0.8582 a t 40°/200 and n 1.4726. The fraction boiling a t 280-282' under 50 mm. pressure yielded a solid pentacosane C25H52 which crystallises in plates and melts at 53-54'; the liquid portion C26H52 had a sp.gr. Oe8580 and n D 1,4725. The portion collected a t 292-294' under 50 mm. pressure was com- posed of a solid hexacosane C26H54 melting a t 58' and a thick viscous oil C2'rH52 which had a sp. gr. 0.8688 at 26' and n 1.4722. The distillate a t 310-31Z0 under 50 mm. pressure furnished a solid octocosane which melted at 60' and had a sp. gr. 05'945 at 70° 0.7927 at 80° and 0.7911 at 90° and a thick oil C,,H,,,~which had a sp. gr. 0.8694 and n 1.480. By ARTHUR HANTZSCH (Bey. 1902 35 2978 -2980)-A discussion of the consti- tution of the additive product of nitrogen trioxide and P-methyl- AF-butylene described by Schmidt (this vol. i,681) for which the author h. G. Desmotropism of Trimethylethylene Nitrosite. R. H. P. CHRle*O*N CIMe2-O* N prefers the formula I I >o.Connection between Bisnitrosyl Compounds and Nitroso- compounds. By OSCAR PILOTY (Ber. 1902 35 3090-3093).- Comparing the properties of the nitroso-compounds described in the two following papers the author concludes that there is no essential difference between nitroso-compounds and the bisnitrosyl compounds which contain the N202 group. Ou the contrary the transition from the one class to the other is gradual ; the typical nitroso-compounds are unimolecular liquids or crystallised solids of a deep blue colour; some nitroso-compounds form colourless solids which become blue when melted or dissolved and these are bimolecular in the cold and contain the N20 group. The difficulty of resolving the N20 group into two NO groups increases until finally the typical bisnitrosyl compounds are arrived at and these no longer shorn the blue colour under any conditions.J. McC. Constitution of +-Nitroles and some Bromonitrosohydro- carbons. By OSCAR PILOTY and A. STOCK (Ber. 1902,36,3093-3101). -Propyl-$-nitrole prepared from /I-bromo-p-nitrosopropane by shakingORGANIC CHEMISTRY 735 in ethereal solution with silver nitrite forms white crystals which melt at 76". p-Bromo-p-nitrosobutu~~ formed when methylethylketoxime in aque- ous solution is treated with bromine in presence of pyridine is a deep blue volatile liquid which boils a t 2 8 O under 19 mm. pressure and has a sp. gr. 1.360 a t 2 2 O . With silver nitrite it gives butyl-+-nitrole which melts at 6 8 O . I n the same way from diethylketoxime PJworno-p-nitrosopentacne is formed as a liquid which boils at 4 9 O under 17 mm.pressure and has a sp. gr. 1.325 a t 20°; with silver nitrite it gives amyl-enitrole melting a t 63.5'. By the action of bromine in presence of pyridine on the oxime obtained by treating pinacolin with hydroxylamine y-bromo-y-nitroso- /3/3-dimet?~ylbutccne is produced It forms volatile blue crystals with an odour recalling that of camphor. The formation of bromonitroso-compounds is a useful test for ketones. The solution to be tested should be made neutral and to it a drop of a 10 per cent. solution of hydroxylamine hydrochloride and one of a 5 per cent. solution of sodium hydroxide added. A large drop of pyridine is introduced and a thin layer of ether poured on after which it is shaken with sufficient bromine to impart a yellow colour to the ether.If on addition of hydrogen peroxide the ether becomes blue the presence of a ketone or ketonic group may be concluded. When butyl-+-nitrole is dissolved in anhydrous hydrogen cyanide a t - 10") the solution is colourless ; the depression of the freezing point of the hydrogen cyanide was observed and again after standing when the solution had become quite blue. It was found that the second de- pression was exactly double the first indicating that in the colourless form the +-nitrole has a doubled molecular formula. From the transformation of the bromonitroso-compounds into +nitroles with silver nitrite the authors conclude that the former are true nitroso-compounds. J. McC. Halogenated Nitroso-compounds of Diketocyclohexamethyl- ene and a Secondary Nitrorso-compound By OSCAR PILOTY and HERMANN STEINBOCK (Bey.1902,35,3101-3117).-By the action of bromine in presence of pyridine on the dioxime of p-diketocyclo- hexane 1 4-dib~omo-1 4-dinit~osocyclohexane is formed ; i t crystal lises in deep blue rhombic pyramids melts a t 89" and is very easily soluble in alcohol acetic acid ether or benzene. I n this reaction it is the cis-tram-modification which is formed and there is also produced 1 4-dibrorno-1 4-bisnityosyloyclol~exane which is colourless and insoluble in ether. Nitric acid or chromic and acetic acids transform the nitroso- compound into 1 4-dibromo-1 4-dinitrocyclohexane which melts at 168" and is insoluble in water but easily soluble in alcohol ether or acetic acid. When a current of chlorine is passed through a cooled hydrochloric acid solution of p-diketocyclohexanedioxime the cis-trcms-modifica- tion of 1 4-dichloro-1 4-dinitrosocyclohexane is produced.It is formed much more easily than the corresponding bromo-compound and does not require the presence of pyridine. It forms deep blue monoclinic 3 f 27'36 ABSTRACTS OF CHEMICAL PAPERS prisms melts at 108*5' and is easily soluble in the common organic solvents. When hydrogen chloride is passed through a solution of it i n glacial acetic acid it changes into 1 4-dichloro-l 4-bisnitrosyZcyclo- hexane which separates in colourless crystal& This represents a new class of intermolecular bisnitrosyl compounds for which the formula AH CH,\ developed is CClLg202L'CCl. It is soluble in methyl alcohol \cH,-cH,/ acetone or acetic t o colourless solution which when heated becomes blue and again colourless when cooled.This characteristic reaction is attributed to its conversion into a nitroso-compound at the higher temperature. With chromic and acetic acids the chloronitroso- compound gives 1 4-dichloro-1 4-dii~itrocyclohexune as a greenish substance which melts a t 178" and is soluble in the ordinary organic solvents. By the action of chlorine on benzaldoxime a very unstable blue substance is formed which the authors believe t o be o-cldoro-w-nitroso- toluene CHPhC'l* NO. With acetaldoxime in hydrochloric acid solution chlorine gives mdnochloronitrosoethane which can be obtained i n colourless plates ; it dissolves in ether or methyl alcohol with a deep blue colour and melts at 65" to a blue liquid which becomes colourless on solidifying.It is spontaneously transformed into acetohydroximic acid chloride (CHMeCI-NO - CMeCl:N*OH) which solidifies at - 3". When dis- solved in hydrochloric acid and treated with chlorine this hydroximic acid chloride gives dichZoronitrosoethane CH,*CCl,*NO as a liquid which boils at 68'(corr.) ; it is miscible with alcohol ether or benzene but not with water and has a sp. gr. 1.2521 at 19'. The constant for the molecular depression of the freezing point of anhydrous hydrogen cyanide has been determined t o be 21.7 and a normal molecular weight has been found for dichloronitrosoethane in this solvent. J. McC. Formation of Alcohols by the Electrolysis of the Salts of the Fatty Acids.By HANS HOFER and M. MOEST (Annalen 1902 323 284-323).-Methyl alcohol is produced when sodium acetate is electrolysed in aqueous solutions containing sodium per- chlorate ; under similar conditions the corresponding propionate and n- and iso-butyrates give rise to ethyl and n- and iso-propyl alcohols respec- tively. Sodium succinate yields hydracrylic acid instead of ethylene glycol. Other inorganic salts induce this reaction namely chlorates sulphates carbonates and hydrogen carbonates. The aldehydes corre- sponding with the alcohols are also formed during the electrolysis. Only small quantities of the alcohols and aldehydes are obtained on electrolysing valerates and hexoates. The communication includes a detailed account of the apparatus employed and tables indicating the composition of the gases produced with solutions of varying concentration (compare Abstr.1894 i 228 ; 1896 i 10 664). By Lours HENRY (Bull. Acacl. Roy. Belg. 1908 445-494).-The action of alcohols on esters is not G. T. M. Action of Alcohols on Esters.ORGANIC CHEMISTRY. 737 dependent simply on the reactive intensity nf the alcohol (measured by its esterification velocity for acetic acid) except in the cases of the action of methyl or ethyl alcohol on amyl glyceryl and cellulose nitrites (compare Bertorii Abstr. 1886 217 and 1887 458) and of the same alcohols on mixed acid anhydrides (compare Behal Abstr. 1899 i 734) which the author regards as a class of esters. In many cases the action is modified by the reactive intensity of the acid residue of the ester thus pyruvyl formate CH,Ac*O*CHO is decomposed by methyl alcohol with the liberation of pyruvyl alcohol (a small amount of the corresponding ether melting at 130' i& also formed) whilst pyruvyl acetate is not attacked. Temperature is also an important factor thus whilst amyl nitrite is decomposed in the cold by methyl or ethyl alcohol it is not attacked by propyl or butyl alcohol until heated although these possess higher reactive intensities than amyl alcohol.I n some cases the effect of temperature is to invert the action altogether thus glycol when boiled with diethyl succinate liberates ethyl alcohol although the reactive intensities of the two alcohols are respectively 66% and 53.9 the abnormality being due to the greater volatility of ethyl alcohol (compare Vorlander Abstr.1895 i 17). It is probable also that solubility plays a considerable part in influencing actions of this type. Functional inertia of the alcohol may also be overcome by greatly increasing ifs reacting mass relatively to that of the ester (compare Walker Abstr. 1893 i 500 and Vorlander loc. cit.) Reactive intensity in a homologous series of alcohols decreases as the series is ascended and the same result is produced by the intro- duction of negative groups such as OH C1 CO the effects of these increasing with their proximity t o the original OH group of the alcohol (compare Heintx AnmZen 1861 114 440 ; Bertoni Zoc. cit. ; Richter this Journal 1877 ii 439; Rose Abstr. 1881,251 ; Bachmann Abstr. 1883 726 ; Behal Zoc.cit. ; Henry Abstr. 1901 i 577 ; Vor- lander Zoc. cit.) where reactions illustrating this general statement are to be found. In the original paper explanations of these reactions embodying the foregoing views are given. T. A. H. Mono-ethers of Bivalent Alcohols. By M. H. PALOMAA (Ber. 1902 35 3299-3301).-By treating ethylene glycol with sodium and an alkyl iodide the mono-ethers are obtained. Glycol monomethyl ethsr OMe*CH,*CH,*OH boils at 124-125O has an ethereal odour and a sp. gr. 0.9703 at 19O/19O and is miscible with water. With acetic anhydride it gives an acetate of the formula OMe*CH,-CH,*OAc which boils at 144.5-145O and has a sp. gr. 1.0090 at 19"/19". The mono-n-propyl ether of ethylene glycol Pr*O*CH,*CH2*OH boils at 152-153O and has a sweet odour and a sp.gr. 0.9159 at 19'/19O. J. McC. Products which are Formed by simultaneously passing Dry Sulphur Dioxide and Ammonia into Absolute Alcohol dis- tilled over Sodium. By ALWIN GOLDBERG and M. R. ZIMMEBMANN (Zeit. angew. Chern. 1902 15 898-906).-The ammonium sulphites,738 ABSTRACTS OF CHEMICAL PAPERS. obtained by passing sulphur dioxide and ammonia into absolute alcohol were first prepared by Muspratt (Annabn 1844 50 269) and sub- sequently studied in detail by Schumann (Abstr. 1900 ii 271). Divers (Trans. 1899 75 533) prepared ammonium ethyl sulphite by using carefully dried alcohol and a low temperature - 15'. The authors have prepared the same compound which they call dmnzonium ethoxysulphinate a t the ordinary temperature ; it is decomposed by hot water into ammonium pyrosulphite and alcohol. Ammonium methoxgsulphinate OMe*SO*ONH is prepared similarly as are also the analogous derivatives of amyl alcohol methylethylcarbinol and trimethylcarbinol. The co?xpound from allyl alcohol is formed by union of 3 mols.of ammonia and sulphur dioxide respectively and 2 mols. of allyl alcohol; from the fact that only two-thirds of the sulphur dioxide can be titrated by iodine the salt is represented by the formula ONH,*SO*O*[CH,'],*SO,*CI-12*CH(NH,)*CH2*O*S0*ONH,. On leading ammonia into molten ammonium ethyl sulphite a t 99' ammonium aminosulphinccte NH,*SO*ONH is formed. When am- monium ethyl sulphite is heated ammonium sulphate is formed; when heated under pressure with absolute alcohol or ethyl bromide am- monium sulphate and thiosulphate are produced ; if the salt is heated alone under pressure besides ammonium sulphate and sulphur a yellow oil C,HI,O,S which is volatile with steam is obtained.Ammonium methyl sulphite decomposes in a similar manner. Action of Acid Chlorides and Anhydrides of the Fatty Series on Trioxymethylene. By MARCEL DESCUD~ (Bull. Xoc. Chim. 1902 [iii] 27 867-871. Compare Abstr. 1901 i 644 and this vol. i 149 339 451)-When trioxymethylene reacts with acetyl chloride in presence of zinc chloride there are formed chloromethyl acetate dichloromethyl oxide and methylene diacetate ; the last which boils tit 170° is also formed by the action of acetic anhydride on trioxymethylene in presence of zinc chloride. In this reaction there is also produced methyleneoxide diucetate (Me*CO,*CH,),O which distils a t a temperature of 204-207'.I n a similar manner there have been prepared chloromethyl propionate boiling a t 128-130° sp. gr. 1.140 ; mthylene dipropionccte boiling a t 190-1 92' sp. gr. 1 a503 ; chloromethyl isobutyrate boiling a t 138-140° sp. gr. 1.080 ; methylene diisobutyrate boiling at 197-199' sp. gr. 0.998 ; chloromethyl butyrate boiling a t 150° sp. gr. 1.094; methylene dibutyrate boiling at 215-216" sp. gr. 1.017 ; in all cases the boiling points were determined under a pres- sure of 745 mm. and the sp. gr. taken at 20°/20'. Some of the commercial specimens of trioxymethylene are not suit- able for the above reactions but a suitable specimen can be obtained by slowly evaporating a solution of formaldehyde.By H. G. BYERS and PAUL HOPKINS (J. Amer. Chem. Xoc. 1902 24 764-771).-When the wood was distilled at temperatures below 400° there were obtained (A) 47.5 per cent. pyroligneous acid containing acetic acid 3.47 per cent. and methyl alcohol 4-16 per cent.; (B) 7.5 per cent. of tar containing light oil 18.0 creosote oil 23.0 pitch 39.0 and water 20.0~per cent ; (C) 30.0 per cent of charcoal; K. J. P. 0. A. F. Wood Tar of the Douglas Fir (Pseudotsuga Taxifolia).ORGANIC CHEMISTRY. 739 and (D) 15.0 per cent of gas. At temperatures below 700" there were obtained (A) pyroligneous acid 34 per cent containing acetic acid 2.9 and methyl alcohol 2.9 per cent.; (B) tar 17.7 per cent. contain- ing light oil 8-0 creosote oil 10.0 pitch 18.0 and water 64.0 per cent. ; (C) charcoal 29 per cent.and (D) gases 19.3 per cent. The gas is non-illuminating; the charcoal is soft and contains little ash. The creosote oil boiled from 160-250° and contained 17 per cent. of creosote of which 9.5 per cent was guaiacol. The light oil which boiled between 40Oand 150° was fractionated and contained small amounts of aldehydes and ketones and considerable amounts of the methyl and ethyl esters of formic acetic propionic and butyric acids. The results of the fractionation and tohe yield of the products are tabulated in the original. Behaviour of Certain Acyl Chlorides towards Agents which eliminate Hydrogen Chloride. By EDGAR WEDEKIND (Annalen 1902 323 246-257).-Acetyl chloride when treated with triethylamine dissolved in benzene loses hydrogen chloride and 4 mols.of the residue condense to form dehydracetic acid; its next homologue propionyl chloride behaves differently under these condi- tions giving rise t o a trimeric condensation product. Compounds of similar complexity have also been obtained from phenylacetyl chloride and dihydrocinnamyl chloride. Dehydracetic acid also results from the action of ferric chloride on acetyl chloride. The homologous chlorides of the fatty series when condensed with dry metallic chlorides yield high-boiling oils the con- stitution of which is not yet known. Benzoyl chloride and phenyl- acetyl chloride do not give rise to ketones under the influence of ferric chloride. The aromatic acyl chlorides containing a t least three carbon atoms in the side chain condense to form cyclic ketones ; dihydro- cinnamyl chloride yields hydrindone whilst phenyl-n-butyryl chloride and phenyl-n-valeryl chloride furnish a-ketotetrahydronaphthalene and pheno-a-ketocycloheptane respectively.Cinnamyl chloride does not however condense to form an indenone. Aluminium chlorido also serves to promote these condensations. I n ethereal solutions the acyl chlorides under the influence of the an- hydrous metallic chlorides give rise to the ethyl esters of the corre- sponding acids. G. T. M. T. A. H. Nature of Radicles. By EDGAR WEDEKIND (Annalen 1902,323 267-264. Compare Vorlander this vol. i 309 ; ii 250).-Ethyl chlorocarbonate does not form additive products with the strong tertiary bases although it is readily decomposed by these substances the action being accompanied by an elimination of hydrogen chloride.It follows therefore ,that this acyl chloride conforms t o the author's rule that two negative groups one of which is a strongly acidic radicle do not under ordinary conditions form additive products with the tertiary amines. The author's study of the interaction of acyl chlorides and the tertiary bases leads to the following conclusions. The more rapid and complete is the interaction of these reagents the740 ABSTRACTS OF CHEMICAL PAPERS. greater is the probability. of an elimination of hydrogen from the molecule of the acyl chloride and the consequent formation of bye- products. On the other hand the slower the elimination of hydrogen chloride the greater is the tendency for the intervention of' moisture leading to the production of acid anhydrides.Pyidine picrgl chloride C,NH,Cl*C H (NO,) results from the addition of picrgl chloride to pyridine6; St is a yellow amorphous powder readily decomposed by water or the hydroxylic solvents with the production of pyridine picrate. Triethylamine appears to yield a similar product but no addition takes place in the case of tripropyl- amine. G. T. M. Linseed Oil. By S. FOKIN (J. Russ. Phys. Chem. Soc. 1902 34 501-503).-Contrary to the observations of some other investigators the chief constituent of linseed oil is found to be linolic acid together with 23-25 per cent; of linolenic acid and about 5 per cent. of solid fatty acids. The linolic acid contained in linseed oil is apparently isomeric with those obtained from cotton-seed oil and sunflower oil.The tetra- bromostearic acid prepared from linseed oil is difficult to obtain in a solid state and then forms an amorphous mass melting a t 98-101° whilst the similar acid from other oils is distinctly crystalline and melts at 114-1 15O. T. H. P. Action of Organic Acids on Antimony Oxides. By EDUARD JORDIS (Zeit. angew. Chem. 1902 15 906-91 I).-The power possessed by organic acids of dissolving antimonious oxide depends entirely on the relative strength of the acids. The recent publications of Moritz and Schneider (this vol. i 703) are criticised. K J. P. 0 Electrolytic Study of Pyruvic Acid. By GEORGE W. ROCKWELL (.I Amer. Chem. SOC. 1902 24 719-734).-When pyruvic acid dissolved in alcohol is oxidised electrolytically in presence of sodium hydroxide or carbonate or of sulphuric or hydrochloric acid used as electrolytes there are formed in quantities varying with the concentration temperature current strength and voltage employed acetaldehyde ethyl acetate carbon monoxide and dioxide but no acetyl peroxide.When the acid is electrolytically reduced using the same electrolytes the amount of lactic acid produced is similarly dependent on the same factors. T. A. H. Condensation of Carbon Tetrachloride with Ethyl Malonate and Ethyl Cyanoacetate. By OTTO DIMROTH (Ber. 1902 35 2881-2884).-1n the hope of synthesising allene derivatives (*C:C:C*) carbon tetrachloride and ethyl disodiocyanoacetate were caused to interact ; the sodium salt of ethyl dicyanoglutaconate (Errera Abstr. 1898 i 297; and Ruhemann and Browning Trans.1897 73 280) was obtained and identified by conversion into the ester (m. p. 181-183O); on boiling with alcohol the latter yielded the ammonium salt of ethyl 2 6-dihydroxypyridine-3 5-dicarboxylate (m. p. 199'). Qn reinvestigation of the zlleqe derivative ethyl allene-ORGANIC CHEMISTRY. 741 tetracarboxylate which was prepared by Zelinsky and Doroschewsky (Abstr. 1895 i 129) by the action of ethyl disodiomalonate on carbon tetrachloride it was found t h a t this substance was ethyl ethoxycoumalindicarboxylate (m. p. 94') originally prepared by Guthzeit and Dressel (Abstr. 1889 860) by the action of heat on ethyl dicarboxyglutaconate Further the first product of the action of carbon tetrachloride and ethyl disodiomalonate is not ethyl ethoxy- propylenetetracarboxylate as Zelinsky and Doroschewsky believed but ethyl dicarboxyglutaconate (Conrad and Guthzeit Abstr.1884 297). Carbon tetrachloride and the disodio-derivatives of ethyl cyano- acetate and ethyl malonate yield the same products as chloroform and the monosodio-derivatives of these esters. K. J. P. 0. Isomeric Lactonic Acids Derived from pyy-Dimethyl-P-hydr- oxypentanedioic Acid. By LUIGI BALBIANO (G'axxettcc 1902 32 i 485-494).-The acid described by the author (Abstr. 1899 i 867) as yy8-trimethylpentane-pc-olidoic acid is now found to be a mixture of two isomerides one yy8-trimethylpentane-pe-olidoic acid and the other pyytrimethylpentane-/3€-olidoic acid identical with the acid obtained by Blanc (Abstr. 1901 i 119).It follows from this that the acid C,H120 obtained as the chief oxidat ion product of camphoric acid does not possess the constitution C0,H.CO*CMe2-CHMe*C02H assigned t o i t by Tiemann and Mahla (Abstr. 1895 i 678) since such an acid should give on reduction exclusively yy8-trimet hylpentane-Be- olidoic acid; as however this acid C,H,,O when reduced gives a mixture of the two isomerides mentioned above it must have the formula Pry- Trimethylpent ane-,&-o lidoic mid O<g$z$g;>CMe2 melts at 165-166' and crystallises in the monoclinic system [Zambonini cc b c = 0'54867 1 1*0S63. B= 52'5'30"]. yy8- Tqim et h y Zpen t ane-PE-olid oic acid O<cHc Co-CH"e>CMe CO,H also forms monoclinic crystals melting a t 163-164' '[Z/mbonini CL 6 c= 0.47994 1 1.3802.The calcium salt crystallises with 4H,O ; the lead salt ( + 3H20) separates from water in mammillary t u l t s of small needles melting at 110-112° whilst in the anhydrous form it softens at 176' and me1t.s at 184-185'. The mixture of the two acids does not melt at 110-120' as Blanc (Zoc. c d . ) stated but a t 158-160O. /3 = 83'38'1. T. H. P. Camphoric Acid. XII. Synthesis of Trimethylparaconic Acid. By WILLIAM A. NOYES and AUSTIN M. PATTERSON (Amer. Chem. J. 1902,28,228-232 ; Ber. 1902,35 2940-2942).-Trirnethyl- paraconic acid (?'e2* ">O obtained by heating a mixture of sodium trimethylsuccinate trioxymethylene and acetic anhydride in a sealed tube at 120-140' for two days crystallises from hot benzene or dilute alcohol and melts and decomposes at 256-251'; its ethyl CO,H*CMe*CH,742 ABSTRACTS OF CHEMICAL PAPERS.ester melts a t 34.5O. When the acid is warmed with sodium hydroxide it is converted into sodium trirnet?qZitamaZate C0,Na*CMe,*CMe(CH2* OH)*CO,Na ; the corresponding silver salt was prepared and analysed. Diethyl trimethylitamalate was obtained as a viscous oil ; when treated with phosphorus tribromide it is converted into e thy1 trimethylparaconate By €5. H. J. TER BRAAKE (Rec. trav. chirn. 1902 21 155-185).-The author has investigated the optical rotation of ethyl monosodium and monopotassium tartrates and of disodium and dipotassium tartrates in alcoholic solution special precautions having been taken to avoid the absorption of water from the air. The substances are all lsvorotatory a fact which is contrary to Guye's hypothesis.The rotation of the last two compounds could not be determined exactly. The rotatory power of the monosubstituted esters increases as the concentration is increased and as the temperature is lowered. The rotatory power of the above compounds also under- goes change with time owing to the formation of ethyl mono- and di-sodium and potassium mesotartrates and of ethyl mono- and di- sodium and potassium racemates ; in the case of ethyl monosodium E. G. Anaxopolarimetry. tartrate t h i major portion is transformed into the mesotartrate. A. F. Action of Water on the Ethyl Monosodium and Mono- potassium Tartrates. By 16. H. J. TER BRAAKE (Rec. trav. chinz. 1902 21 186-190. Compare Mulder Abstr. 1890 595).-By the action of water on the ethyl monosodium and monopotassium tartrates a gelatinous precipitate separates consisting of a mixture of ethyl sodium or potassium tartrate and of disodium or dipotassium tartrate.A. F. Action of Halogen-substituted Esters of Fatty Acids on the Sodio-compounds of Saturated and Unsaturated Derivatives of Ethyl Malonate. By MAX GUTHZEIT and MAX ENGELMANN ( J . pr. Chem. 1902 [ii] 66,104-129. Compare thisvol. i 658).-Ethyl Aa-but~Zerze-ayys-tetracarboxyZcl.te CO,Et*CH CH*C( CO,Et),*CH,*CO,Et prepared by the action of ethyl bromoacetate and sodium ethoxide on ethyl isoaconitate is an oil which boils a t 216-218Ounder 14 mm. pressure and when hydrolysed by 50 per cent. hydrochloric acid yields Aa-bzctylene-ays-tricccrboxylic acid which melts a t 148O is easily soluble in water or acetone but sparingly so in ether benzene or chloro- form and gives precipitates in neutral solution with silver lead and copper salts.Ethyl butc~ne-a~ps-telracarboxylate obtained by the action of ethyl bromoacetate and sodium ethoxide on ethyl carboxyglutarate (b. p. 161O under 12 mm. pressure ; compare Abstr. 1899 i 261) is a colourless liquid which boils a t 200-205' under 15 mm. pressure and when hydrolysed by 10 per cent. hydrochloric acid yields ap6-butane- tricarboxylic acid which melts a t 1113-120" (compare Abstr. 1892 42) is easily soluble in acetone but sparingly so in ether or chloro- form and when neutralised with ammonia gives precipitates with copper iron silver and lead salts.ORGANIC CHEMISTRP. 743 The action of ethyl chloromalonate on ethyl sodiodicarboxy- glutaconate leads to the formation of a n oil probably ethyl A'-butyle?ze- auyy88-hexacarboxyhte which commences to decompose at 230' under 15 mm. pressure and on hydrolysis with dilute hydrochloric acid yields Aa- butylene-ay8-tricarboxylic -acid.Ethyl bromoacetate reacts more easily than ethyl chloroacetate with ethyl sodiodicarboxyglutaconate giving a better yield of ethyl butyl- enepentacarboxylate (this vol. i 659) which is hydrolysed by dilute hydrochloric acid t o butylenetricarboxylic acid. Ethyl butanepenta- carboxylate formed by reduction of the unsaturated ester with zinc dust in glacial acetic acid solution boils at 218-220' under 12 mm. pressure. The action of ethyl bromoacetate on ethyl sodiobutanepentacarboxyl- ate in absolute alcohol leads to the formation of ethyl yentane-aP/366c- hexacarboxy~ccte which crystallises from light petroleum in nacreous leaflets melts a t 62' boils a t 230-240' under 12 mm.pressure is easily soluble in ether chloroform or benzene b u t more sparingly so in alcohol or light petroleum and on hydrolysis with 15 per cent. hydrochloric acid yields pentune-a~6~-tetracccrboxyZ~c acid (methylene- disuccinic acid) CH,[CH(C02H)*CH,.C02H]2 which forms crystalline nodules melts and effervesces at 214-216' is sparingly soluble in cold water or acetone and almost insoluble in ether benzene or chloroform. The zinc and barium salts are precipitated only in boiling solutions and redissolve on cooling. Ethyl pentane-app88ehexacarboxylate can also be obtained in a 30 per cent.yield by the action of ethyl bromoacetate on ethyl disodio- dicarboxyglutarate. There is formed i n the same reaction an oil which boils at 195-200' under 12 mm. pressure and must be ethyl propane-aPPy-t e tracar boxy la te CO,E t *CH,*C( CO E t) 2* CH,* C 0,E t (Bischoff Abstr. 1883 46) or ethyl propane-aapy-tetracarboxylate CO,Et~CH,*CH(CO,Et)*CH(CO,Et) (Emery Abstr. 1891 424) as 011 hydrolysis it yields tricarballylic acid. The action of methyl chloromalonate on methyl disodiodicarboxy- glutarate leads to the formation of methyl trimethylenetetracarboxyl- ate (m. p. 73") and methyl ethanetetracarboxylate (m. p. 137-138'). Methyl heptane-ayycc~-hexacurboxykute CH2[C(C0,Me),*CH,*CH,*C0,Me]2 formed by the action of methyl P-iodopropionate on methyl disoclio- dicarboxyglutarate melts at 87' and boils at 170-190' under 14 mm.pressure. Ethyl dicarboxyglutarate is more easily obtained in a pure state by the action of rnethylene iodide on ethyl sodiomalonste than by the action of formaldehyde on ethyl malonate in the presence of diethyl- amine. Ethyl pentane-aaycc-hexacarboxylate (compare Bottomley and Perkin Trans. 1900 77 294) which is formed in the later reaction yields with ammonia a hexa-ccmide C(CO*NH2),[CH,*CH(CO*NH2),]? which sinters above 210' melts at 230-235' and on hydrolysis with hydrochloric acid forms pentane-aye-tricarboxylic acid. G. Y. Cystein. I. By CARL NEUBERG (Ber. 1902 35 3161-3164. Compare Baumann Abstr. 1882 l),-isoEthionic acid is produced when744 ABSTRACTS OF CHEMICAL PAPERS.cystein is oxidised with nitric acid of sp. gr. 1.2. This would indicate that the sulphydryl and amino-groups are attached to different carbon atoms in the cystein molecule which therefore should have the con- stitution CO,H*CH(SH)*CH,*NH or CO,H*CH( NH,)*CH,.SH. J. J. S. A New Method of preparing Trithioformaldehyde. By Lun- WIG VANINO (Bey. 1902 35 3251-3252).-When a n acid is added to a solution of sodium thiosulphate containing formaldehyde no precipi- tation of sulphur takes place in the cold. On warming the mixture some sulphur is separated and ultimately trithioformaldehyde is precipitated. J. McC. Preparation of Diacetyl and a Polymerisation Product of Diacetyl. By OTTO DIELS and HANS JOST (Ber. 1902 35 3290-3299).-Diacetyl can be conveniently prepared from methyl ethyl ketone by treatment with amyl nitrite and boiling the isonitroso- ketone formed with an acid.Diacetyl when shaken with concentrated hydrochloric acid is converted into termoleculav diucetyl C,,H,,O which melts at 105' boils at 280' and is sparingly soluble in water but easily so in organic solvents. This polymeric diacetyl does not reduce Fehling's solution permnnganate or silver solution. It is quite stable i n presence of alkalis but mineral acids decompose it into diacetyl acetic acid and other substances not yet identified. With acetic anhydride it gives a nzonoacetyl derivative which melts a t 93'. It forms a PJtenyZurethane which crystallises from benzene with one mol. of benzene of crystallisation melts at 86" or after freeing from benzene at 132' (corr.).With phenylhydrazine in presence of acetic acid it gives the ordinary osazone of diacetyl. It forms a p-nitro- phenylhydraxonc which melts at 200" (corr.) a n oxime which melts at 174-175" (corr.) and a semicurbaxone melting at 238' (corr.). The acetyl derivative gives a semicarbaxone which melts at 206' (corr.). When reduced with sodium amalgam the polymeric diacetyl yields p-xylGquinol and a substance which is probably dimethyl- cyclohexanone. The latter gives a ssmicarbaxone melting a t 198" (corr.). From the behaviour of the polymeric diacetyl it is evident that i t contains a hydroxyl radicle and a ketonic group as well as four in- different oxygen atoms ; the formula provisionally suggested for it is OH*CMe*CH,-C-CMe /\ /\ 0 0 0 0 .\/ \/ J. McC. I COMe MeC-CMe Action of Soluble Ferments and Top Yeast on Gentiobiose. By EMILE BOURQUELOT and HENRI HERISSEY (Compt. rend. 1902 135 399-401. Compare this vol. i 713).-The soluble ferments of Aspergillus completely hydrolyse gentiobiose into 2 mols. of dextrose. Emulsin which hydrolyses gentiobiose has only a slight action on gentianose causing its solution to become more dextrorotatory. TopORGANIC CHEMISTRY 745 yeast on the other hand partially hydrolyses gentianose but does not attack gentiobiose. Sucrose raffinose gentianose and manneotetrose are all partial1 y hydrolysed by invertin with the liberation of 1 mol. of laevulose; gentiobiose on the contrary is not affected by this reagent. I n order to hydrolyse gentianose completely by these ferments it is therefore necessary to treat it successiveIy with invertin and emulsin. 0.T. M Formaldehyde (Methylene) Derivatives of Sugars and Glucosides. By CORNELIS A. LOBRY DR BRUYN and WILLIAM ALBERDA VAN EKENSTEIN (Proc. K. Akad. Wetensch. Amsterdam 1902 5 175-177. Compare Abstr. 1900 i 619).-A number of mono- and di-formal derivatives can be obtained when sugars (and glucos- ides) are fused with trioxymethylene. Diformalxylose melts n t 56-57' has [ a] (2 per cent. solution in methyl alcohol) + 25.7' and sublimes readily. Diformalarabinose is an oily colourless liquid boiling a t 1 5 5 O under 32 mm. pressure; [a] (2 per cent. solu- tion in methyl alcohol) - 16'. Methylenegalactoside (mono-formal derivative) is an indistinctly crystalline substance melting at 203' ; [a] (2 per cent.aqueous solution) + 124.89 Formalmethylene- fructoside melts a t 92' and has [aID (2 per cent. aqueous solution) - 34.9'. From d-sorbose a derivative has been obtained melting a t 54' with [.ID (2 per cent. aqueous solution) - 25' ; from rhamnose a product melting a t 76' and with [a] (0.4 per cent. aqueous soiution) - 18' ; mannose also yields a crystalline derivative. Crystalline formal derivatives were obtained from methylmannoside (111. p. 12'7'; [a] +10.5) from P-methyl-d-glucoside (m. p. 136' inactive) and from a- and P-methyl-d-galactosides. The derivatives obtained from a-methyl-d-glucoside and amyl- and ethyl-d-glucosides are viscous liquids. J. C. P. Preparation of Osones from Osszones derived from Sugars. By EMIL EISCHER and E.FRANKLAND ARMSTRONG (Ber. 1902 35 3141-3144).-Herzfeld (Ber. 1895 28 442) has shown that beaz- aldehyde may replace hydrochloric acid in the decomposition of phenyl- hydrazones. A similar method cannot be adopted in the case of tlie phenylosazones of the monosaccharides since in most cases they are not sufficiently soluble in water. The phenylosazones of disaccharides however are completely decomposed when their aqueous solutions ai e boiled for a short time with benzaldehyde and good yields of the osones are obtained. The method is also applicable to the osazones of arabinose and xylose which are soluble in hot water. Maltosone has been obtained in the form of a syrup which sets to a vitreous amorphous mass. It reduces Fehling's solution and reacts with phenyl hydrazine yielding maltosazone ; with p-bromophenylhydrazine it yields p-brornophenylrnaltosazone which crystallises in yellow needles melting and decomposing a t 198' and only sparingly soluble in the ordinary solvents with the exception of hot alcohol. Yeast enzymes hydrolyse maltosone to glucosone.Melibiosone in aqueous solution has a low dextrorotation and is746 ABSThACTS OF CHEMICAL PAPERS. hydrolysed by emulsin. p-Bromophenylmlibiosaxone crystallises in yellow needles melting a t 1S2'. J. 3. S. By EMIL FISCHER and E. FRANKLAND ARMSTRONG (Ber. 1902 35 3144-3153. Compare E. Fischer Abstr. 1891 41 3).-Three new disaccharides have been obtained by the action of tetra-acetylchlorodextrose on the sodium derivative of galactose and by the action of tetra-acetflchlorogalactose on the sodium derivatives of dextrose and galactose.It is probable t h a t these compounds are similarly constituted t o the glucosides and they are respectively named glzccosidogulactose galactosidodextrose and galaclosidogalactose. They yield phenylosazones which are relatively readily soluble in water Top yeasts do not ferment the three disaccharides and they may be freed from monosaccharides by the action of these yeasts. Bottom yeasts decompose glucosidogalactose and galactosidoglucose but not galactosidogalacl ose. All three disaccharides are hydrolysed by emulsin after contact for several days at 35' but not by kephir lactase. Galactosidoglucose is probably identical with melibiose; its phenylosazone melts at 173-174' and the p-bromophenylosazone a t 181' both a few degrees lower than the corresponding compounds from melibiose.Phenylglucosidogulclctosazone melts a t 175-1 77" (corr.); it is some- what less soluble in benzene or toluene than galactosidoglucosazone. ~heny~gakc~ctos~doga~c~ctosaxone melts a t 176-1 78' (corr.) is only sparingly soluble in chloroform benzene or toluene and insoluble in ether or light petroleum. All three osazones yield osoces when their aqueous solutions are boiled with benzaldehyde. Kephir lactase partially converts solutions of pure galactose into a new disaccharide isolactose the osazone of which crystallises in yellow needles melting at 193-196' (corr.). The sugar is not fermented by Synthesis of New Disaccharides. top but is by bottom yeasts and is' also hydrdysed by kephir lactase.J. J. S. Isomeric Acetohalogen Derivatives of Sugars and Synthesis of Glucosidss. 111. By EMIL PISCHER and E. FRANKLAND ARM- STRONG (Bey. 1902 36 3153-3155. Compare Abstr. 1901 i 257 671 and this vol. i 263).-~-Hepta-acetylbromomaltose C26H35027Br obtained by the action of drp liquid hydrogen bromide on octa-acetyl- maltose in sealed tubes a t the ordinary temperature crystallises from light petroleum in colourless prisms melting at S4' (corr.) It reacts with sodium phenoxide yielding heptcc-ncetylpiien?llmoltoside C,,H,,O, which melts at 157-158" (corr.) and is only sparingly soluble in hot water or dilute acids On hydrolysis with barium hydroxide it yields P-phenylmcdtoside C,,H,,O,,*OPh in the form of small colourless prisms melting at 96' and with [aID + 34.0' a t 20'.Tetra-acetyZethyE- gcdactoside may be readily obtained by the action of ethyl alcohol on P-tetra-acetylchlorogalactose in the presence of silver carbonate ; it melts at 88" (corr.) and Kas [a] -29.8' at 20'; on hydrolysis with barium hydroxide it yields /3'-etiqZgalactoside melting at 153-155' and with [..ID -4.0' a t 20'. P-Methyl- P-ethyl- and P-phenyl-galactosides are hydrolysed by emulsin and also by kephir extract J. J. 8.ORGANIC CHEMISTRY. 747 Optical Rotatory Power of Sucrose when dissolved in Amines. By GUY MAURICE WILCOX (J. Physical Chem. 1902 6 339-342).-1t was found that rotation of sugar in solutions in allpl- amine amylamine and isopropylamine is considerably greater than in water. In amylamine and allylamine solution the rotation was found t o decrease with increasing concentration; in the case of isopropyl- amine solution only one observation was made so that the effect of concentration mas not determined.L. M. J. Isomerism of the /?-Naphthylhydrazones of the Sugars. By WILLIAM ALBERDA VAN EKENSTEIN and CORNELIS A. LOBRY DE BRUYN (Bey. 1908 35 3082-3085 Compare Abstr. 1896 i 588; 1897 i 41).-The results recently obtained by Hilger and Rothenfusser (this vol. ii 479) on the /?-naphthylhydrazones of some sugars do not agree with the former observations of the authors (Zoc. cit.). Thirs difference is due to the formation of stereoisomeric compoungs. The gaZactose-~-rzuphthyZhyd~*axone obtained by the authors melts at 167' and has [a] + 24' whilst that obtained by Hilger and Rothenfusser has [ Q ] + 10'.Dextrose-P-naphthylhydrazone has been obtained as a very soluble substance melting a t 95'with [a]auer + 40'; as a substance melting at 1 2 5 O and with lower rotatory power and in a third form melting a t 158-159' and having From lavulose two isomeric /3-naphthylhydrazones can be obtained according to the conditions. + 22'. J. McC. Synthesis of Carbohydrates and the Explanation of Natural Processes based thereon. By JULIUS WALTHER (Chem. Zeit 1902 26 763-771. Compare this vol. ii 203).-The author has confirmed his former observations (Zoc. cit,) and discusses their bearing on the physiological processes of plants and animals K. J. P. 0. Reaction between Benzene and Cellulose. 11. By A. M. NASTUKOFF (J. Buss Phys. Chem.SOC. 1902 34 505-508 Com- pare this vol. i 362).-The compound obtained by the action of benzene on a sulphuric acid solution of cellulose which the author previously thought to be tetraphenylcellulose (Zoc. cit.) is now found t o contain sulphur. The composition of the product when dried at the ordinary temperature in the desiccator is Cl,,HI,,02,S whilst when dried at 105-110' i t has the formula C,,,Hl,,02,S,,; these formule correspond with 6 mols. of tetraphenylcellulose + ZSO less 9 and 12H20 respectively. The main product obtaired on dry distillation of this compound is toluene whilst when oxidised with potassium permanganate it yields benzoic acid ; hence the phenyl groups present must be directly connected with carbon atoms. T. H. P Crystalline Forms of Platinichlorides of the Aliphatic Amines By A.RIES (Zeit. Kryst. Min. 1902 36 321-385).- Detailed crystallographic descriptions are given of the platinichlorides of the primary secondary and tertiary fatty amines and quaternary ammonium compounds and of 8 few of the corresponding compounds'94.8 ABSTRACTS OF CHEMICAL PAPERS. containing bromine iridium or tin. The results are compared and discussed,-especially with respect to their morphotropic relations. L. J. 8. Action of Formaldehyde on Creatine and Creatinine. By MAX J A F F ~ (Bey. 1902 35,2896-2901).-0n treating a cold aqueous solution of creatine with dilute formaldehyde no reaction takes place but on heating a substance C6H1,03N,,2H,0 separates in very long colourless needles which lose water a t 100-105" decompose a t 250° and are fairly soluble in water and other solvents ; it does not react with the usual formaldehyde reagents.On benzoylating by the Schotten-Baumann method a dibenzoyl derivative C,H,O,N,Bz is obtained as colourless needles melting a t 265-2669 Creatinine yields the same substance on treatment w i t h formaldehyde. ably has the formula O H * C H 2 * N C < ~ ~ ~ ~ ~ 1 > C 0 . It prob- I K. J. P. 0. Reactions between Acid and Basic Amides in Liquid Am- monia,. By EDWARD C. FRANKLIN and ORIN F. STAFFORD (Amer. Cizem. J. 1902 28 83-107).-Franklin and Kraus (Abstr. 1900 ii 382) have shown that a close analogy exists between liquid ammonia and water as electrolytic solvents and that acid and basic amides bear a relation t o liquid ammonia similar in many respects to that of ordinary acids and bases to water.From these considerations it seemed probable that reaction would take place between an acid and a basic amide in liquid ammonia with the facility which marks the inter- action of ordinary acids and bases in water. This has been found to be the case by means of a large number of experiments carried out in a specially devised apparatus. Potassamide i s very soluble in liquid ammonia and separates from concentrated solutions as a C O ~ O U I ~ B S ~ well crystallised hygro- scopic mass. When potassamide (I mol.) and acetamide (1 mol.) are allowed to react in presence of liquid ammonia hydrogen is evolved and crystals of potussiumacetumide CH,*CO*NHK,nNH separate from the solution ; this substance is also formed by the action of potassium on a solution of acetamide in liquid ammonia.When left in the air the crystals lose their ammonia of crystallisation and become opaque. By the action of potassium amide (2 mols.) on acet- amide (1 mol.) a dipotussiumacetamide CH,*CO*NK? is produced. The mono- and di-potassium derivatives of benzamlde benzenesulph- onamide m-methoxybenzenesulphonamide p-methoxybenzenesulphon- amide sulph'amide and carbitmide and the mono-potassium derivatives of phenlyacetamide and p-toluenesulphonamide were also prepared. Benzoicsulphinide yields a potassium compound probably NHK* CO*C,H,*SO,*NHK. The reactions between potassamide and formamide dichloroacet amide thioacetamide cyanoacetamide p-chlorobenzamide succinimide thiocarbamide allylthiocarbamide picramide and m-nitro-p-toluidine were also studied but although in each case action evidently occurred the products could not be isolated.ORGANIC CHEMISTRY. 74'3 When sodamide (1 mol.) is brought in contact with acetamide (1 mol.) in solution in liquid ammonia sodiumacetamide CH,CO*NHNa,nNH3 is produced ; this compound is also formed by the action of sodium on a solution of acetamide.Magnesium was found t o react with acetamide benzenesulphon- amide benzoicsulphinide benzamide phenylacetamide cyanoacetamide and cyanamide whilst formamide toluenesulphonamide succinamide and sulphamide were without appreciable action. M~gnesium-cLcetcLmide -benxenesu~~~onumide and -cyanamide were prepared and analysed. Magnesium sodium and potassium readily react with solutions of ammonium salts; when magnesium is treated with solution of am- monium nitrate or bromide magnesium nitrate or bromide separates from the solution.E. G. Action of Mercuric Bromide on the Alkali Thiocyanates. By HERMANN GROSS~IIAN (Bey. 1902 35 2945-2946).-Meihcuric bromide dissolves in solutions of the alkali thiocyanates forming two series of salts. One series contains one mol. of each constituent the cmmoniu~n salt HgBr2,NH,SCN which crystallises in stable needles being described. The other series contains two mols. of the thiocyanate to one mol. of mercuric bromide. HgBr2,2NH,SCN,H,O of this series is deliquescent but the potassium salt HgBr2,2KSCN is crystalline and stable in air. Action of Ethyl Iodide on Potassium Stannite. By PAUL PFEIFFER (Ber.1902 35 3303-3307).-When a strong alkaline solution of stannous hydroxide is boiled with ethyl iodide and alcohol the resulting solution deposits t i n diethyl oxide. The formation of this compound is probably due t o the action of the alkali on the potassium ethylstannite at first formed according t o the equation 2SnEtO.OK = SnEt,O + Sn0,K2. Genesis of Naphthenes and Naphthenecarboxglk Acids By OSSIAN ASCHAN (An~aclen 1902 324 1-39).-The author's experimental results support; the theory which assumes t h a t the naph- thenes and their carboxylic acids are secondary products of the distil- lation of mineral oil in the earth's interior being formed by the polymerisation of compounds of the olefine series which result from the initial decomposition of fossil fat.Although ethylene when dissolved in carbon disulphide and treated with anhydrous aluminium chloride does not at the ordinary tempera- ture undergo any polymerisation yet under these conditions the crude amylene derived from amyl alcohol gives rise to saturated hydro- carbons. The products of lowest boiling point contained in the fractions 32-35" and 35-40' consist chiefly of a saturated hydro- carbon C5HI0 closely resembling methylcyclobutane. The next fraction 56-62' contains a hexane C6HI4 which corre- sponds in boiling point with &-dimethylbutane or /3-methylpentane. The addition of a methyl group t o the amylene carbon chain by the action of aluminium chloride has hitherto not been observed. The ammonium salt R. H. P. R. H. P. VOL. LXXXII.i. 3 9750 ABSTRACTS OF CHEMICAL PAPERS. The fraction 76-81' contains a saturated hydrocarbon C6H12 The fraction 150-200' appears to consist of a mixture of paraffins When pure amylene (b. p. 37-39'} is employed in these experi- ments the fraction 55-40' probably contains a branched chain hexane whilst the fraction 260-265' consists chiefly of naphthenes mixed with small quantities of the paraffins C,,H,,. The tarry residues of these fractionations when distilled under diminished pressure yield a hydrocarbon C38H66 boiling a t 190-220' under 30 mm. pressure. I n one series of experiments cyclohexane when heated with fuming hydriodic acid a t 300° became converted into methylcyclopentane. A negative result was obt'ained in a second series of experiments. cycZoHexane also undergoes transformation when left in contact with anhydrous aluminium chloride.It was not found possible to oxidise methylcyclopentane to a cyclic monocarboxylic acid ; dibasic acids only were obtained namely suc- cinic adipic and a trace of glutaric acid. I n one case act-dimethyl- propionic and isovaleric acids were identified these products being prob- ably due to the oxidation of the paraffins present in the methylcyclo- pentane. When treated with dilute nitric acid the cyclic hydrocarbon becomes oxidised to a mixture of acetic and succinic acids. corresponding in composition with cylcohexane. (AOH22' CllH24' and Cl2H26* G. T. M. Methylcyclohexenes and Methylcyclohexenones. By OTTO WALLACH (Ber. 1902,35,2S22-S825) -Cyclic alcohols when dehydr- ated with phosphoric oxide or zinc chloride often form unsaturated ring hydrocarbons which are isomerides of those which would be expected from the constitution of the alcohol.These iromerides form less soluble nitrosyl chlorides and nitrosates than the untransformed hydrocarbans. The tetrahydi*otolueize obtained when I-methylcyclohexan-3-01 is dehydrated by zinc chloride differs from that previously described (Abstr. 1896 i 310). 1.44234 a t 20' and U + 17'45' in a 1 dcm. tube. The nitrosate re- acts with piperidine forming the nitrolepiperidide which is a beauti- fully crystalline compound melting a t 152-153". When the nitrosate is warmed with alcoholic potash a liquid rnethylcyclohexenoneoxirne C,H,,:NOH is obtained which when hydrolysed with sulphuric acid yields a niethylcyclolzexenone C,H,,O.This ketone boils at 1 79-1S1° is soluble in water has a sp. gr. 0.97 and n 1.4843 a t 2l0 forms a semicnrbazone which melts a t 207-208' and therefore differs from the methylcyclohexenone described by Knoevenagel (Abstr. 1897 i 606). The exact constitution of these compounds has not been de- termined. R. H. P. It boils a t 106-107° has a sp. gr. 0.799 Action of Sulphur Chloride on Benzene. By EDUARD LTPPMANN and JSIDOR POLLAH (Moncctsh. 1902 23 669).-If com- mercial benzene is warmed on a water-bath with 15 per cent. of sulphurORGANIC CHEMISTRY. 751 chloride until the evolution of hydrogen chloride ceases (1 92 hours) and is then washed with dilute sodium hydroxide solution and dried over calcium chloride it distils a t 81' and is free from thiophen.G. Y. Organic Additive Compounds. By PAUL LEMOULT (Compt. trend. 1902 135 346-348).-l-Chloro-2 4-dinitrobenzene combines with tertiary bases of the diphenylmethane series t o form coloured additive products. The compounds C6H3C1( N0,)2,CH,(CGH4*NMe,)2 and C,H3CI( NO,),,CH,( C,H,* NEt,) crystallise in reddish-brown needles and melt at 72' and 42.5' re- spectively. I-Chloro-2 4 6-trinitrobenzene and 4 4'-tetramethyldi- aminodiphenylmethane give rise t o the compound which separates in black flakes and melts at 71'. The 2 4-dinitrophen- oxide OH°CGH,(NC~2)z CH,(C,H,*NATe,) separates in large black crys- tals melting a t 72' ; the @crates OH*C,H,(N0,),CH,(C6H4*N~~e,)~ and OH*C,H,( N02),,CH2( C6H4* NEt,) crystallise in yellow leaflets and melt respectively a t 185' and 190".Picramide gives rise to the com- pound NH2*C,H2(N0,),,CH2(C,H,*NMe2)2 crystallising in lustrous black leaflets and melting at 106'. These substances are all readily dissociated into their generators even in their solutions in the organic solvents. C,H2CI(NO2)3 CHz( C,H4*NAfe,) G. T. M. Nitroethylbenzene and its Tetrazo-dye. By GUSTAV SCHULTZ and J. FLACHSLANDER (J. p r . Chem. 1902 [ii] 66 153-172. Com- pare Abstr. 1884 902 and Beilstein and Kuhlberg Annnlen 1870 156 206).-o-Nitroethylbenzene melts at - 23Oand boils a t 223-224'. p-Nitroethylbenzene melts a t -32' boils at 241-242' and forms a sodium suZphonccte NO,*C,H,Et*S0,Na,2H2O which crystallises in long needles and is easily soluble in water. Diaminodiethyldiphenyl prepared from o-nitroethylbenzene (Schultz Zoc.cit.) f o r m a dihgdrochloride C,,H2,N2,2HC1 which crystallises in mother-of-pearl leaflets and is easily soluble in water o r hot alcohol and a dibenxylidene derivative cl,H16N,(CfHPh) which crystallises from alcohol in yellow needles melts at 124-125' is easily soluble in hot alcohol more sparingly so in cold alcohol or ether and is hydro- lysed by dilute mineral acids. The cli@crute formed in alcoholic solu- tion in presence of excess of picric acid crystallises in glistening golden leaflets decomposes without melting a t 225O and on recrystal- lisation from alcohol is hydrolysed to the monopicrate which separ- ates in glistening yellow needles decomposes at 225-230' and is only sparingly soluble in water or alcohol.Benzidine forms a dipicrate which decomposes at 190" is sparingly soluble in ether but easily so in water or alcohol; it is stable in absolute alcohol but is completely hydrolysed t o benzidine and picric acid on recrystallisation from aqueous alcohol and more slowly on con- tact with aqueous alcohol in the cold. Tolicline dipicrate decomposes at 215' is stable in absolute alcohol and on recrystallisation from aqueous alcohol is hydrolysed but more slowly than the benzidine salt. When left with aqueous alcohol in the cold tolidine dipicrate 3 9 2752 AESTRACTS OF CHEMICAL PAPERS. is only partly hydrolysed probably to the monopicrate. The mother liquor from the preparation of 4 4’-diamino-3 3‘-diethyldiphenyl con- tains o-aminoethylbenzene and a base which is obtained as a thick syrup soluble in alcohol or ether and may be 4-amino-3 2’-diethyl- diphenylamine or less probably 2 4’-dinmino-3 3’-diethyldiphenyl.It forms a hydrocldovide C1,H2,N2,ZHCl which crystallises in leaflets from alcohol in which it is sparingly soluble a benzylidens derivative C,,H,,N,:CHPh which crystallises in glistening leaflets melts a t 110-112” and is soluble in alcohol or benzene and a picrate CI6H2,N2,C1,H,O7N which crystallises from alcohol in golden- yellow leaflets decomposes at 235-240° and is only sparingly soluble in water or alcohol. With ferric chloride i n dilute hydrochloric acid solution the base gives a blue-green coloration which disappears on addition of concentrated hydrochloric acid. When diazotised with 2 mols.of sodium nitrite and coupled with a-naphthylamine-4-sulphonic acid benzidine o-tolidine and diamiao- diethyldiphenyl yield similar dyes (sodium salts). The reaction takes place most easily with benzidine least easily with diaminodiethyldi- phenyl. The new dye forms green glistening crystals and is less soluble in water and more stable towards light and acetic acid than the dye derived from o-tolidine which is also less soluble and more st;tble than the benzidine dye. Of the dyes (sodium salts) obtained by coupling with P-naphthyl- amine-6-sulphonic acid that derived from benzidine is insoluble in water those from o-tolidine and diaminodiethyldiphenyl are soluble. Dyes have also been obtained by coupling diazotised diaminodiethyldi- phenyl with salicylic acid and with 8-amino-a-naphthol-3 6-sulphonic acid.G. Y. Study of Bisnitrosylbenzyl and the Bye-products obtained in its Formation. By WILHELM BEHRENS and ROBERT BEHREND (Anncdeiz 1902 323 265-278. Compare Bamberger and Renauld Abstr. 1898 i 20 ; Bamberger and Szolayski Abstr. 1901 i 84).- The compound obtained as a bye-product in the preparation of bis- nitrosylbenzyl by oxidising P-benzylhydroxylamine with chromic acid is benzaldoxime anhydride (C,H,*CH*N),O corresponding in its pro- perties with the substance produced by the aerial oxidation of the same hydroxylamine derivative. I n the former reaction the anhydride is accompanied by an oily mixture of benzaldehyde benzyl benzoate and benzonitrile (1). Bisnitrosylbenzyl when dissolved in chloroform and treated with hydrogen chloride undergoes a complicated change giving rise to benzoylhydrazine benzoylbenzylidenehydrazine hydrazine benzyl chloride benzaldehyde tarry products and probably a trace of benzo- nitrile. Bisnitrosylbenzyl is scarcely attacked by bromine in hot chloroform solution and is not affected by permanganate solution ; with nitric acid i t yields a mixture of nitrobenzoic acids.G. T. M Electrolytic Oxidation of Naphthalene. By A. PANCHAUD DE BOTTENS (Zeit. EZektroclzent. 1908 8 673-675).-When a coldORGANIC CHEMfSTRY. 753 solution of naphthalene in a mixture of acetone and sulphuric acid is electrolysed some a-naphthaquinone is formed a t the anode and a considerable quantity of a brown non-crystalline substance. Naph- thalene-a-sulphonic acid or its sodium salt and 1-amino-/3-naphthol- 4-sulphonic acid dissolved in water or a mixture of acetone and sulph- uric acid gave small quantities of phthalic acid.T. E. Halogen-substituted Dini tronaphthalenes. By FRITZ ULLMANN and FORTUNATO CONSONNO (Bey. 1902,35 2802-281 1).-5-Bromo-a- naphthylamine obtained by reducing Guareschi's 5-bromo-a-nitro- naphthalene with stannous chloride melts at 69" and yields an acetyl derivative crystallising in pale pink twinned needles and melting at 2 1 5 O . 5-Bromo-1 8-dinitronaphthalene is produced by nitrating 5-bromo-a- nitronaphthalene or a-bromonaphthalene ; when heated with alcoholic ammonia it yields 4 5-dinitro-a-naphthylamine which separates from glacial acetic acid in reddish-brown crystals melting at 243". 4 5-Di- nitro-a-naphthytmethylamine is produced in a similar manner by the use of methylamine ; it forms brick-red crystals and decomposes at 259". 4 5-Dinitro-a-naphtlyldimethpZa~ine prepared by the interaction of 5-bromo-1 8-dinitronaphthalene and dimethylamine crystallises in dark red needles and melts a t 176".4 5-Dinitro-a-naphthol resulting from the action of sodium carbonate solution under pressure on the bromonitro-compound decomposes at 208". Friedlander gives the decomposition temperature as 230" (compare Abstr. 1900 i 150). 4 5-Dinitronaphthyl methyl ether produced by heating 5-bromo-l 8-di- nitronaphthalene with an alcoholic solution of sodium methoxide separates from ether in yellow feathery crystals melting a t 216'. 4 5-Dinitronaphthpl ethyl ether crystallises in nacreous leaflets and melts a t 182O (compare Heermann Abstr.1891 1379.) 8-Chloro-a-nitronaphthalene the product of the action of chlorine on a-nitronaphthalene in the presence of ferric chloride on reduction yields 8-chloro-a-naphthylamine which melts at 89" and gives an acetyl derivative crystallising in colourless needles and melting a t 137". 4-Chloro-1 5-dinitronaphthalene melting a t 1 38" results from the nitration of the preceding nitro-compound ; it yields 4 8-dinitro- a-naphthylamine when heated with alcoholic ammonia this product crystallising in brick-red needles and decomposing at 197". 4 8-Dinitro-a-naphthol produced from the corresponding bromo- dinitro-compound by the action of sodium carbonate solution at 135O melts at 2 3 5 O not at 135' as formerly stated.G. T. M. Constitution of Primary Dinitrohydrocarbons. By ROLAND SCHOLL (J. pr. Chem. 1902 [ii] 66 206-207. Compare Ponzio this vol. i 334).-The author draws attention to his observations on the reduction of diphenyldinitromethsne (Abstr. 1891 315). Ponzio's suggestion that in the fatty dinitro-compounds only one nitrogen atom is attached to carbon bas been made before but can no longer be maintained (compare Abstr. 1896 i 198 ; 1901 i 495). G. Y.754 ABSTRACTS OF CHEMICAL PAPERS. Tervalent Carbon. IV. By MOSES GOMBERG (J. Amev. Chem. Soc. 1902 24 597-628. Compare Abstr. 1901 i 78).-When a solution of iodine is added to triphenylmethyl or one of its additive products dissolved in an appropriate solvent 80 per cent of the theoretical yield of triphenyliodomethane is formed (Zoc.cit.). When the solvent is petroleum the substance separates in yellow prisms which melt a t 131-132’ and are soluble in benzene carbon disulphide and hot ethyl acetate but insoluble in ether. It reacts like the corresponding bromo- and chloro-derivatives w hen treated with water alcohol and metals and like them forms coloured additive compounds with the chlorides of tin zinc and antimony. With ammonia and amines triphenyliodomethane also reacts in the usual manner furnishing with ammonia triphenylaminomethane ; with ethylamine triphenylmethyl- aminomethane ; and with aniline toluidine &c. similar derivatives. When the amount of iodine calculated for the formula CPh,I,I is added to a solution of triphenyliodomethane prepared as already described there separates a penta-iodide of the above formula as dark blue lustrous needles which melt a t 90’.With sodium thiosulphate only the “external” iodine is attacked with the formation of triphenyliodomethane and ultimately triphenylcarbinol. Alcohol converts the penta-iodide into triphenylmethane but if the hydrogen iodide first formed be removed by addition of zinc dust triphenylcarbinyl ethyl ether is obtained. Zinc dust when added to neutral solutions of the periodide furnishes triphenylmethyl.. Triphenylbromomethane penta-iodide CPh,Br,I (compare Abstr. 1899 i 155) prepared by addition of the calculated quantity of iodine to solutions of triphenylbromomethane separates as an oil which becomes crystalline in it few seconds.It is slightly soluble in benzene or carbon disulphide but readily so in ether. Its reactions are similar to those of the preceding compound. The author points out that the results recorded in this and previous papers are all i n favour of the view that the hydrocarbon which he has named triphenylmethyl has the constitution CPh in which carbon is tervalent. T. A. H. Dibenzylanthracene. By EDUARD LrPPMANN and ISIDOR POLLAH (Monatsh. 1902 23 672-679)-5 10-Dibenzylanthracene prepared by heating anthracene with benzyl chloride and zinc dust in carbon disulphide solution crystallises from benzene in glistening whitish- yellow needles melts a t 239-240°,.has a sp. gr. 0.1787 a t 1 6 O and is only sparingly soluble in benzene ether carbon disulphide or glacial acetic acid and insoluble in alcohol or light petroleum On oxidation with chromic acid in glacial acetic acid solution i t gives an almost quantitative yield of anthraquinone melting at 2 7 3 O .On bromination i n carbon disulphide solution dibenzylanthracene yields a bromo- derivative CH,Ph*C1,H,*CHBrPh which crystallises in glistening yellow leaflets commences to lose hydrogen bromide a t 160’ and melts at 187”. It is easily soluble in benzene or carbon disulphide but only sparingly so in alcohol or ether. When boiled with water containing potassium carbonate or with glacial acetic acid i t is converted into hvdroxydibenzylanthrncene CH,Ph*C14H,*CHPh*OH which formsORGANIC CHEMISTBY 755 yellow crystals melts at 225-226' and is easily soluble in ether benzene or carbon disulphide but only sparingly so in alcohol.The ethgZ ether crystallises in soft leahts melts at 218q and forms 8 fluorescent solution in benzene. By FRITZ ULLMANN and W. BORSUM (Ber. l902,35,2877-2881).-0n attempting to prepare triphenylmethane by the reduction of triphenylmethyl chloride with zinc in acetic acid solution hexaphenylethane CPh,*CPhs was formed when the reduction was carried out with zinc and stannous chloride in acetic acid solution in the presence of hydrochloric acid the yield amounted to 60-70 per cent The hydrocarbon can be also obtained by reducing triphenylcarbinol in a similar manner. It forms small colourless crystals soluble in benzene or toluene which melt at 231' (corr.) and boil a t a higher temperature than sulphur. It is oxidised by chromic acid only with great difficulty yielding triphenylcarbinol ; b y nitric acid i t is converted into a hexanitro-derivative which melts at 265'.When the reduction of triphenylmethyl chloride is carried out in the complete absence of water only the triphenylmethyl peroxide (m. p. 185') prepared by Gomberg (Abstr. 1901 i 77) is obtained. a. Yh Hexaphenylethane. K. J. P. 0. Action of Ethylene Dibromid? on p-Nitrosodimethyladline. By HENRY A. TORREY (Amer. Chem. J. 1902,28 107-121).-When p-nitrosodimethylaniline is h'eated with an excess of ethylene dibromide di-p-nitrosodimethylaniline-ethy lene and pnitrosodimet hylaniline hydro- bromide are produced. Di- pnit rosodimet hy Zani line-e th gene NO* C,H,*NMe,:CH*CH:NMe2* C,H,*NO crystallises from amyl alcohol in deep red needles decomposes at 230-240° and is soluble in chloroform or glacial acetic acid ; the picrate melts and decomposes at about 1 5 5 O .If p-nitrosodimethylaniline is heated with an alcoholic solution of ethylene dibromide the red ethylene derivative first formed suffers decomposition with production- of tetra- methyldiaminoazobenzene ; the same compound is obtained when the red ethylene derivative itself is heated with p-nitrosodimethylaniline and alcohol. When the ethylene derivative is treated with dilute nitric acid decomposition occurs with formation of formic acid 23-nitrosodimethylaniline nitrate which melts and decomposes a t 162' and a su6atunce which crystallises in yellow plates melts a t 255-256' and does not contain oxygen.p-Nitrosodimethylaniline hydrobi*omide forms yellow crystals and decomposes at 207'. The platinichloride obtained by the action of platinic chloride on an alcoholic solution of the hydrochloride differs from the two platinum salts described by Schraube (Bet-. 1875,8 616). The picrate decomposes at about 140'. Influence of the Solvent on the Orientation of the Isomerides obtained on Nitration in the Aromatic Series. By CARL SCHWALBE (Ber. 1902,35 3301-3303).-A preliminary note on the influence of the solvent during the nitration of ring compounds. Benzylideneaniline when nitrated in concentrated sulphuric acid solu- tion with nitric acid st 5' yields p-nitroaniline only but in glacial E. Q.756 ABSTRACTS OF CHEMICAL PAPERS. acetic acid solution with nitric acid and acetic anhydride gives rise to a mixture of p- and o-nitroaniline (see Pictet and Genequand this vol.i 584). R. H. P. isovaleryl-p-toluidide and m-Bromoisovaleryl-p-toluidide. By FRANCESCO MAFFEZZOLI (Chem. Centr 1902 ii 504-505 ; from Boll. Chim. Farm. 41 458-459).-isoVale~yl-p-toZuidide C,H,Me*NH* CO*CH,-CHMe prepared by the action of phosphorus trichloride on a mixture of p-toluidine and isovaleric acid crgstallises from a large volume of boiling water in colourless monoclinic plates has R slight odour of valeric acid melts at 98" and is very readily soluble in alcohol ether chloroform or benzene but only slightly so in cold water. The m-brom+derivative forms small colourless needle-shaped crystals is odourless melts a t 95O and is very readily soluble in alcohol ether or benzene but only slightly so in water; on hydrolysis it forms m- bromo-p- toluid ine me1 t ing a t 2 6'.Production of Acylamines. By FREDERICK L. DUNLAP (J. Amer. Chem. Soc. 1902 24 758-763).-When 2 gram-mols. of sodium acetate are intimately mixed with 1 gram-mol. of aniline hydrochloride and bhe mixture is heated in sealed tubes at 165' for three hours 71-72 per cent. of the theoretical yield of acetanilide is obtained. Variations in proportion of reacting ingredients or of temperature or time of heating diminishes the yield as does also the substitution of calcium acetate for the sodium salt. By the same reaction with appropriate reagents acetyltoluidide acetamide benzog lanilide benz- amide and methylbenzamide have been prepared but formanilide could not be obtained by the action of sodium formate on aniline hydrochloride a t 185'.Action of Phenylcarbimide on the Esters of some Oxy- acids. By EUG~NE LAMBLTNG (Bull. Soc. Chim. 1902 [iii] 27 871-875. Compare this vol. i 537 603).-On heating together a t 175-1 78' ethyl diethylglycollate and phenylcarbimide the phenyl- urethane of ethyl diethylglycollate NHPh*CO*O*CEt;CO,Et is obtained which crystallises from aqueous alcohol in slender needles melting at 68'; it is soluble in ether chloroform or benzene. On saponification with sodium hydroxide it yields diethgloxulanilide which crystallises in lozenge-shaped plates melting a t 91'. Similarly by heating ethyl benzilate with phenylcarbimide there is obtained the phen$urethune of ethyl benxilate NHPh*CO* O*CPh,*CO,Et ; it crystallises in slender white needles melts at 151' and is soluble in alcohol,.ether chloro- form or benzene. On boiling with excess of a solution of sodium hydroxide it yields benxilanilide which crystallises in microscopic prisms melting at 174-175O; i t is insoluble in water but soluble in alcohol ether chloroform or benzene. The phenyluretham of methyl salicylate obtained by heating methyl salicylate with phenyl- carbimide crystallises in white microscopic needles melting at 96'. On saponification with sodium hydroxide there is obtained salicyl- anilide which crystallises in slender needles melting a t 135'. E. W. W. T. A. H. 11. A. F.ORGANIC CHEMISTRY. 757 Some Derivatives of P-Naphthylamine. By ALBERT REYCHLER (Bull. Soc. Chirn.1902 [iii] 27 sg2-888).-EthyLP-nap~~t~~yZc~mi~e cccmphorsdphonate formed by the direct union of the acid and base dissolved in ethyl acetate forms white compact crystals melting at 11 7" ; it dissolves in water but undergoes hydrolytic dissociation. Diethyl-P-naphthylamine hydriodide crystallised from a mixture of ethyl acetate and alcohol forms hard colourless prisms melting at 152-153'. Diethyl-P-naphthylamine obtained by the action of alkali on the hydriodide is a n almost colourless liquid boiling a t 318-319" ; a dilute ether or benzene solution exhibits a slight violet fluorescence. The hydyochloride forms deliquescent crystals melting at 177-1 78'. The cumnphorsulphonate could be obtained only as a gelatinous residue which refused to crystallise. ~rriethyl-P-nap~~thylummonizcm iodide obtained by heating diet hylnaph- thylamine with a slight excess of ethyl iodide crystallises in colour- less lustrous striated rectangular plates melting at 174" Trimethyl- P-naphthylammonizcm iodide prepared by the repeated action of methyl iodide on P-naphthylamine crystallises in colourless plates melting a t 190" with intumescence.Dimet~~yl-~-Izaphthylamine was obtained by distilling the quaternary base obtained from the iodide by the action of silver hydroxide ; i t forms a crystalline mass which melts at 46' and boils at 304.5-305". Dimethyl-P-nc~~thylamine hydrochloride forms a felted mass of white slender needles or colourless non-deliquescent prisms melting at 159'. The camphorsuZphonccte forms colourless laminae melting at 115".A. F. Preparation of Aminohydroxyphenanthrenes. By JULIUS SCHMIDT and in part with A. KAMPF (Ber. 1902 35 3129-3133. Compare Pschorr this vol. i 672).-9-Amino-10-hydroxyphenanthrene may readily be obtained by the reduction of phenanthraquinonemon- oxime with hydrogen sulphide and isolated as its hydrochloride. When the hydrochloride is .boiled with acetic anhydride it yields anhydroacetgl-9-amino-1 O-hydvoxyphenanthrene C,,H, NAc in the form of yellowish glistening needles melting at 1 46-1H0 and dissolving 111 dilute mineral acids t o deep blue solutions. The mother liquor from this anhydro-base yields Pschorr's 9-acetylamino-lO-acetoxyphenanthrene. Di-9 -?~?ldrox~phenant~~~wy l- 1 O-amine (0 H -C +H8) 2N H is obtained when water is added t o an alcoholic solution of the base produced by the reduction of phenanthraquinonemonoxime with hydrogen sulphide ; it crystallises in glistening brown prisms melting and decomposing at 3-Nitro-l0-( or 0-) -ninino-9- (or 1 O-)-Iiydvox~pl~e?accIttI~ren~ obtained by the reduction of 3-nitrophenanthraquinonemonoxin~e with alcoholic hydrogen sulphide yields a I&rochloride crystallising in yellow needles.On treatment with aqueous solutions i t is converted into 3-nitro-9 10-dihydroxyphenanthrene. A small amount of 3 10-(or 9-)-diamino-9 (or IO-)-FYyd?.ozyp7Lentacrt- tlwene may be obtained when t h e nitroquinonemonoxime is very care- fully reduced with stannous chloride. It forms reddish-yellow needles melting at 264-265'. 168-1 70". J. J. S.758 ABSTRACTS OF CHEMICAL PAPEBB.Nitration of ZAminofluorene. By OTTO DIELS EMIL SCHILL and STANLEY TOLSON (Bey. 1902 35 3284-3290).-2-Acetylamino- fluorene (Strassburger Abstr. 1884 754) when nitrated in acetic acid solution gives a mixture of two mononitro-compounds which i t has not been possible to separate. On saponification a mixture of two nitroaminofluorenes is obtained which can be separated on account of their different basicities. The less basic one l-nitro-2-aminoJuorene NH2*C1,H,*N02 melts a t 206' (corr,) and is comparatively insoluble in alcohol ether or benzene but soluble in acetic acid It forms a hydrochloride which however suffers hydrolysis in water. When reduced with zinc and hydrochloric acid i t gives 1 2-diarninoJuorene which is a monoacidic base forming the hydrochloride Ci3H1,N,,HC1.The free base can be obtained from the hydrochloride by means of methylamine j i t forms white crystals which melt a t 193' (corr,) and a n alcoholic solution becomes green when treated with ferric chloride. With diacetyl the diamino-compound forms a quinoline derivative of t'he formula CI7Hl4N which crystaliisos in long colourless needles. The more basic nitro-compound 7-nit~o-2-uminoJuorene crystallises in orange-red prisms melts a t 232' (corr.) and is easily soluble in alcohol or acetic acid When reduced with zinc and hydrochloric acid i t gives 2 7-diaminofluorene (Schultz Abstr. 1880 814). J. McC. Molecular Rearrangement of Thiocyanoacetanilides into Labile $-Thiohydantoins and the Molecular Rearrangement of the Latter into Stable Isomerides.By HENRY L. WHEELER and TREAT B. JOHNSON (Amer. Chem. J. 1902,28 121-15S).-By the action of potassium thiocyanate on chloroacetanilides Grothe (Abstr. 1901 i SO) obtained a series of compounds which he believed were thiocyanoacetanilides NH R* CO*CH2* SCN. Prerichs and Beckurts (Abstr. 1901 i SO) repeated his experiments and came to the con- clusion that all his compounds with the exception of the supposed thiocyanoaceto-p-toluidide were normal thiocyanates ; they found however that by the action of potassium thiocyanate on an alcoholic solution of chloroacetop-toluidide for only a short time a labile com- pound which they regarded as thiocarbiminoaceto-p-toluidide C,H,Me*NH*CO*CH,*NGS was produced ; they further observed that when the solution was warmed this labile compound was rapidly con- verted into a substance supposed t,o be thiocyanoaceto-p-toluidide and that the latter was quickly changed into p-tolylthiohydantoin.The present authors have prepared the thiocyanoacetanilides according to Grothe's directions and have found that although the aniline o-toluidine and p-xylidine compounds are correctly described the so-called t hiocyanoace to-p- to1 ui dide and t hioc yanoacety 1-p- phene t- idide are neither thiocgano- nor thiocarbimino-derivatives ; the p-tolu- CK,-S co<iY(C,H4Me)*&NH ' idine compound is a labile $-tlpiohydantoin whilst the p-phenetidine compound is the stable p-phenetyl-$-thio- hydantoin 'O< .(!J~N.(T~,.OEL,' The molecular rearrangement CH2* SORGANIC CHEMISTRY. 759 of thiocyanoacetanilides into the stable hydantoins does not involve the formation of a thiocarbimino-derivative a t any stage.Thiocyanoacetanilide crystallises in colourless acicular prisms and melts a t about 91" ; if recrystallised from alcohol it melts at S6-SS0 and when crystallised from benzene it contains benzene of crystallisa- tion which is rapidly lost on heating or on exposure to -the air. By the action of the calculated quantity of thioacetic acid on it acetylthio- glycollarzilide SAc*CH,*CO.NHPh is produced which crystallise8 from alcohol in colourless needles and melts at 97-98'; the same compound may be obtained by the action of sodium thioacetate on chloroacetanilide. I n two experiments in which thiocyanoacet- anilide mas heated with an excess of thioacetic acid a substance (prob- ably an acetyldithiourethane) was obtained which crystallises in slender needles and melts and decomposes at 192'; in other experi- ments a dithiouretlmn.e NH,*CS*S*CH,*CO*NHPh was produced which crystallises in square plates melts a t 162O and is converted by the action of alkali hydroxide into alkali thiocyanate and a salt of thio- glycollanilide. When thiocyanoacetanilide is treated with sodium hydroxide phenylthiohydantoic acid is formed melting a t 185-1 90'.If thiocyanoacetanilide is heated for a few minutes at its melting point i t is converted into the labile yhen?ll-~-tlLiol~ydanto~n (i-keto-2- which crystallises imino-3-phenyltetrahydrothiazole) CO< from benzene in orthorhombic prisms [a 6 c = 0.97 1 1 *35] and melts a t 148' to a blood-red liquid ; its hydrochloride melts at 192-193O and the picrccte a t lS0'.If the labile thiohydantoin is CH,-y NPh*C:NH' warmed with thioketic acid hydrogen sulphide is evolied and an is produced which melts at acetyl derivative CH,-Y Co<NPh*C:NA.c' 191-192'; the same compound may be obtained by the action of acetic anhydride on phenylthiohydantoic acid or on thiocyanoacet- anilide. The labile thiohydantoin is dissolved by sodium hydroxide with formation of phenylthiohydantoic acid. When the labile thio- hydantoin is heated to 165' it is converted into the stable phenpl-4- - . CH,*F thiohydantoin CO<NH-C:NPh which forms triclinic crystals [a:b:c=1.508:1 0,859; a=10s025' p=113'15' y=96'35']; the hydroclLlos.ide melts at 203' and the diacetyl derivative a t 161-162'.By the action of benzyl chloride on the sodium salt of the stable thio- hydantoin phenylbenzylthiohydantoin is produced melting a t 124-1 25'. Thiocyanoaceto-o-toluidide melts a t 102-103' as stated by Grothe but if warmed with ether for two hours or repeatedly crystallised from benzene it melts a t about 109'. By the action of thioacetic acid it is converted into an acetgldithiourethane NHAc*CS*S*CH,*CO*NH*C,H,Me which melts and decomposes a t about 200'. Thiobenzoic acid reacts with thiocyanoaceto-o-toluidide to form benxoyltl~ioglycoll-o-tolzcidide which crystallises in long needles and melts at 141-142'. When thiocyanoaceto-o-toluidide is treated with alkali hydroxide o-tolyl- cyanamide is produced. By heating thiocyanoaceto-o-toluidide for760 ABSTRACTS OF CHEMICAL PAPERS.half-an-hour at 'I lo' o-tolylthiohydantoic acid is obtained together with the labile o-tolyl-$-thiohydantoin ; the latter compound melts at 131-132' and is thereby converted into the stable o-tolyl-$-thio- hydantoin described by Dixon (Trans. 1897 71 623). When the stable hydantoin is heated with acetic anhydride a diacetyl derivative is formed melting at 91-92'. o-Y'olylthiohydantoic ucid crystallises in thin plates and melts and decomposes between 208' and 230'. o-Tolylthiocarbamide melts a t 162' and not a t 155" as stated by Staats (Abstr. 1880 386). Thiocyanoaceto-p-toluidide C,H,Me NH-CO * CH * SCN forms acicular prisms and melts at 85'. By the action of thioacetic acid i t is converted into a dithiourethccne C,H,Me*NH*CO*CH,-S*CS.NH,. When heated above i t s melting point labile p-tolyZ-$-thio~~ydarLtoin i s produced which melts at 125-126" ; its a c c t ~ l derivative crystallises in colourless plates and melts a t 175-176".If the labile thiohydan- toin is treated:with alkali hydroxide p-tolylthiohydantoic acid is formed which melts and decomposes a t 210-2 12'. The stable p-tolyl-+-thio- hydantoin obtained by heating the labile form for a short time at a temperature near its melting point crystallises in needles and melts a t 183'; its sodium salt forms thin plates and its dincetgl derivative crystallises in pale yellow prisms and melts a t 163-164". Labile a-o-xylyl-$-thiohydantoin melts at 11 1' ; by the action of thio- acetic acid i t is converted into the stable hydantoin melting a t 179'.a-o-XylyZthiol&dantoic acid formed in the preparation of the labile hydantoin melts and decomposes a t about 208". Thiocyanoacety 1-p-xylid ide C,H3Me2*NH.CO*CH,*SCN [Me NH Me = 1 2 43 is converted by thioacetic acid into ncet~lt~~Liogl~coZl-p-xyZidicZe S Ac *CH,*CO*NH. C,H,Me which crystallises in colourless prisms and melts at 139-140'. By the action of sodium hydroxide on thiocyanoacetyl-p-xylidide p-xylyl- cyanamide is produced which melts at 118'. When thiocyanoacetyl-p- xylidide is boiled with ether for one to two hours the labile p-xylyl-+- thiohydantoin is obtained which crystallises in needles melts a t 109-1 lo" and is converted by alkali hydroxide into p-xylylcyan- amide. p-Xyl~lthiol~yclantoic acid C,H,Me,*N( NH,) C S CH,* CO,H decomposes at about 200° and when dissolved in alkali hydroxide yields p-xylylcyanamide. The s table p - x y lyl-+-thiohy dsntoin crystallises in minute prisms and melts a t 161-162'.Labile p-plhenetyl- +-thiohydantoin melts at 128" and is converted by thioacetic acid into the ctcetpl derivative which crystallises in needles or prisms and melt2s at 155'. When the labile hydantoin is heated at 140-145" for half-an-hour the stableform is produced which melts at 163-1 64". p-Phenet?/lthio~~ydantoic acid melts and decomposes a t 21 3'. E. G. Thiocyanates and isoThiocyanates (Thiocarbimides). IV. By HENRY L. WHEELER and TEEAT E. JOHNSON (J. Amel.. Chem. Xoc. 1902 24 680-690. Compare Abstr. 1902 i 28 537).-/3-k~omo- isobutane reacts with potassium thiocyanate t o form P-thiocyanoiso- butane a coloiirless pungent oil which with thioacetic acid is con-ORGANIC CHEMISTRY.761 ver ted into isobutyl acetylditlbiocudamute NHAc*CS,*CMe forming yellow crystals melting at 112-113O and a second substance crys- tallising in colourless plates from benzene. a-Bromoisopropylbenxene prepared by brominating the hydrocarbon at 115-120" reacts with potassium thiocyanate to form +-cyanogen sulphide and a n oil of unknown composition. Dip?benylbyomoethane CPh,BrMe prepared by brominating the hydrocarbon at 100-105° decomposes when heated in a vacuum into hydrogen bromide and diphenylethylene. The latter together with +-cyanogen sulphide is also produced by the action of potassium thiocyanate. Methyl a-bromohgdratropate CMePhBr*CO2Me prepared by bromin- ating the ester at 150' is a n oil which decomposes when heated in a vacuum.It reacts with potassium thiocyanate forming a n oil of un- known composition and $-cyanogen sulphide. The latter also results from the interaction of potassium thiocganate and ti.icccrbethox?lmethyZ bromide a colourless oil which boils at 162-165" under 16 mm. pres- sure and is obtained by bromiiiating tricarbethoxymethane at 100'. Ethyl bromomethylmalonate when kvarmed with alcoholic potassium thiocyanate yields ethyl t?~ioc~unollzetl~~l~~aaZonate NCS*CISlle(CO,Et) a pungent oil which boils at 139-142' under 9 mm. pressure. With t hioacet ic acid in benzene solution it furnishes 4- ke t o- 2- t hio-5-met hyl- >NH s- cs CHMe- CO thiazolidine I Ethy2 phenylb~omomalonate CPhBr(CO,Et) obtained by brominating the ester at 140-150' is a colourless oil which boils a t 192' under 20 mm. and at 177-178' under 11 mm.pressure. With potsss- ium thiocyanate i t yields et?ql p?~en~lt?~ioc~ccno~~aulonu~e a colour- less oil which reacts with thioacetic acid t o form 4-keto-Z-thio-5-phenyl- thiccxolidine. This crystallises in yellow prisms and melts at 178-1 79". Ethyl thiocyanoisobutyrate reacts with thiobenzoic acid to form the ethyl isobutyrccte derivative of benxo~lEit?~iocu~~bc~n~rcte N H Bz*CS,* C Mez C O,E t which crystallises from a mixture of petroleum and benzene in yellow prisms melts a t 113-114" and dissolves readily in alcohol. Ethyl diphenylchloroacetate when treated with potassium thiocyan- ate yields ethyl clil3~en?llt~biocyanoucetc6t~.The latter does not react with thioacetio or thiobenzoic acids but with aniline is converted into tripi~enyZ-$-thioh?/dantoin Y*C(NPh)>NH which crystallises from alco- cPb,-cO hol in colourless prisms and Gelts at 250'. This with hydrochloric acid is converted into 2 4 - t l i k s t o - 5 - d i ~ ~ ? ~ e n y l t e t r a ~ ~ y ~ ~ ~ o s-co >NH which crystallises in colourless prisms from alcohol bPh,* CO and melts at 144-145'. Ethyl phenylchloroacetate when treated with phenylthiocarbamide yields diphenyl-$-thiohydantoin identical with that previously obtained by the interaction of aniline and ethyl phenylthiocyanoacetate (loc. cit.). When treated with hydrochloric acid the diphenyl-+-thiohydantoin furnishes 2 4-cliketo 5 3-diphenyltetrahydrothioazole as white needles which melt a t 173-174'. Benzylphenyl $-thiohydantoin (compare762 Al3STRACTS OF CHEMICAL PAPEKS. Dixon Trans.1897 71 620) results when phenyl-$-thiohydantoin is treated with benzyl chloride in presence of sodium ethoxide or when benzylphenylthiocarbamide is warmed with ethyl chloroacetate and therefore has the formula C€€2<~~~~"Ph.CH,Ph which confirms that proposed by Dixon (loc. cit.) for the parent phenyl-$-thiohydantoin. T. A. H. Thiocyanates and isoThiocyanates (Thiocarbimides). V. By HENRY L. WHEELER and GEORGE S. JAMIESON (J. Amer. Chem. Xoc. 1902 24 743-754. Compare Abstr. 1901 i 514 and 1902 i 2S).-Phenyl- p-tolylmethyl bromide CMePhEr*C,H,Me obtained by the action of dry hydrogen bromide on phenyl-p-tolylcarbinol a t loo' is a thin red oil which reacts in benzene solution with potassium thiocyanate to form phen yl-p-tolylrnethylthiocarbirnide C,H,Me*C HPh NCS a mobile red- dish-coloured oil giving off irritating vapours.This reacts with thio- acetic acid to form phen yl- p-t o Z ylmeth y Zacet arnide NHAc*'CHPh*C,H,Me which crystallises from ether in flat rectangular prisms and melts at 129.5-131'. The thiocarbimide reacts with alcoholic ammonia aniline and P-naphthylamine to form respectively phenyl-p-tolyheth?/lthiocarb- arnide C,H,Me*CHPh*NH*CM*NH separating in rosettes of colourless needles which melt a t 162-1 6 3" phengll-p-tolylmethylphenplthiocarb- arnide C,H,Me*CHPh*NH=CS*NHPh crystallising from alcohol in flat prisms which melt a t 159' and p?LenyZ-p-toZ~lmethyZ-/3-napl~thyZthiocarb- arnide C,H,Me*CHPh*NH*CS*NH*CloH7 crystallising from alcohol in slender needles and melts at 170'.p-Benxgltolyl bromide prepared by brominating the hydrocarbon at 130-135' is a heavy yellowish oil which boils a t 179-180° under 11 mm. pressure. Potassium thiocyanate converts it into the corre- sponding tltiocyunate. This however with ammonia and /3-naphthyl- amine,. gives small quantities of the thiocarbamides described in the preceding paragraph. PhenyZ-a-nccp?~t~~ylr,zet~~yZ bromide reacts with potassium thiocyanate to form the corresponding thioccwbimide C,,,H?*CHPh*NCS which crystallises in small plates melting a t 76-77'. With thioacetic and thiobenzoic acids respectively this furnishes p?~enyZ-a-nnp~~tiLyZrnethyE acetamide NHAc*CHPh*C,,H7 which crystallises in small needles and melts a t 2 1 0') and phen~Z-a-na~~l~t~yZi~zetTzylbenxamide NHBz*CHPh*CIOH7 which melts at 158'.The thiocarbimide reacts in the usual manner with ammonia and amines and the following thiocarbamides were thus prepared. C ,H *CB Ph NH* CS*NH2 forming rectangular prisms which melt at 197-1 98'; phenyl-a-nuphthyl- methylmeth ylthiocurbnmide C,,H7*CHPh NH CS N HRle cry s t allising in pxisms which melt at 175 -1 76' ; p~~en~Z-a-naphthylinet~~Zdiet~ylthio- ccwbumide CloH7*CHPh*NH*CS*NEt forming flat prisms which melt at 1 1 2 - 1 1 3' ; pheng I-a-nccph th ylnae thy ldii obuty 1 thiocaq*bnmide C,,H7*CHPh*NH* CS*N( G4H& which melts at 14 3-1 43'; phenyl-a-napAtlzy/lnzet1zy Zz~l~enylthiocurbamide Pheny2-a-naphtl~yliiaethy Zthiocarbamide,ORGANIC CHEMISTRY.763 Cl,H7*CHPh*NH*CS*NHPh forming colourless prisms which melt at 185' ; phenyl-a-naphtlq ZmethyZphenyZmeth ylthiocarbamide C,,H,*CHPh*NH*CS*NHPhMe which melts a t 182-1 83' ; p?~enyl-a-naphthyZn~thyl-m-c7~Zorophenylthio- carbumide C,,H7*CHPh*NH*CS*NH*G,H,C1 crystallising in acicular prisms which melt at 172-1 73' ; phenyl-a-nuphthylmethyl-m-nityo- phenyltliiocurbamide C,,H,*CHPh*NH*CS *NH * C,H,*NO forming light yellow prisms which melt at 191' ; and pherql-a-naphthyl?nethyF /3-naphth ylthiocarbamide C,,H7 CHPh*NH*CS *NH*Cl,H7 crys tallising in needles which melt a t 195'. The thiocarbimide also reacts with phenglhydrazine to form phenyl- a-mphthylmethyZphen yZtlLiosemicaYbaxide which melts first at 154" then solidifies when further heated and remelts at 174-175'.After re- crystallisation from alcohol it melts a t 178-1 79'. The transforma- tion occurring is represented thus Cl,H7*CHPh*NH*CS*NPh*NH2~ C,,H,*CHPh-NH*US*NH*NHPh (compare Busch and Holzmann Abstr. 1901 i 234). Di-a-naphthylmethane CH,(C,oH7)a prepared by condensing naph- thalene with chloromethyl acetate in presence of zinc chloride when brominated at 135-145" furnishes di-a-naphthylmethyl bromide which crystallises from benzene in acicular prisms melts at 181-182' is readily soluble in chloroform but less so in light petroleum. This reacts with potassium thiocyanate t o form di-a-nap~~thylmet~~yzt~~io- carbimide CH(C,,H,),*NCS which crystallises from alcohol in rect- angular prisms and melts at 124-125'.With aniline methylaniline and naphthylamine it; reacts t o form respectively di-a-naphthyl- methyZp?Aenylthiocarbamide CH(C,,H7),*NH-CS*NHPh which crystal- lises in needles and m'elts a t 225-226' ; di-a-ncLphthylmet?~ylp~enyl- methylthiocarbamide CH(Cl,H7),-NHoCS*NPhMe forming needles which melt at 2 10-21 1' ; and di-a-naphthylnaethyl-p-naphthplthiocarb- anzide CH(C,,Hp),*N H*CSoNH(Cl,H,) which crystallises in spherical masses of needles and melts at 218-219'. Thiocyanoethylbenzene CHMePh-SCN reacts with thioacetic acid t o form the ethylbenxene derivative of dithiocarbamic acid CH(C1,HT)@ NHAc*CS,;CHPhMe. With thiobenzoic acid isopropyl thiocyanate forms benxoyldithio- isopropylcccrbamcte NHEz*CS,Pr. This crystallises in brilliant yel- low plates and melts a t 74-75" Bromodinaphthaxanthone does not react with potassium thiocyanate whence the author prefers for this substance the formula proposed by Werner (Abstr.1902 i 50) rather than that suggested by Posse (Abstr. 1901 i 604). which crystallises in slender yellow prisms and melts at 99-100'. T. A. H. Thiocyanoacatic Acids and Thio-fatty Anilides. By HEINRICH BECKURTS and GUSTAV FRERICHS (J. pv. Chern. 1902 [ii] 66 173-193. Compare Abstr. 1900 i 478 ; 1901 i 80).-When boiled with water carbaminethioglycollanilide yields thioglpcollanilide and cyanic acid the formation of carbon dioxide and ammonia being due to hydrolysis of the cyanic acid (compare Itizzo Abstr. 1898 i 659).76 4 ABSTRACTS OF CHEMICBL PAPERS. The formation of cyanic acid is determined by conversion into carbamide.The formation of diphenylcarbamide when carbaminethioglycollanilide is treated with aniline and the formation of methylthioglycollanilide when the carbamine is heated with methyl iodide and sodium methoxide (Rizzo) are explained by the decomposition of the carbamine into thio- glycollanilide and cyanic acid when warmed with alkalis or organic bases. The decomposition also takes place when the carbarnine is heated above its melting point. Thioglycollanilide melts at 11 1-1 12' (Rizzo m. p. 105-1070) and is best obtained by warming the carbamine with alcoholic ammonia (com- pare Liebermann Anncclen 1881,207 129). A small part of the pro- duct is oxidised to dithiodiglycollanilide which is insoluble in alcohol. Grothe's compounds (Abstr.1901 i SO) are formed when chloro- acetanilides are heated with potassium thiocyanats in alcoholic solution for 15 minutes When chloroacetanilide is heated with potassium thiocyanate in alcoholic solution for several hours phenylthiohydan- toin (m. p. 178") is formed (compare Rizzo Eoc. cit.). When warmed with fuming hydrochloric acid the thiocyanoacet- anilides are converted into carbaminethioglycollanilides. Thiocarb- iminoacetylmethylanilide melts a t 79" (Grothe m. p. 69") and is con- verted by fuming hydrochloric acid into cc~i~baiizinet~~iogZ~colZmet~~~l- anilide CN*S*CH ,*CO*"teYh which crystallises in glistening leaflets and melts at 247". The following derivatives of the thio-fatty anilides are described Dithiodiglycollanilide melts at 160-161" (Rizzo m.p. 165') and is best prepared by oxidation of thioglycollanilide with ferric chloride in alcoholic solution. Thioglycollanilide yields a copper derivative Cu,(S*CH,*CO*NHPh) as a n amorphous yellow powder. EthyltlAiogZy- collccnilide SEt*CH,*CO*NHPh prepared by the action of ethyl iodide and potassium hydroxide in alcoholic solution forms colourless leaflets melts at 61° and is easily soluble in alcohol but insoluble in water. Bimethylmeth ylenedithiogl ycollanilide CMe,( S*CH,*CO*N HPh) formed by the action of hydrogen chloride on thioglycollanilide dissolved i n acetone crystallises from alcohol in colourless needles melts at 1 70' is soluble in hot more sparingly so in' cold alcohol and insoluble in water. Thiodiglycollanilide formed by the action of potassium hydroxide on thioglycollanilide and chloroacetanilide in aicoholic solution crystal- lises from alcohol in delicate needles and melts a t 166-167" (Rizzo Zoc.cit. m. p. 160-161'; Anschutz and Biernaux Abstr. 1893 i 191 m. p. 1 68'). Carboxyeth~llt~iogtycollccnilide CO,Et'S.CH;CO*NHPh formed by the action of potassium hydroxide and ethyl chlorocarbonate on thiogl ycollanilide crystallises from alcohol in flat colourless needles and melts at 99". a-Cn.l.hns,iinetl~ioluctccs~~Zi~e NH2*CO*S*UHXe*CO*NHPh formed by the action of potassium thiocyanate on a-bromopropionic acid and aniline in alcoholic bolution crystallises in glistening leaflets melts at 11 7" and is easily soluble in alcohol insoluble in water a-2'hioZuct- anilide SH*C)HMe*CO*NHPh formed by the action of ammonia on the carbamine crystallises in colourless leaflets and melts a t 9 1".a-Dithiodi- ZccctasLiZide,S2(CHnle.C0.NHPh),,olotained by oxidation of thiolactanilide with ferric chloride in alcoholic solution crystallises in colourless needlesORGANIC CHEMISTRY. 765 and melts at 1 60°. forms a greenish-yellow powder. a-EthyZt~ioZactaniZi~~ SEt*CHMe*CO.NHPh crystallises in colourless leaflets and melts at 97'. a-Carbanainethio- butyranilide NH,*C:O*S.CHEt*CO*NHPb crystallises in colourless leaflets melts at 120° is easily soluble in alcohol and insoluble in water. a-Thiobutgranilide SH*CHEt*CO*NHPh crystallises in delicate colourless needles and melts at 95". a-Dithiodibutyranilide S,(CHEt*CO*NHPh) crystallises from dilute alcohol in delicate colourless needles and melts at 110'.The copper derivative Cu,(S*CHEt*CO*NHPh) forms a yellow amorphous powder. u-EthyZ- thiobutyyanilide SEt*CHEt*CO*NHPh crystallises in delicate colour- less needles and melts at 68O. G. Y. The copper derivative Cu,(S*CHMe*CO*NHPh) Hydroxamic Acids. By ANGELO ANGELI FRANCESCO ANGELICO and F. SCURTI (Atti h?euZ. Accad. Lincei 1902 [v] 11 i 555-561). -The products of hydrolysis of most compounds such as esters amides &c. are usually the same whether the decomposition is brought about by means of acids or alkalis but with hydroxylaminesulphonic acids benzenesnlphohydroxamic and nitrohydroxylarninic acids this is not the case Thus with alkalis these compounds yield a nitroxyl group and the corresponding acid either sulphurous acid or a sul- phinic acid RHSO and nitrous acid.With acids however the first two of the above compounds yield hydroxylamine together with sulphuric acid or a sdphonic acid R*SO,H whilst nitrohydroxyl- aminic acid loses immediately a mol. of water and gives nitrogen dioxide. To obtain further informxtion as to the mechanism of this hydrolytic action the authors have prepared and studied hydroxamic acids of sulphur of the following types which readily lend themselves to such decomposition R*SO,*NH*OH ; R*SO,*NRl*OH ; R*S02*NH*OR1 ; R*S02*NR1*OR2; R representing an aliphatic or aromatic residue and R1 and R2 aromatic aliphatic or acid residues. The acids studied of the first hype namely C,,H,a*SO,*NH*OH;SO,Et *NH*OH; C,H,( SO,*NH*OH),; and C,,H,(SO,*NH*OH) which are analogous to the acid prepared by Piloty (Abstr.1896,i 555) behavesimilarly to benzenesulphohydroxamic acid The alkaline hydrolysis was carried out in presence of either a n aldehjde or nitrosobenzene the nitroxyl group split off being thus converted into either a hydroxamic acid or nitrosophenylhydroxyl- amine. In the cage however of a-naphthalenesulphohydroxamic acid the residue after the removal of nitroxyl undergoes molecular re- arrangement yielding p-naphthalenesulphinic acid. When sulphohydroxamic acids in which two atoms of hydrogen are replaced by acid radicles for instance C,H,*SO,*~Ac*OAc and C,,H,~SO,*NAc*OAc are hydi olysed in presence of alkali they ex- hibit a similar behaviour to the above. The same is the case with the acid C6H,*S0,*NPh*OH which yields benzenesulphinic acid and nitrosobenzene (corresponding with the nitroxyl residue) and with C,H,.SO,*N(CH,Ph)*OH which gives nitrosotoluene this soon under- going transformation into benzaldehyde.The above behaviour is explained by supposing t h a t i n alkaline VOL. LXXXII. i. 3 h766 ABSTRACTS OF CHEMICAL PAPERS solution these compounds react as if they possessed the tautomerio structure R*SO(OH) NOH. Substituted hydroxamic acids of the type R.SO,*NH*ORl where R1 represents an alcoholic residue do not however exhibit such a reaction. Thus the acid C6H,*S02*NH*O*CH2Ph can be precipitated unchanged from solution in alkali even after long heating. The authors have prepared dibenzenesulphohydroxamic acid which they find to melt a t 126O although Koenigs (Abstr.1878 573) and Piloty (Zoc. cit.) gave the melting point 109'. With alkalis this acid yields benzenesulphinic acid and nitrous acid whilst with sulph uric acid it gives hydroxylamine. The corresponding naph- thalene derivative OH*N(S02*C10H7a)2 when treated with alkalis likewise gives nitrous acid and a sulphinic acid the latter being however the p compound namely P-naphthalenesulphinic acid ; if now the liquid be acidified the latter acid reacts with the nitrous acid giving di-P-naphthalenesulphohydroxamic acid OH*N(S02~CloH,~),. The nitrous acid formed in this alkaline hydrolysis is obtained by the splitting off of water from the radicle N(OH) so that in this case as also in those given above each sulphonic group attached to the nitrogen atom is ieplaced by a hydroxyl group.This also happens in the alkaline hydrolysis of tribenzenesulpho- hydroxylamine (Ph*SO,),NO in which nitric acid is formed. The analogy existing between the behaviour of these various compounds on alkaline hydrolysis is shown by the following scheme (ClOH7*SO2)HN*OH + (OH)HN*OH -+ NOH (C,oH~*SO,),N*OH -+ (OH),N.OH -+ NO,H (Cl,M7-S0,),N0 -+ (OH),NO -+ NO,H T. H. P. The Methyl Ethers of the True Nitrosophenols. o-Nitroso- phenol By ~ D O L F VON RAEYER and EDUARD KNORR (Be?*. 1902 35 3034-3037).-The 0- and p-nitrosoanisoles can readily be prepared by the action of Caro's reagent on the corresponding anisidines. p-Nitrosocmisole has not been obtained quite free from nitroanisole but the impure compound cry stallisas in large bluish-green prisms melting at about 32-44' forms bluish-green solutions i n all organic solvents except light petroleum readily volntilises in steam and decomposes in the air.Dilute acids and alkalis readily hydrolyse i t with formation of p-nitrosophenol. o-Ll'itrosoccnisole is not accom- panied by the nitro-compound and can readily be obtained pure; it crystallises in colourless six-sided plates melts at 1 0 3 O is stable in the air dissolves to some extent in cold? and more readily in hot water form- ing greeq solutions and is readily volatile in steam. It is only slowly attacked even by conceutrated aqueous potash whilst acids convert it into a resinous mass. o-Nitrosophenol (0-quinoneoxime) can be prepared from o-nitroso- anisole by gradually adding a n aqueous solution of the latter to boil- ing aqueous potassium hydrogen sulphate. The free nitrosophenol has hitherto only been obtained as an oil.The sodium salt crystallises in dark red plates with a green surface lustre and decomposes explosively when heated. The barium salt is sparingly soluble in water; the .ORGANIC CILEMISTRY. 767 silvei- salt is a heavy microcryst alline almost black precipitate which decomposes explosively when heated or brought into contact with a drop of sulphuric acid or fuming nitric acid. The properties of this o-nitrosophenol seem to indicate that it is an o-quinoneoxime. A. H. Nitrosophenol Dyes. I. By HERMANN DECHER and BASIL YON SOLONINA (Bey. 1902 35 3217-3225).-The blue compound formed by the action of fuming nitric acid on thymol ethyl ether (Kehrmann and Messinger Ber.1901 34 1626) was obtained in thin plates belonging to the rhombic system and melting constantly at 62-63O ; it is formulated as an oxonium salt NO,*OHE t *C,H,MePr *NO :C,H,MePr:OE t *NO two alternative formuls being also given. form it passes into a red indophenol derivative or OEt*C6H2MePr*NO:C,H,MePr:0. This compound gives Lieber- mann's reaction with sulphuric acid being thereby converted into a compound OH*C,H,MePr*N C,H,MePr 0. The blue oxonium salt is reduced by sulphurous acid hydrogen sulphide or stannous chloride to ditlbynolylamine dietlbyl ether NH(C,H,MePr*OEt) ; this separates from alcohol in beautif ~11 colourless crystals belonging to the triclinic system melts at 70-71° distils in part without decomposition dissolves in acids is not acted on by alkalis and gives an intense indophenol reaction with concentrated sulphuric acid.The hydrochlode C,,H,,O,NCl forms white needles and gradually oxidises in air t o a red compound. 2'hynzoquinone tlrp,oZ- irninoether OEt*C,H2~~ePr.N:CGH2MePi~:0 prepared by oxidising the preceding compound with ferric chloride crystallises from alcohol melts a t 96-97' has a dark red colour is insoluble in water or alka- lis and dissolves in organic solvents with a deep violet-red colour. It is reduced by sulphurous acid hydrogen sulphide or stannous chloride to ditl~y~nolyZ~~nainorlzonoet?~yZ ethei; OEt*C6H2%lePr'NH* G,H,MePr*OH ; this was not isolated but mas hydrolysed in the manner usual with a n indophenol t o thyrnoquinone and a n aminophenol sulphate.Hydrogen iodide reduces the indophenol ether in a similar manner to t h a t just described but also hydrolyses it to ditiynzolyZanzine NH(CGH,MePr*OH) ; the lqdriodide of this was obtained in colour- less crystals; the base dissolves in alkalis to a colourless solution which is at once oxidised in the air and deposits dark blue glistening crystals of a salt of tiiyntopui.12o)2ethy~~aoli?nine OH 9 H,Me Pr N ~,H-oMePr 0. The series of changes here described proves the constitution of the dithymolylamine diet'hyl ether and renders probable the formula assigned to the original blue salt. Partial and Complete Reduction Products of 2 6-Dinitro- thymyl Ethyl Ether. By G. OTTO GAEBEL (Ber. 1902 35 2793-2803).-Ethy1-2 6-dinitrothymyl ether is most conveniently obtained by treating the silver derivative of 2 6-dinitrothymol with ethyl iodide in alcoholic solution.When dissolved in chloro- OEt *C,H,MePr*N :C,H,MePr 0 T. M. L. 3 h 2768 ABSTRACTS OF CHEMICAL PAPERS. %Nitro. 6-aminothymyl ethgl ether produced by reducing the dinitro-compound either with alcoholic ammonium sulphide or with the calculated amount of stannous chlor- ide i n alcoholic solution crystallises from this solvent in rhombic plates melting at 11 1-1 12" ; the ?hydrochloride separates from dilute hydrochloric acid in white needles melting a t 195" and decomposing at 200' ; the sulphate forms white silky needles ; the acetyl and benzoyl derivatives separate from dilute alcohol in white needles and melt at 119" and 138" respectively. The amino-ether when treated with bromine dissolved in carbon disulphide yields a homo-derivative crystallising from dillite alcohol or ether in yellow rhombic plates melting at 75".The hydrocTJoride separates in white needles on pass- ing hydrogen chloride into the ethereal solution of the bromo-com- pound ; it is dissociated by water and decomposes a t 156'. The benaoyl derivative OEt*C,MePrP( NO,)*NHBz crystallises from dilute alcohol in white quadratic plates and melts at 171'. When 6-amino-%nitrothymy1 ethyl ether is diazotised with sodium nitrite and sulphuric acid in alcoholic solution it yields a n oily pro- duct which is probably a nitrothymyl ether because on reduction i t yields Z-arnirzotlqmyl ethyl ether OEt*C,H,MePrP*NH which is characterised by means of its Jqdrochloi-ide a salt crystallising from dilute hydrochloric acid in white needles decomposing at 204'.The pkatinicl~loride forms reddish-yellow needles and decomposes a t 169-170" ; the acetyl derivative separates from dilute alcohol in white needles and the benxoyl derivative in white plates ; the former melts at 109" and the latter at 144". The constitution of the preceding compounds was determined by comparing the above derivatives of the oily nitrothymyl ether with those of 6-nitrothy my ethyl ether. The hydrochloride acetyl and benxoyl derivatives of the latter compound crystallise in white needles and melt respectively at 227-230' 136' and 151-152'; the amine reduces platinic chloride and hence the double salt was not obtained. 2 6-Biaminothy~nyl ethyl ether hydrochloride OEt*C,HMePd( NH,HCl) resulting from the complete reduction of the corresponding dinitro- compound separates from a mixture of concentrated hydrochloric acid alcohol and ether as a snow-white powder decomposing at 215' ; the tetya-ucetyl derivative crystallises from dilute alcohol in white flakes melting at 146'.By W. FEUERSTEIN and ANDREAS LXPP (Bsr. 1902 35 3852-3256).-When a mixture of anisole (2 mols.) benzaldehyde (1 mol.) and glacial acetic acid is addeci t o well-cooled sulphuric acid containing some acetic acid and after some time is poured on to ice phenyldiunis?/lmethane CHPh(C,H,*OMe) separates out. It melts at 1OO-l0lo and is sparingly soluble in cold alcohol but dissolves easily in concentrated sulphuric acid I t has been proved that the benzylidene group is in the pccm-position t o the methoxy-groups because the same substance has been cbtained by the methylation of 4 4'-dihydroxydiphenylmethane.G. T. M. Action of Benzaldehyde on Anisole.ORGANIC CHEMISTRY 769 With p-tolyl methyl ether a substance of the formula CHPh(C,H,Me*OMe) [CHPh Me OMe = 1 3 51 is formed which melts at 107-109O and is soluble in concentrated sulphuric acid to a violet solution. The same condensation takes place with p-cresol the phenol CHPh(C,H,Me*OH) [CHPh Me OH = 1 3 61 being obtained ; this melts a t 15S-160° is soluble in the ordinary organic solvents and sulphuric acid and gives a diacetyl derivative which melts a t 121-122O. When subjected to distillation this phenyl- di-p-tolylmethane yields 1-phenyl-2 7-dinzethylxanthen C H M e ~ g ~ c 6 H 3 % which crystallises in white silky needles and melts at 191-1915° ; it is insoluble in alkalis but dissolves in concentrated sulphuric acid giving a green fluorescent solution.The condensation with o-tolyl methyl ether leads to a substance which melts a t 101-102° the constitution of which is probably cwPhiC-R Ma*nMP\ rcm - M~ - nMa = 1 R a AI -1 MPC Dibenzylideneacetone and Triphenylmethane. By ADOLF VON BAEYER and VICTOR VILLIGER (Ber. 1902 35 3013-3033. Com- pare this vol. i 380).-Trianisylmethane does not as was a t first believed form coloured salts and hence this substance like triphenyl- methane is not halochromic and the distinction between ammonium and oxonium salts which was founded on the apparent halochromism of these substances,.cannot therefore be maintained The properties of triphenylcarbinol in many re-spects differ from those of both alcohols and acids and are more closely allied to those of aldehydes or ketones.A close analogy exists between the behaviour of the carbinol to many reagents and that of nitrous acid. The carbinol slowly combines with sodium hydrogen sulphite to form sodium triphenylmethylsulphonate CPb3*S03Na 2H,O which crystallises in large lustrous plates. The free acid crystallises in sparingly solu- ble needles. When the carbinol is heated with aniline and acetic acid the anilide which has been previously prepared from aniline and triphenylbromomethane is formed. Phenylhydrazine yields with the carbinol a substance which melts a t 108.5O and is probably identical with the triphenylmethylazobenzene obtained by Gomberg from tri- phenylbromomethane.The carbinol also reacts readily with hydroxyl- amine yielding a product C38H3202N melting a t 182-184" but the constitution of this substance has not been ascertained. Triphenyl- carbinol readily combines with phenol forming hydroxytetraphenyl- methane CPh3-C6H,*OH which crystallises in needles or plates and melts a t 2829 This substance behaves as a phenol and yields a potassium salt which is readily soluble in alcohol. Friphenyl-p-anisyl- methane is formed from the carbinol and anisole and crystallises in needles melting a t 194'. These reactions with sodium hydrogen sulphite aniline and phenol correspond with the reactions of nitrous acid with the same types of compounds and the analogy is also supported by the ready esterification of the carbinol by alcohols its770 ABSTRACTS OF CHEMICAL PAPERS.union with sulphuric acid and the fortnation of double salts of tri- phenylchloromethane and metallic chlorides. The basicity of a number of methoxyl derivatives of benzglidene- acetone &pd triphenylcarbinol was measured by ascertaining how much dilute alcohol was required to hydrolyse and thus decolorise solutions of molecular proportions of the various substances in a standard solu- tion.of acetic and sulphuric acids. Taking the basicity of dibenzyl- ideneacetone as 1 those of the methoxyl derivatives are as follows mono-pcompound 3.9 ; pp-compopnd 13.5 ; 00-compound 3-7 ; mm-com- pound 1.2. Similarly taking the basicity of triphenylcarbinol as 1 we have mono-p-compound 6.3 ; di-p-compound 34; tri-p-compound 286 ; tri-o-cornpound 7.6 ; tri-m-compound 1.7 ; oop-compound 27.3.I n both cases the effect of the methoxyl group is greatest in the para-position whilst a greater effect is produced by its introduction into triphenyl- carbinol than into dibenzylideoeacetone. Comparing the effect of the introduction of the group in the same position into successive rings i t is found that the basicity increases in geometrical ratio and this leads to the important conclusion that the three phenyl groups of the carbinol have an equal influence on the basicity of the derivatives so that it becomes improbable that the formation of coloured salts can be referred to the presence of a quinonoid group in which only one phenyl group is concerned.The increased basicity produced by the introduction of the methoxpl groups is accompanied by an increase in the chemical activity of the hydroxyl group of triphenylcarbinol. Tri-p-anisylcarbinol is much more easily reduced than triphenylcarbinol and also unites with sodium hydrogen sulphite much more rapidly the reaction taking place at once whilst in the case of the triphenyl-derivative it requires weeks for its completion. The sodium salt produced crystallisss in large colourless plates and has the formula C( C,H,*OMe)3*S03Na,$H,0. Trip-anisylcarbinol is at once acted on by hydrocyanic acid forming tri-p-anisylacetonitrile which crystallises in long rectangular plates and melts at 1285-129O. Triphenylacetonitrile has been prepared by heating triphenylchloromethane with mercuric cyanide.Tri-p-anisyl- carbinol also reacts readily with aniline forming a blue colouring matter. These facts further confirm the conclusion that the activity of the hydroxyl group is conditioned not by any one of the phenyl groups present in the molecule but by the nature of the whole complex with which t.he hydroxyl is united. The following new compounds have been prepared in the course of the work Benzylidene-p-ani8yylideneacetone (p-methoxydibenzylideneacetone) is obtained by the condensation of benzylideneacetone and p-anisalde- hyde and forms nodular crystals melting at 9 6 . 5 O . Di-o-anisylidene- acetone prepared from acetone and o-methoxy benzaldehyde crystallises in bright yellow rhombic plates and has previously peen obtained by Petrenko-Kritschenko. o-Methoxybenzddehyde boils at 114-1 15' under 12 rum.pressure. Di-m-anisyEideneacetme is prepared in a similarORGANIC CHEMISTRY. 771 manner and purified by conversion into tlie hydriodide; i t crystal- lises in yellow needles melting a t 52-54". The methoxydibenzyl- ideneacetones behave towards acids in a similar manner to the'psrent su bstante. Tri-o-anisylcarbinol is prepared by Grignard's method from iodo- anisole and methyl o-anisate and forms colourless lustrous tablets melt- ing a t 181". Tri-m-anisylcarbinol is prepared in a similar manner and crystallises in tablets melting a t 11 9.5'. m-Iodoanisole is prepared by converting m-nitroaniline into m-nitrophenol methylating this with methyl sulphate reducing diazotising and finally treating with hydriodic acid.The methyl m-misate .is prepared from m-hydroxy- benzoic acid. oop- Trianisylcarbi?zol crystallises in large lustrous prisms melting a t 109-llOo and is prepared from o-iodoanisole and methyl p-anisate. Diphenyl-p-anisplcnrbinol prepared from bromo- benzene and methyl p-anisate forms crystalline crusts melting a t Tri-p-anisylchloromethnne is formed when hydrogen chloride is passed into an ethereal solution of the carbinol and is a white powder con- sisting of long prisms ; it melts and decomposes a t 154-156' forming a red liquid which probably contains dimethylamine. Auto-oxidation of Pyrogallol. By CARL D. HARRIES (Ber. 1902 35 2954-2959).-When pyrogallol dissolved in barium hydr- oxide solution is shaken with air it undergoes oxidation forming a hexa- hydroxydiphenyl which probably has the constitution 3 4 5 3' 4' 5'.It crystallises from hot water in white needles which begin to decompose when heated to ZOO" dissolves in alkali hydroxides giving deep coloured solutions and reduces Pehling's solution but yields no quinone when treated with an alcoholic solution of iodine. The acetyl derivative crystallises in small colourless plates and melts at Alkaline solutions of the substance absorb oxygen but yield no trace of purpurogallin; it is therefore probable that for the formation of the latter by the auto-oxidation of pyrogallol (Berthelot Abstr. 1898 i 645) the presence of pyrogallol as well as the hexahydroxy- diphenyl is necessary.Halogen Derivatives of the Phloroglucinols. 111. Decom- position of Tribromophloroglucinol. By JOSEF HERZIG and HERMANN KASERER (Monatsh 1902 23 573-581. Compare Abstr. 1886 232 ; 1895 i 343)-Tribromophloroglucinol is hydrolysed by aqueous potassium or barium hydroxide to carbon dioxide and a substance which forms a sparingly soluble barium salt apparently identical with the barium salt of dihydroxydiketocpclopentane de- 5 8 - G l O . A. H. 162-163". R. H. P. scribed by Hantzsch (Abstr. 1888 132). a. Y. Halogen Derivatives of the Phloroglucinols. IV. Chloro- derivatives of the Ethers of Phloroglucinol. By HERMANN KASERER (Moncxtsh. 1902 23 582-588. Compare preceding abstract).-When acted on by chlorine in carbon tetrachloride solu- tion phloroglucinol trimethyl ether forms trichlorophloroglucinol772 ABSTRACTS OF CHEMICAL PAPERS.trimethyl ether which melts at 230-131' and is identical with Bartolotti's compound (Abstr. 1897 i 558). It can neither be acetylated nor reduced and is not acted on by boiling water or aqueous alkalis. Phloroglucinol dimethyl ether yields on chlorination a tetrachloro- derivative which crystallises from benzene in large pale yellow transparent crystals melts at 115-1 17'' darkens on exposure to light and is soluble in benzene carbon tetrachloride and conxntrated sulphuric acid but more sparingly so in light petroleum It has an odour resembling that of camphor. It is decomposed by alkalis with formation of hypochlorites. The chlorine is only partly eliminated by the action of sodium amalgam or by boiling water.It cannot be acetyl- ated. Reduction with stannous chloride and acetic acid leads to the formation of tricl~loropl~Zorog2zccinoZ dimethyl ether which crystallises from benzene melts at 93-95O is soluble in aqueous alkalis but is not changed by long boiling with alkalis and forms an ucetyl derivative crystallising in large glistening flakes melting a t 58-59' and easily soluble in benzene or light petroleum. Chlorination of phloroglucinol methyl ether leads to the formation of a pentachloro-derivative OMe*C!CI,O which has a yellow colour melts at 72-74" is easily soluble in benzene and carbon tetrachloride but sparingly so in cold light petroleum and has scarcely any odour. Approximately 4 atoms of chlorine are eliminated by boiling with aqueous potassium hydroxide (compare Abstr.1900 i 595). Alkyl Ethers of the Phloroglucinols. V. Constitution of the Mono- and Di-alkyl Ethers of Methylphloroglucinol. By JOSEF HERZIG and KARL EISENSTEIN (Monatsh. 1902 23 563-572. Compare Abstr. 1901 i 206).-The mono-methyl and mono-ethyl ethers of methylphloroglucinol prepared by etherification with alcohol and hydrogen chloride yield on further etherification two methyl- ethyl ethers which are isomeric and must therefore be alkylated in the oppositions. This supports the contention of Bosse (Abstr. 1901 i 207) that direct etherification of methylphloroglucinol takes place in the first instance in the p-position (compare Abstr. 1902 i 463). 1-Methylphloroglucinol 4-ethyl ether crystallises from benzene in colourless glistening needles melts a t 136-137' boils a t 195-200' under 13 mm.pressure and is easily soluble in alcohol or ether. The diacetyl derivative crystallises from alcohol in colourless soft leaflets and melts a t 91'. If 'on etherification of the mono-alkyl ethers with alcohol and hydrogen chloride the reaction be carried too far it results in a non- volatile product but by stopping it before it has completely reached this stage a mixture of the mono- and di-alkyl ethers is obtained by distillation. The di-alkyl ethers which show little tendency to crys- tallise are characterised by means of the dibromo- and acetyldibromo- derivatives. DibrornomethyZphZorogZuci~ol ethyl ether [Me OEt (OH) Br = 1 4 2 6 3 51 crystallises from light petroleum and melts at 115'.3 5-Dibromomet/L;(/ZphlorogZucinoZ 4-methyl ether crystallises from G. Y.ORGANIC CHEMISTRY. 773 light petroleum i n long needles melts at '114" and is easily soluble in alcohol or benzene. 3 5-BibromornethyZphZoroglucinoZ 2-methyl 4-ethyZ ether separates from dilute alcohol in colourless crystals melts at 72-74' and is easily soluble i n alcohol benzene or light petroleum. The acetyl derivative crystallises from alcohol in long prisms and melts a t 77-78' 3 5-Di- bromomethyZphZorogZ.ucinoI 4-methyl 2-ethyZ ether is precipitated from glacial acetic acid on addition of water in colourless hair-like needles and melts at 84-86'. The acetyl derivative forms monoclinic crys- tals from alcohol and melts at 99-101O. G Y. Reduction of Chrysazin with Hydrogen Iodide.By H. SCHROBSDORFF (Bey. 1 902 35 29 30-2 9 3 1) .-Dihy~yoxyanthranoZ (chrysanthvanol) C€€<$~3~o"H"3c.0H crystallises from light petroleum in minute lemon-yellow flakes or needles and melts at 176-177'. The triacetyl derivative crystallises i n yellowish needles melts at 209-210' and is oxidised to diacetylchrysazin. 6 3 T. M. L. Reduction of Quinizarin and A n t h r a r u f l n with Hydrogen Iodide. By B. PLEUS (Be?-. 1902 35 2923-2930).-In addition t o quinizarin hydride hydroquinizarol and hydroxyhydroanthranol which Liebermann and Giesel (Abstr. 1877 ii 494) obtained as reduction products of quinizarin 1 4-dihydroxyanthranol and hydro- a-anthrol have been obtained. 17?.iacetyZhydroquiniaaroZ CH2<cR -C,H,- H,(OAc) >CH*OAc prepared by heating hydroquinizarol with sodiiym *acetat and acetic anhydride forms yellow needles and melts at 79-80" ; it is oxidised by chromic acid in acetic acid solution t o diacetylquinizarin (Abstr.1875 68). 1 4-l)ihydroxyanth?.an~l CH--\CH*OH crys t allises f rorn alcohol in felted orange-red needles melts at 1 5 6 O and when dissolved in alkali and exposed to air becomes blue through conversion into quinizarin. The triacetyl derivative forms small short! yellow prisms melts at 1 88-1S9' and is oxidised to diacetylquinizann. Diacet ylhydroxyhgdroanthruno I CH2$gJEiT>CH *O Ac cry s- tallises in yellow needles and melts at 84-S5O; this and the monf- xcetyl compound are oxidised by chromic acid to acetylerythro-oxy- anthraquinone. Bydvo-a-unthrol C6H,<CW2>C,H3(OH) CH isomeric with Perger's hydroanthranol (Abstr.188 1 607) crystallises in whitish-yellow flakes melts a t 94' and is not very readily volatile in steam. The acetyl derivative forms yellow needles and melts at 82-85'. /-C,H*- "6 H2(0H)2' Two new compounds were also obtained by reducing anthrarufin. 1 5-Bihyd~oxyhydroanthranol CH,<C6H,(OH) C6H3(OHj>CH.0H crys- tallises from dilute alcohol in golden-yellow needles and melts at 241".774 ABSTRACTS OF CHEMICAL PAPERS. The triacetyl derivative crystallises in small yellowish-white needles melts a t 162-163" and is oxidised to diacetylanthrarufin. 1 5-Dihydroxyunth~~noZ CH(CRH3(OH),C*OH c H.(OH)\ crystallises from 6 3 alcohol in glistening golden flakes and decomposes at 200' without melting.The triucetyl derivative crystallises in stout yellow mono- clinic prisms melts a t 184-185O and is oxidised t o diacetylanthra- rufin; it is also formed when the dihydro-compound is dried at 120° two atoms of hydrogen being eliminated. Anthrcmujin monoethyl etheil. OH*C1,H602*OEt crystallises from dilute alcohol in minute short canary-yellow needles and melts a t Acetylanthy*arufin monoethyl ether OAc* C,,H,O,*OEt forms yellowish The diethyl ether crystallises fmm 163-164'. flakes and melts at 172-173". alcohol in long yellow felted silky needles and melts at 178". T. 11. L. Gradual Synthesis of the Benzene Chain. By MAURICE DELACRE (Bull. Acad. rog. Belg. 1902 251-258. Compare Abstr. 1900 i 603).-The results now published extend and correct those recorded in a previous paper ( B u l l .Acud. roy. Belg. 1896 29 849). When a-isodypnopinacolin C32H260 is h a t e d t o 400' in a vacuum i t rapidly decomposes furnishing ( 1 ) a liquid distillate containing ethyl- benzene allylbenzene acetophenone benzaldehyde and benzoic acid ; (2) a semi-solid fraction consisting of triphenylbenzene pyrodypnopinacolin and an uncrystallisable resin which on redistillation under atmospheric pressure decomposes into ethylbenzene polymerised allylbenzene and triphenylbenzene (a). Pyrodypnopinacolin C32H,20 crystallises from alcohol in colourless crystals melts at 166" and distils between 465' and 475'. Its solubilities in the following media at their boiling points and a t the ordinary temperature respectively are acetic acid 2.2 and 0.1 ; alcohol 2.2 and 0.3 ; ethyl acetate and acetone 10 and 1.3 per cent.; i t is also more soluble in hot than i n cold benzene. With acetic acid ethyl acetate benzene acetone and acetyl chloride 2 mols of the substance combine with 1 mol. of these solvents to form crystalline molecular compounds stable at 100-1 05' but which decompose a t 150-160°. The acetic acid additive product crystallises in colourless plates melts a t 162O and is employed as a convenient means of separating pyrodypnopinacolin from the bye-products of its preparation. When reduced in alcoholic solution by means of sodium amalgam or when treated with zinc ethyl pyrodypnopinacol alcohol C,,H2,0 is produced. The latter forms characteristically grouped colourless needles melts at 156Oand distils a t 310-328' under 15 mm.but when heated under atmospheric pressure (or in a vacuum if impure) it decomposes into benzaldehyde and a solid hydrocarbon C2gH,q (P). It dissolves in alcohol acetic acid o r benzene but is insoluble in llght petroleum Pyrodypnopinulcolene C32H22 is produced when pyrodypnopinacolin is treated with hydriodic acid (with concentrated acid triphenylbenzene is also formed) or when pyrodypnopinncolyl alcohol is dissolved inORGANIC CHEMISTRY. 775 ncetyl chloride or acted on by phosphorus pentachloride. It crystallises in silky needles which melt a t 136' or in large transparent crystals which melt at 154-156' and boils at 330-333O under 15 mm. pressure Its solubilities in the following media a t their boiling points and a t the ordinary temperature respectively are alcohol 1 and 0.1 1 ; acetic acid 13.7 and 1.6; benzene 153.8 and 35.6 per cent.When heated in alcoholic solution with sodium or when oxidised by nitric acid it is converted into dehydropyrodypnopinacolyl ulcohol C,,H,,O. This forms colourless crystals melts a t 203.5' and distils in a vacuum a t 300-320' with slight decomposition. I t s solubilities in the following media- a t their boiling points and at the ordinary temperature respectively are alcohol 0.74 and 0.15 ; acetic acid 4.16 and 1.13 ; benzene 20.8 and 2.8 per cent. With the latter an additive compound appears to be formed. When heated with hpdriodic acid pyrodypnopinalcolene is re-obtained. With acetyl chloride d e h y d r o ~ y r o d ~ ~ n o ~ ~ n a c o l y l acetate C,,H,,O forming colourless crystals which melt at 200' is pro- duced.This dissoldes readily in benzene less so in acetic acid and alcohol. On saponification the alcohol is not regenerated. When repeatedly recrystallieed from acetic acid i t appears to be converted into the pyrodypnopinalcolene already described. The author supposes that a-isodypnopinacolin may be represented by the formula C,H,OPh in which case pyrodypnopinacolin might be written C,H,OPh or C,H60Ph2(C6H4)2 or CsH4O(CBH4) the second or third expression being the more probable. By JULIUS TROEBER and CHR. BUDDE (J. pr. Chem. 1902 [ii] 66 130-152. Compare A bstr. 189 7 i 223),-Di-m-x yly Zethy Zenedisulphome C',H,( SO2*CSHg) formed by the action of a n alcoholic solution of ethylene dibromide on sodium m-xylenesulphinate prepared by Gattermann's method frvm 1 3 4-xylidine crystallises from alcohol in rosettes of needles melts at 163' is easily soluble in hot alcohol more sparingly so in ether.When boiled with 30 per cent. potassium hydroxide solution it yields m-xylenesulphinic acid and a semi-solid oil which is a mixture of m-xyEyZsu~~~onetiiylic alcohol C,H,*SO,*CH,*CH,*OH and its ether (C,LI,*SO,*C,H,),O. The proportion of ether is increased if the hydro- lysis be carried out under pressure. A preparation of di-m-xylylethyl- enedisulphone obtained from a sulphinic acid prepared by reduction of m-xylenesulphonic chloride with zinc dust melted a t 146' and on hydrolysis yielded a xylenesulphinic acid melting at 55' and an oil consisting apparently of only xylylsulphonethylic alcohol.The fol- lowing disulphones were obtained by prolonged warming of ethylene dibromide with the corresponding sodium sulphinate in alcoholic solu- tion. Di-p-xylyletlzylenedisulphone which crystallises from alcohol in needles melts at 174' and on hydrolysis yields the sulphinic acid and p;xy~ylsul~~~onet~~ylic alcohol C,H,*S0,*C2H,*OH as a light coloured oil. Di-$-cumylethylenedisulphone C2H,(S02*CgH,,) which separates from alcohol in needles melting a t 241' and on hydrolysis with potass- ium hydroxide solution a t 150° yielding a mixture of $-cumylszclphon,- eth ylic ulcohol and its ether (C,H,,*SO,*C,H,),O. Di-a- nap?ithyEeth ylene - disulphone C,H,(S0,*CloH7)2 which crystallises from alcohol in T. A. H. Aryl-sulphonated Alcohols and Acids.776 ABSTRACTS OF CHEMICAL PAPERS.needles melts a t 194" and on hydrolysis yields a-naphtlbylsulp?hon- ethylic ulcohol CloH7*S0,*CH,*CH2*OH; which is an oil. Bi-p-naphthyk ethylenedisulphone which crystallises from alcohol in needles melts at 258' and yields P-napht~~ylsulphonetT~ylic alcohol as a white crystalline powdbr melting at 88-90'. Di-p-chlorophenyZethyZenedisuZphone C2H4( SO,*C,H,Cl) c r y s t a h i n g from alcohol in microscopic needles which melt at 255' and on hydrolysis yielding the sulphinic acid and p-chlorophenylsulphonethy lic ulcohol C,H,Cl SO,*C,H,*OH as a thick brown oil. Di-p-bromophenylethyZenedi$ulphone which melts at 261' and yields p-bromophenylsulphorzethylic alcohol which forms a crystalline mass and me1 ts at 50-5 2'.C,H,(SO,*C,H,*OMe) which forms needles melts at 175' and yields o-anisylsulphonethylic alcohol OMe*C,H,*SO,*C,H,*OH which forms a crystalline mass and melts a t 82'. These arylsulphonethylic alcohols are easily soluble in alcohol or ether more sparingly so in water. The following arylsulphonacetic acids have been prepared by the action of ethyl chloroacetate on the corresponding sodium sulphinate and hydrolg sis of the ester so obtained. m-XylylsuZpJbonacetic acid C H *SO,*CH,-CO,H is crystalline and melts at 56'. p-Xylylsulphon- acetzc acid is an oil. ~-CumylszLl~honacetic acid C,H,,*SO,*CH,*CO,H forms granular crystals and melts a t 62'. a-NaphthylsulpAonacetic acid C1,H7*S0,*CH2*C0,H crystallises in glistening leaflets and melts a t 168". p-iVapAthylsulphonacetic acid Cl,H,oO,S,H,O forms a white crystalline powder and melts at 90" ; the ethyl ester C,,H7~S0,*CH2*C0,Et,~€€20 melts a t 82' the sodium sah crystallises from alcohol in white needles.p-C'hloropiLenylsulpho~~acetic acid C6H,C1*S0,* CH,*CO,H cryetallises in small glistening leaflets and melts a t 122" the ethyl ester is an oil. p-Bromopi~enylsulp~~onacetic acid C,H,BroS0,*CH2*C0,H crystallises in needles and melts a t 143' the ethyl ester C,H,O,SBrEt,H,O crys- tallises in silky needles and melts at 52'. o-Anzs~lsulphonacetzc acid OMe*C,H,~SO2*C1H,*CO2H crystallises in needles and melts a t 138" the ethyl ester is obtained as an oil which slowly solidifies. The following a1 kylsulphones C,H,Me2*S0,R have been obtained by the action of alkyl haloids on sodium m-xylenesulphinate m-Xylyl- methylsulphone forms crystals from alcohol and melts a t 55'.m-Xylyl- ethylgulphone solidifies on standing and melts at 53'. m-Xylyl-n-prop& sulphone crystallises from dilute alcohol in needles and melts a t 68-69'. m-XylyLisopropyZ- butyl- amyL and cetyl-sulphones are .oily substances and could not be obtained free from halogen. m-XylyZallyl- sulphone is obtained sometimes crystalline sometimes as an oil; the compound !ast mentioned combines with bromine forming a crystal. line dibromide which melts a t 56-57'. o-Anisylmeth ylsulphone OMe*C6H,*S0,1\~e crystallises from alcohol and melts at 84". Di-o-anisylethylenedisuZphone 8 P G. Y. p-Hydroxytriphenylcarbrbinol. 11. By AUGUSTIN BISTRZYCKI and CARL HERBST (Bey. 1902 36 3133-3141. Compare Abstr. 1901 i 'i'Ol).-Crude orange-coloured p-hydroxytriphenylcarbinol may be obtained perfectly colourless by repeated crystallisation from aceticORGANIC CHEMISTRY.777 acid and water or by conversion into its acetyl derivative and sub- sequent hydrolysis with alkali and crystallisation from acetic acid. The sodium derivative ONa*C,H,*CPh,*OH forms colourless plates. p-Ethoxytriphenylcadinyl ethyl ether OEt*C,H,*CPh,*OEt crystal- lises from aqueous alcohol in ColQurless microscopic plates melting at 87". It may be obtained by the action of alkali and ethyl iodide or of hydrogen chloride and alcohol on the hydroxycarbinol. The methyl ether OMe*C,H,*CPh;OMe melts a t 74' and is readily soluble in most organic solvents with the exception of light petroleum When boiled with glacial acetic acid acetyl chloride or acetic anhydride the ethyl ether is converted into p-ethoxyti.iir,hen?tZnzetl~nne CHPh,*C,H;OEt which crystallises in well-formed doubly refractive plates melting at 70-719 The methyl ether when similarly treated yields p-methoxy- ts.iphenn?/lcarbinol melting at 84". p-Nydrox~triphenylmelhane obtained by the reduction of the corre- sponding curbinol with zinc and acetic acid crystallises i n microscopic plates melting at 110'.The nzethyl ether melts at 61' and the acetgl derivative at 84". Dibromo-p-ethoxytriphenn?/Zqarbin$ ethyl etier OEt*C,H,Br,*C'Ph,=OEt obtained by alkylating the dibromohydroxycarbinol (Abstr. 1901 i 701) crystallises i n well-formed plates melting at 105". The dimethyl compound crystallises in microscopic prisms melts at 9So and when boiled with acetic anhydride yields a n ether O(CPh,*C,H,Br,*OMe) melting a t 133".The diethyl compound under similar treatment yields dibromo-p-ethoxytriphenylmethme melting at 1 32". Dibronao-p-hyds.oxytrip?maylmethane obtained by the reduction of t h e carbinol crystallises in small prisms melting at 131' and yields an acetyE derivative melting at 11 2-1 13". Most of the ethers described do not give correct results for ethoxy- or methoxy-estimations by the Zeisel method. J. J. S. Constitution of a New o-Chlorodinitrobenzoic Acid and of 0-Chloro-sn-nitrobenzoic Acid. By ATTILIO PURGOTTI and A. CONTARDI (Gaxxetta 1902 32 i 526-537).-The authors have determined the constitutions of the two following acids The dinitro-o-chlorobenzoic acid described by Kalle (D.R.-P.106510) and melting at 199-200". This acid is best prepared by heating at 130-140" a mixture of o-chlorobenzoic acid sulphuric acid and fuming nitric acid in suitable proportions. It boils at 240-241° and at 253" decomposes and for the most part explodes ; it is slightly soluble in water but almost insoluble in the other solvents. Since when nitrated in the cold with a mixture of sul- phuric and nitric acids o-chlorobenzoic acid yields the nitro-o-chloro- benzoic acid melting at 165' described by Hubner (Abstr. 1884 599) and this at higher temperatures gives with the same nitrating mixture Kalle's acid the latter as well as Hiibner's acid must have a nitro- group in the 3- or 5-position. Further the dinitro-acid gives a n almost theoretical yield of the methyl ester in presence of hydrogen chloride and as position 2 is occupied by chlorine position 6 must according to778 ABSTRACTS OF CHEMICAL PAPERS Victor Meyer's rule be free.When heated with excess of ammonia solution the acid yields the dinitroaminobenzoic acid [XH 2N0 = 2 :3:51 which with dilute sodiym hydroxide solution gives the corre- sponding dinitrosalicylic acid hence Kalle's acid has the constitution [Cl NO NO = 2 3 51. . When boiled with excess of barium hydroxide solution i t yields o-p-dinitrophenol. The acid may also be prepared synthetically by heating m-dinitrosalicylic acid with phos- phorus pentachloride. The o-chloro-m-nitrobenzoic acid described by Hubner (loc. cit.) when boiled for some time with excess of concentrated potassium hydroxide solution yields the nitrosalicylic acid [CO,H OH NO = 1 2 51.The constitution of the acid must hence be CO,H C1 NO - 1 2 5. %:H. P. Derivatives of o-Chlorodi-m-dinitrobenaoic Acid 11. By ATTILIO PURGOTTI and A. CONTARDI (Gaxxetta 1902 32 i 573-579. Compare preceding abstract).-The following derivatives of o-chlorodi- m-dinitrobenzoic acid have been examined The silver sa!t crystdlising in thin white needles ; the sodium salt forming yellow scales ; the potassium mmonium barium calciwm copper nickel martganese cobalt and lead salts were also prepared. The methy? ester forms small acicular crystals which have a pungent odour melt at 8 7 O .and dissolve in methyl alcohol and to a less extent in ether water or benzene.The etlql ester forms plates melting a t 54O and is soluble in alcohol or ether. When heated with three molecular proportions of aniline the acid reacts according to the equation C,H,Cl( NO,),*CO,H + 3NH,Ph = NHPh*C,H,( N0,),*C02H,NH,Ph + NH,Ph,HCl. The aniline o-phenylarnino-di-m-nitrobemonte thus ob- tained crystallises from water in slender shining red needles which begin t 6 decompose a t 1.41' and a t 253' melt and carbonise. The free acid forms orange-yellow needles which melt a t 215' and are readily soluble in alcohol or benzene; the potassium salt forms bright red shining leaflets. The action of hydrazino hydrate on o-chlorodi-m-dinitrobenzoic acid yields %n internal ccnlydride of the constitution C,H,(NO,),<~!>NH which separates from water in yellow prisms decomposing without melting a t 185-215'.T. H. P. Methylanthranilic Acid. By GUSTAV SCFIULTZ and J. FLACHS- LANDER (Chem. Centv. 1902 ii 448 ; from Zeit. Fcwb. Textilclhem. 1902 1 3 5 3 - 3 5 4 ) . - i ~ e t ~ ~ ~ Z a n t ~ r a ~ ~ Z ~ c acid NHMe*C,H,*CO,H pre- pared by the action of methyl iodide on anthranilic acid crystallises from alcohol in leaflets which show a greenish lustre melts a t 177" and is soluble in alcohol or ether forming solutions with a blue fluores- cence ; i t is almost insoluble in water. When the acid is heated above its meleing point it decomposes forming methylaniline and when melted with alkali it yields indigo. The hpdrochloride C,H,O,M,HCl crystallises in needles melts a t 141° and is readily soluble in alcohol but only slightIy SO in water or ether.Acetylnzet~ylcntl~ranilic m i d NAc%le*C,H,-CO,H crystallises in needles melts at! 1924 and is readilyORGANIC CHEMISTRY '779 soluble in hot water or. alcohol but only sparingly so in ether Methyl rnethylanthrccnilate NHMe*C6H,*C02Me is liquid has the odour of jasmine and boils at 129O under 13 mm. pressure. Nitrosomethyl- anthrccnilic acid NO*NMe*C,H,*CO,H crystallises from benzene in reddish-yellow crystals has not a definite melting point and is readily soluble in alcohol ether or hot water. The hydrochloride of p-nitroso- meJhylanthmnilic acid NHMe*C,H,(NO)*CO,H,HCl dissolves in water or alcohol forming a green solution and on heating forms p-nitroso- methylaniline with elimination of carbon dioxide. E.W. W. Action of Formaldehyde on Anthranilic Acid. By GUSTAV HELLER and GEORG FIESSELMANN (Annalen 1902 324 118-1 37. Compare Abstr. 1901 i 710).-et7~ylenebisanthran~l~c acid CH,( NH*C,H,*CO,H) prepared by adding 40 per cent. formaldehyde solution to an alcoholic solution of anthranilic acid separates from acetone as a white crystalline powder which becomes yellow a t 150' and decomposes a t 158'; i t also crystallises from ethyl benzoate. It dissolves in alcohol but does not crystallise from this solvent and it undergoes transformation when treated with glacial acetic acid. The ammoniacal solution of the compound yields precipitates with solutions of the salts of the heavy metals but not with those of magnesium and the alkaline earth metals. CH,(NAc*C,H,*CO,Na) *NAc*C,H,* CO,H prodficed by heating the preceding acid with acetic anhydride and anhydrous sodium acetate is a colourless crystalline powder decom- posing at 284"; it is readily hydrolgsed by dilute hydrochloric acid into formaldehyde and acetylanthranilic acid.The methylene compound when dissolved in pyridine and treated with benzoyl chloride loses its methylene group and yields benzoyl- snthranil. Potassium cyanide decomposes the methylene compound into anthranilic acid and anthr milinoncetnnitrile The diacetyl derivative CN.CH,*NH.U,H,*CO,H. obtained by heating the methylenebisanthranilic acid with dilute hydrochloric acid is isolated in the form of its hydrochloride Ci5HlGO,N,Cl by adding to the product excess of the concentrated reagent. The acid set free by the hy(Jro1ytic dissociation of its hydro- chloride in aqueous solution crystallises in needles and decomposes a t 254".When heated with dilute hydrochloric acid at ZOO" i t readily loses carbon dioxide yielding 4 4'-diaminodiphenylmethane. A solu- tion of the neutral sodium salt of t h i s acid yields a crystalline calcium salt CIjH,,O,N,Ca when treated with calcium chloride ; similar in- soluble salts are obtained by the interaction of solutions of other metallic salts. The ethyl ester CH,[C,H,(NH,)*CO,Et] produced by heating the hydrochloride with ethyl alcohol and concentrated sulphuric acid separates in aggregates of slender needles melting a t 109" ; the methyl ester prepared in a similar manner has already been described (Abstr. 1901 i 470). The dicccetpl derivative CH,[C,H,(NHSC)*CO,H]~ prepared by Pin- 4 ~'-Diccminodipl~eny~~~t~~ane-3 ; 3'-dzca~boxylic acid CH&!!H,(N H3) CO3H_'9,'is0 ABSTRACTS OF CHEMlCAL PAPERS.now's method is insoluble in the ordinary organic solvents excepting glacial acetic acid but dissolves in solutions of sodium acetate or alkali hydroxides and carbonates ; it decomposes a t 259-261'. The dibenzoyl derivative produced by the Schotten-Baumann reaction crystallises from glacial acetic acid in needles decomposing a t 268' ; it also dissolves in ppridine or in hot acetone or alcohol. This com- pound forms soluble alkali salts which are precipitated by excess of the alkali hydroxide or carbonate. Dibenxoyldiantl~yc~izil~~~net~c~ne CH,( C6H3<x:z) resulting from 9 the action of benzoyl chloride on the diphenylmethane derivative in pyridine solution crystallises from this solvent in needles or from toluene in sheaf-like aggregates and melts at 2S7-28So ; it is in- soluble in dilute solutions of the alkali hydroxides but when heated with excess of these reagents becomes converted into the alkali salt of tbe preceding benzoyl derivative.The action of benzoyl chloride on anthranilic acid in pyridine solu- tion also leads to the formation of the inner anhydride which in this case is benzoylanthranil. G. T. M. Substituted Aminobenzyl Cyanides and Iminobenzoyl Cyanides. By FRANZ SACHS and MAX GOLDMANN (Bey. 1902 35 3319-3361).-A continuation of previous work (Abstr. 1899 i 884 and 1901 i 272). The general methods of preparing substi- tuted aminobenzyl cyanides CN-CHPh-NHR and their oxidation products the iminobenzoyl cyanides CN*CPh:NR are described in detail.I. Devivatives of Priniuq Monoun&es.-Anilinobenzyl cyanide (Zoc. cit.) yields a ?tityoso-derivative CN*CHPh*NPh*NO which crystallises in clusters of needles melts at 55O and when treated with benz- aldehyde benzotrichloride and zinc chloride for rns derivatives of triphenylmethane. p-Toluidinobenzyl cyaaide crystallises from light petroleum in prisms melting at l l O o and the m-compound in trans- parent leaflets melting at 97". m-Z'olyliminobenxoyl cyanide crystal- lises i n yellow needles melting at 43'. a-Napl~thylamiitobelnzyl- cyanide crystallises in leaflets melting at 113O and the corresponding imznobenxoyl cyanide in lemon-coloured needles melting at 1 0 3 O .P-2Crup?~thyZaminobenzyZ cyanide crystallises in colourless clusters of laminze melting at 1 19-120° and the irninobenxoyl cyunide in small yellow rods me1 ting at 124". p-Bromoanilinobenx?/l cyanide crystallises in white leaflets melting at 99" and the corresponding oxidation pro- duct in yellow felted needles melting at 1 ISo. o-Carboxyanilinobenzyl cyanide and the corresponding acid (this vol. i 467) are completely destroyed by permanganate. The potassium salt of p-sulphanilinobenzyl cyanide was obtained as a crystalline,'white powder and the potassium salt of p-sulphophenyl- iminobenzoyl cyanide as lustrous long pale yellow prisms. m-Nitro- anilinobenzyl cpaide crystallises in Cine yellow needles melting at log" yields a nityosoarnine which crystallises in yellowish compact prisms melting and decomposing at 90-9lo and when hydrolysed the corresponding acid which crystallises in slender yellow needles meltsORGANIC CHEMISTRY. 781 at 151° and forms a nnitcosoamine melting at 156O ; m-nitrophenylimino- benxoyl cyanide forms long yellow feathery silky crystals melting a t 120'. p-NitroanilinoberLxyl cyunide crystallises in bright yellow rhombic laminze melting a t 1%" and the axomethine in long lemon-coloured prisms melting a t 128".11. Derivutives of Diumines and Aminopheno1s.-p-YhenyZenediumino- dibenxyl cyanide C,H,(NH*CHPh*CN) crystallises in microscopic prisms melting a t 163" and its oxidation product in orange-yellow prisms melting at 233'. The condensation product of acetyl-p-phenyl- enediamine and mandelonitrile crystallises in quadratic leaflets melting a t 180° and its oxidation product in orange-red needles melting a t 146".The corresponding compounds from benzoyl-m-phenylenediamine and mandelonitrile were also prepared ; phenyl-p-cy&nazomethine-3- benxoyluminophenyl CN*CPh:N*C,H,*NH*COPh crystallises in yellow needles melting a t 139". The hydrolysis of p-dimethylaminophenyl- aminobenzyl cyanide yields the corresponding amide which crystallises in straw-coloured needles melts a t 154-155' is readily oxidised to the corresponding axomethine which crystallises i n orange-yellow needles and melts and decomposes at 170° and when hydrolysed yields benzylidene-paminodimethylaniline. p-Hydroxyanilznobenxyl cyanide crystallises from alcohol in white leaflets but is very unstable as it readily evolves hydrogen cyanide and yields benzylideneaminophenol.p-Ethoxyanilinobenxyl cyanide crystallises in yellow rhombic laminae melts a t 8 5 O and when oxidised yields phenyl-p-cysnazomethine-4- h y droxy pheny 1. Benzidine condenses with benzylidenecyanohydrin forming bis-a cyurco- benzyl-p-cliaminodiphenyl which crystallises in octahedra melts at 201-202' and when oxidised yields the corresponding axomethine which crystallises in yellow needles and melts at 252". 111. Derivatives of Aminoaxo-compound8.-p-Axophnyl-a-cyanobenxyl- ccniline crystallises in bronze-coloured needles melts a t 11 6' and forms a platinichloride which crystallises in large red laminze with a metallic lustre ; the corresponding uxomethine forms an orange-red crystalline powder and melts a t 138-139'.The analogous compound from benzeneazo-P-naphthylamine crystallises in red lamin2e melting at 142" and the uzomethine in small needles which decompose at 198'. Benzylidenecyanohydrin and benzeneazo-a-naphthylamine condense forming a colourless compound C,,H17N,,. of undetermined constitu- tion which melts at 198O and is probably identical with the compound obtained by Goldschmidt and Rozell (Abstr. 1890 i 614) by the con- densation of benzaldehyde aud benzeneszo-a-naphthy lamine. IV. Derivatives of Secondary Monoumines. - MethylanilinobenxyZ cyanide crystallises in compact white prisms melting at 67' forms an unstable nitrosoamine which crystallises id yellowish-green plates de- composing a t 80-83" and a mononitro-derivative which melts nt 12 7'.The axomethine N0,*W,H,*C(CN):N*C6H,*NMe*CHPh*CN is a dark red crystalline powder which melts and decomposes a t 174'. The umide obtained by the hydrolysis of methylanilinobenzyl cyanide crystallises in white needles melting at 133" and forms a more stable nitroso-derivative which decomposes at 185-1 86' a p-nitro-derivative VOL. LXXXII. i. 3 i792 ABSTRACTS OF CHEMICAL PAPERS. which melts and decomposes a t 210° and a dinitro-derivative which decomposes at 170-1 72". The azomethine NO,* C,H,* C( CN ) N* C,H,*NMe*CH Ph* COO NH crystallises in small dark purple pyramids sinters a t 1 8 2 O and de- composes a t 200O. Ethylanilinobenxyl cyanide is an oil which yields a crystalline amide melting at 135". Benxylaminobenzyl cyanide crystallises in white needles melting at 134'. The triphenylmethane derivatives nitroso- amines and condensation products with nitrobenzyl cyanide of these two nitriles and their amides were also investigated. Attempts to obtain the corresponding acids from these amides were unsuccessful. R.H. P. Dibromocinnamic Acids and Dihalogen-indones. By A. GLAWE (Ber. 1902 35 2936-2940).-By the action of concentrated sulph- uric acid P-dibromocinnamic acid is converted after twenty hours the dibromoindone into dibromodiketohydrindene C6H4<CO>CBr2 co co C,H4<CBl>CBr which is first formed being also converted into the same compound. a-Dibromocinnamic acid behaves in a similar manner but only when heated to 110" Dichloroindone does not behave in this way.Bromodimethoxylbydrindone C6H4<$:2>CBr prepared by the action of sodium methoxide on dibrornoLndon6 crystallises from dilute methyl alcohol and melts at 79". The corresponding chloro-compound melts a t 85". Bromodiethoxyhy drindone C6H4<~$~$~>CBr separates from dilute alcohol as a white crystalline powder and melts a t 60-61O. Cldoroethoxyindone C,H,<&~~~>CCI which results from the action of sodium ethoxide on dichloroindone crystallises from alcohol in yellow needles and melts a t 69-70' ; chlorodiethoxyhydrindone appears aIso to be produced. Dinitrocinnamic Acid. By PAUL FRIEDLANDER and R. FEITSCH (Monatsh. 1902 23 534-542. Compare Abstr. 1885 1137),-o-p- Binitrocinmamic m i d prepared by Perkin's reaction from op-dini tro- benzaldehyde crystallises from water or toluene in light yellow needles melts at 179" is easily soluble in hot water benzene alcohol or glacial acetic acid and dissolves on warming in sodium acetate solution.The sodium potassium ammonium barium zinc ailver Zead iron mangunese and cobalt salts are described j they all explode when heated. The ethyl ester crystal!ises from dilute alcohol in yellow needles melts' at 94" is insoluble in water or light petroleum and easily soluble in benzene or alcohol. C,H,( NO,),*CHBr*CHBr*CO,H formed by combination of bromine and op-dinitrocinnamic acid crystallises from dilute alcohol in large yellow needles melts at 212" is easily soluble in alcohol ethyl acetate or glacial acetic acid is par. T. M. I; The dib~omide,ORGANIC CHEMISTRY. 783 tially decomposed by hot water and on addition of sodium hydroxide t o the cold alcoholic solution immediately yields sodium bromide.Reduction of op-dinitrocinnamic acid with ferrous sulphate and ammonia leads to the formation of a reddish-brown amorphous pre- cipitate On reduction with stannous chloride and hydrochloric acid aminocarbostyril is formed which crystallises from dilute alcohol in long colourless needles becomes gradually red in colour melts above 250" is easily soluble in alcohol glacial acetic acid or hot water less readily so in cold water is dibasic and forms crystalline salts. op-Dinitrobenzylidenentnlonic acid C,H,( NO,),*CH:C(CO,H) formed by the action of dinitrobenzaldehyde on malonic acid in presence of acetic acid crystallises fram water in colourless delicate crystals con- taining 1H,O melts a t 49'; the anhydrous acid melts at 167" but evolves carbon dioxide slowly at 150".The b a ~ i u m and silwey salts are described The diethyl ester formed from dinitrobenzaldehyde and diethyl malonate in presence of piperidine crystallises from benzene in colourless needles and melts at 97". G. Y. Synthesis of Polycyclic Hydrocarbons. By MAURICE DEL- ACRE (BUZZ. SOC. Cluim. 1902 [iii] 27 875-S82).-By the action of ethyl trichloroacetate on benzene in presence of aluminium chloride the author has obtained fluorenecarboxylic acid which is sparingly soluble in the ordinary solvents ; the solutions are generally fluor- escent. If slowly heated the acid melts at 209-21Oo but if i t is first plunged into a bath heated t o 180" i t does not melt until 216-217O.It readily sublimes at 200' and undergoes decomposition a t 2S0-290° carbon dioxide being evolved and fluorene formed. The fluorene so obtained crystallises from alcohol in dazzlingly white pearly scales melts at 1 1 5 O and is quite unaltered by light. The acid obtained i n this manner agrees in properties with that obtained by Fried- lander (Abstr. 1877 492) but the ethyl ester obtained from i t is quite diflferent forming glassy crystals which melt at 60" and are very soluble in alcohol The above synthesis appears t o be a general one and applicable t o the formation of substituted fluorenes. A. F. Affinities of the Halogenated Hydroxybenzoic Acids in Relation t o their C o n s t i t u t i o n .By ANGELO COPPADORO (Guxxatta 1902 32 i 537-572).-The author has measured the affinities of a large number of derivatives of benzoic acid containing at the same time one or more halogens and hydroxyl groups. The entry of a hydroxyl group into benzoic acid in either the ortho- or meta-position produces a n increase in the affinity constaut whilst in the para-position a diminution takes place ; when other hydrbxyl groups now enter the molecule they produce in some cases a n increase in others a decrease in the affinity constant. Ostwald's method was used in the author's measurements the temperature employed being 25". The melting points of the acids exzmined are given in brackets. 5-Chlorosalicylic acid (172") is 1.9 times as strong as salicylic acid ; 3 5-dichlorosalicylic acid (219*5O) 2.4 times as strong as 5-chlorosali- cylic acid ; 5-chloro-2-ethoxybenzoic acid (21 So> 1.6 times as strong 3 i 2784 ABSTRACTS OF CHEMICAL PAPERB.as 2-methoxybenzoic acid ; and 3 5-dichloro-2-methoxybenzoic acid (166*5' 10 times as strong as 5-chloro-2-ethoxybenzoic acid. 2-Chloro 3-hydroxybenzoic acid (156-157') and 6-chloro-3-hydroxy- benxoic acid (178') have equal affinity constants which are almost the same as that of 6-chloro-3-methoxybenzoic acid (1 68-1690) ; 2 6-dichloro-3-hydroxybenzoic acid (122-124') has an affinity about 16 times as great as these. 2-Chloro-6- bromo-3-hydroxybenzoic acid (116-118') has almost the same affinity as 2 6-dichloro-3-hydroxy- benzoic acid which confirms the constitution given by Martini (this vol.i 150). Only about 1-1.5 per cent. of these acids are esteritied by Fischer and Speier's method (Abstr. 1896 i ZOl) whilst Martini's 6-chloro-2-bromo-3-hydroxybenzoic acid (1 94- 195') (Zoc. cit.) has an affinity 12 times as great as those of its two isomerides and can be esterified to the extent of more than 70 per cent. by either V. Meyer's or Fischer and Speier's method; hence the bromine atom cannot be in the position 2 but must be at either 4 or 5. 3-Chloro-4-hydroxybenzoic acid (169-170O) has an affinity constant about double t h a t of p-hydroxybenzoic acid ; this is about the same change as is produced when a chlorine atom enters in the meta-position to the carboxyl in either benzoic or salicylic acid. The two dichlaroprotocatechuic acids ( +.3H20 220') and (239') show when the dilution is great almost equal ailinities and these are about the same as that of dichloroveratric acid (182-183').The methyl (+ 1.$H20 193') and ethyl (+ 24H,O 155') esters of gallic acid have about equal dissociation constants greater than that of pyrogallol. The affinity of the methyl ester of monochlorogallic acid (+H,O 159-160') is about 2.6 times and that of the ethyl ester ( + H,O 106-107') about twice that of t,he corresponding gallic ester. The methyl (+ l$H,O 160-170') and ethyl (+ liH,O 151-153') dichlorogallates have respectively 2.4 and 2-33 times the affinities of the above corresponding monochloro-compounds ; methyl dibromogallate (+ l&H,O 169') gives still higher values for the affinity constant. The results obtained with ethyl dibromogallate (+1$H20 137') and methyl (+lhH,O 162-163') and ethyl ( + 1 .$H,O 134-135') chlorobromogallates were unsatisfactory. T.H. P. Reactions of Hydrocoumarone. By JOHAKNES BOES (Chem. Centr. 1902 ii 370 ; from Apoth.-Zeit. 17 422).-Hydrocoumarone dissolves in concentrated sulphuric acid forming a yellowish-red solution. The sulphonic acid and its salts are difficult to obtain in a crystalline f0r.m. I~~drocoumaronesuZp~~onic chloi-ide cry stallises from alcohol in needles and melts at 8 lo. H~d./.ocounaaronesulphonunzi~~ C8H,0,NS crystallises from alcohol and melts at 163'. Attempts to isolate an isomeric sulphonamide failed. Hydrocoumarone resembles hydrindene in its behaviour towards halogens forming monohalogen hydrocoumarones which have penetrating odours and do not boil under the ordinary pressure without decomposition.When sodium hydrocoumaronesulphonate is fused with potassium hydroxide a hydroxy-compound is formed. E. W. W.ORGANIC CHEMISTRY. 785 Anesthetics. By CARL GOLDSCHMIDT (Chenz. Zed. 1902 26 743). -From p-phenetidine and its homologues and ethyl orthoformate compounds of the type of methenyldi-p-phenetidine have been pre- pared which have an anzesthetic action. From p-aminobenzoic acid and ethyl orthoformate by 10 minutes' boiling in alcoholic solution R compound C02H*C,H4;NH*CH:N*C6H4*C02H is obtained ; it melts a t 235" and is soluble In alkalis and alkali carbonates ; it acts both as a n anzesthetic and an antiseptic. The analogous compound froni m-aminobenzoic acid melts a t 250'.From athyl p-aminobenzoate and ethyl orthoformate the compound CO,Me*C,H,*NH*CH N*C6H4* CO,Me melting at 240" and the compound C'O,Me*C,H,*NH*CH(OEt) melting a t 209' are obtained. Methyl p-aminobenzoate reacts with formaldehyde in the presence of hydrogen chloride yielding the com- pound CO,Me*C,H,-NH*CH,Cl which with alkalis gives an amorphous -base. K. J. P. 0. Direct Conversion of Cinnamic Acid into a-Truxillic Acid. By C. N. Rrmm (Bey. 1902 35 2908-2909).-Liebermann (Abstr. 1895 i 470) showed that cinnamylidenemalonic acid was converted under the influence of light into an isomeric acid which the author (this vol. i 617) has proved t o be a tetramethylene derivative ; on oxidation the latter yields a-truxillic acid Since both cinnamic and a-truxillic acids are found in the leaves of Erythroxylon coca it seemed possible that the action of light on the former gave rise to the forma- tion of the latter acid.Very finely powdered cinnamic acid was exposed t o light for three-and-a-half weeks during which however there were only 50 hours of bright sunshine. Seventy per cent. of the acid was found to have been changed into a-truxillic acid CI8Hl6O4 which crystallised in needles melting at 275' and yielded a methyl ester (m p. 173'). On distillation cinnamic acid is re-formed. K. J. P. 0. Dibromo-a-truxillic Acid. By R. KRAUSS (Bey. 1902 35 2931-2933).-Ethyl dibromotruxillate C22H290,Br crystallises from alcohol in colourless needles and melts at 124-126'. The acid C1,H1,O,Br2 crystallises from acetic acid in small colourless needles melts a t 260-264' does not reduce permanganate but when distilled is converted into bromocinnamic acid which can then be oxidised t o (p)C6H4Br*FH*FR*CO2H p-bromobenzoic acid.The constitution is therefore assigned to the acid. CO,H* CH* CH-C!H4Br(p) T. M. L. Dyes of the Esculetin Series. 11. By CARL LIEBERMANN~~~ 8. LINDENBAUM (Ber. 1902 35 2919-2923. Compare Abstr. 1901 i 736).-When reduced in small quantities with sodium amalgam at 100" in a stream of carbon dioxide aesculetin gives hydrosesculetin and mscztletirt dihydride C,H,O ; the latter which was separated by ex tracting the acidified solution with ether crystallises from hot water in white flakes and melts a t 198-200'; it is only slightiy soluble in cold but dissolves easily in hot water and partially remains in'786 ABSTRACTS OF CHEMICAL PAPERS.solution ; similarly when dissolved in ether i t separates as an oil and oniy becomes crystalline when heated ; it is therefore probable that i t adds on a mol. of water perhaps with formation of a trihydroxy- phenylpropionic acid 0-yo C6H2(0H)2<CH2. CH + H,O = C,H,(OH),*CH2*CH,*C0,H and is dehydrated on heating. The dihydride is not identical with Schiff's para-amuletin (Annulem 1872 161 84) and when treated with ammonia exhibits a striking series of colour reactions T. M. L. 1 :2-Diketopentamethylene (A2-cycloPentene-l-one-2-ol) and Derivatives. By WILHELN DIECKMANN (Ber. 1902,35,3201-3217). -Ethyl 1 2-diketopentamethylene-3 5-dicarboxylate (Abstr. 1894 i 324) CH,< C(Co2Et):(?*oH ,has strongly acid properties; its aqueous alcoholic solution reddens blue litmus it dissolves in dilute alkalis and alkali carbonates and also dissolves readily in sodium acetate solution; dry ammonia precipitates the ammonium salt as a colourless powder ; it is stable towards alkalis and is not hydrolysed by concentrated C( CO Et) y*ONa is hydrochloric acid ; the sodium derivative CH2< C(C0,Et) :C*ONaf only slightly soluble in excess of alkali and is obtained either anhydrous or with 14H20 ; the iron salt forms a dark brownish-red crystalline powder which dissolves sparingly- with a violet coloration in ether.The copper derivative C,,H,,O,Cu is a clear green crystalline salt insoluble in all solvents and melts at 230". The oscmone C,,H1,O,N crystal- lises from alcohol in minute yellow needles and melts at 112'.The phenc&ae Cl7H,,O4N separates on warming an alcoholic solution of the ester with o-phenylenediamine in minute yellow needles crystal- lises from alcohol and melts at 204'. CH"C(Co,Et)=C.o€€ C(CO,Et):C*OH The rnononnilide CH(CO,Et)*y:NPh or CH,< C(CO,Et):y*NHPh ' C(C0,Et) C O H separates from methyl alcohol in yellowish crystals melts at 107O dissolves in alkalis and is precipitated unchanged by acids. 1 2-Diketopentamethylene CH,< '* :?'OH (Abstr. 1897 i 462) is best prepared by hydrolysing the ester with 20 per cent. sulphuric acid ; it is oxidised by alkaline hydrogen peroxide to glutaric acid. The benxogll derivative,. CH C'oBz separates from methy1 CH,* CO alcohol in colourless crystals and melts a t 72-73O.Thephenylwethane CH ' ?*o*Co*NHPh crystallises from benzene and melts at Y 122". The phenccaine derivative CH2<CH2*(?iN>C6H4 separates C H,*C.N from alcohol or water in colourless needles k e l t s at 102-103" and distils without decomposition at about 290" ; its solubility in water reaches a maximum at 70".ORGANIC CHEMISTRY. 787 Phenylaxo-1 2-diketopentametly Zene FH2' CH2>C N NHPh co-co or yH2-cH2>C*N:NPh forms a red crystalline precipitate melts at CO C(OHb 1 30° &nd 'dissolves readily in alkalis and alkali carbonates. ccl ' ?'OH is probably identical with the compound which Hantzsch (Abstr. 1889 853) described as chloro-1 3-diketopentamethylene. Cldoyodibromo-1 2-di- ketopentamethyler probably CH2<CC1=(?*oH prepared by brominat- ing the preceding compound crystallises from carbon tetrachloride or water and melts a t I2.1-122O. 3-Anilino-1 2-diketopentamethylere- CH,<OH2*C0 3-Chloro- 1 ; 2-diketopentctmethglene CBr2*C0 2-monoanil hgdrocldoride CH,< CH,*c NHPh prepared by the CO-C*NHPh,HCl action of aniline on a solution of the chloro-compound in acetic acid forms yellow crystal flakes and becomes brown and decomposes and melts a t 260'.3 5 Ei-Tdwomo- 1 2-diketopentamethylene forms colourless crystals and melts a t 155'. 3-Bromo-1 2-diketopenturnethylene melts at 155'. T. M. L. Acetylation of Cochenillic Acid. By CARL LIEBERMANN and S. LINDENBAUM (Ber. 1902 35 2910-291 9).-An acetylcochenillic anhy- dride OAc*C,HMe(CO,H)<~>O [4 6 1 2 3 or 4 6 3 1 21 is obtained by acetylating cochenillic acid with a mixture of acetic anhydride and acety! chloride; it crystallises from acetic acid in colourless plates and melts and decomposes a t 152-153'.The silver salt C,,H707Ag forms minute white needles is somewhat soluble in water and is readily decomposed. OAc*C,HMe( C O ~ ! k ) < ~ ~ > o from the silver salt and methyl iodide crystallises from ether in plates and melts a t 136-138'. Dimethyl acetylcochenillate OAc*C,H(C0,Me),*C02H prepared by boiling the preceding substance with methyl alcohol crystallises from ether and melts at 149'. By acetylating with acetyl chloride only an ucetylcochenillic acetic arnhydride OAc*C,BMe( CO,H),*CO*OAc was obtained in large clear crystals which gradually became opaque ; it softens and melts with decomposition at 230'.When exposed to air it is hydrolysed into acetic acid and acetylcochenillic acid ; the latter melts at 118-124O resolidifies and melts again with decomposition at 230'. Trimethyl acetylcochenillate OAc*C,HMe(CO,Me) prepared by heat- ing the preceding compound with silver oxide and methyl iodide crys- tallises from dilute acetic acid in needles and melts a t 106-108'. It is hydro1 ysed by decinormal sodium hydroxide giving tyimethyl cochenillate OH*C,HMe(CO,Me) which fsrms white needles crystallises from water melts a t 136-13So and gives a violet coloration with ferric The methyl ether,788 ABSTRACTS OF CHEMICAL RAPERS. chloride. By heating acetylcochenillic acid or its acetic anhydride at 70-80' an acetylcocJLenillic anhydride is obtained isomeric with that described above; it melts at 140-148° and on exposure to air is hydrolysed to acetylcochenillic acid ; the latter when heated a t 1 IS0 is converted by the loss of a mol.of water into cochenillic anhydride OH*C,HMe(CO,H)<~~>Oj melting a t 215-223' with decomposi- crys- tion. Benxoylcoclmwillic anhydride OBz*C,HMe(C02H)<CO>0 co tallises from benzene and melts at 187-189'. T. 33. L. Action of Light on Cinnamylidenemalonic Acid. By ELMER P. KOHIIER (Amer. Chem. J. 1902 28 233-240).-An investigation of the white compound obtained by Liebermaqn (Abstr. 1895 i 470) by the action of light on cinnamylidenemalonic acid has shown that i t is a diphenyltetrarnethylenebismethylenemalonic acid C(C0,H)2:CH*CH<~Hph>cH*cH:C(C02H)2 CHPh a conclusion already arrived at by Riiber (this vol.i 617). This acid readily combines with 2 mols. of hydrogen chloride; when its solution in methyl alcohol is saturat,ed with hydrogen chloride a methyl ester C,,H,,O,Cl is produced which is soluble in hot acetone crystallises in thick needles and melts and decomposes a t 19'7-1 98' ; the correspond- ing ethyl ester C,oH3,0sC12 melts and decomposes a t 185'. When the acid is treated with bromine an unstable additive compound is pro- duced which decomposes with elimination of carbon dioxide cind hydrogen bromide and formation of diphenyltetramethylenebisbromo- methyleneacetic acid C 0 2 H * C H C B r * C H < ~ ~ ~ ~ > C H * CBr CH*CO,H ; the last-mentioned substance crystallises in colourless plates melts and decomposes a t 245O is readily soluble in alcohol or acetone and yields a-truxillic acid on oxidation with alkaline permanganate ; its methyl ester melts a t 115'.Diphenyltetramethylenebismethylenemalonic acid unites with 2 mols. of potassium hydrogen sulphite with forma- tion of an additive compound. When the acid is dissolved in concen- trated sulphuric acid and the solution is poured into water cinnamyl- idenemalonic acid is precipitated. E. G. Study of Lichens. X. By WILHELM ZOPF (Annalen 1902 324 39-78. Compare Abstr. 1899 i 716).-The name proto- lichesteric acid is given to a colourless acidic substance obtained from Cetraria cucullata this lichen yielding 2.2 per cent. of the compound whilst C. chlorophylla furnishes only 0.5 per cent.; this acid can also be extracted from C .complicata and C. islandica provided that ether is employed and not alcohol the latter solvent causes the transformation of the subtance into its isomeride lichesteric acid (m. p. 124-125O); this cbange is also effected by hot acetic anhydride. Protolichesteric acid C,,H,,O crystallises from benzene light petroleum ether or alcohol in nacreous rhombic leaflets melting a t 103-104O. When separating slowly from dilute alcoholic solutions i t assumes the form of pyra- midal hernimorphous rbombic crystals having an extinction parallelORGANIC CHEMISTRY. 789 to the principal axis The acid has aD 12.1' a t 1 9 * 5 O it dissolves in sodium hydrogen carbonate solution and in the presence of alkalis immediately decolorises potassium permmngmate.Mineral acids re precipitate the unchanged substance from its solutions in the alkali hydroxides and although partly transformed into amorphous products protolichesteric acid is not converted into lichesteric acid when heated above its melting point. I n C. chlorophylla protolichesteric acid is accompanied by a small quantity of atranoric acid C. complicata also furnished protocetraric I-usnic and atranoric acids. The lichesteric acid isolated from C. isladdica by Schnedermann and Knop is in reality the product of the transformation of protolichesteric acid and when ether or benzene is employed in the extraction only the latter substance is obtained. The amorphous dilichesteric acid extracted from C. islandica var. vulgccris by Hesse is a decomposition product of protolichesteric acid formed by treating the latter substance with glacial acetic acid a t 80".C. tubulosa (C. juniperina var. tubulosa) yields usnic vulpic and pinastric acids the last being identical with the substance isolated from C. pinastri. I n addition to these compounds C. tubulosa furnishes a new substance cetrariulic acid which separates in lustrous pale olive- brown leaflets sparingly soluble in cold alcohol ether or benzene but dissolving more readily on warming. I n dilute potassium hydroxide solution the new acid dissolves with evolution of gas; it is also soluble in an aqueous solution of sodium hydrogen carbonate. Barbatic acid isolated from Usnea longissima (Abstr. 1898 i 99) forms a characteristic sodium salt which crystallises in rosettes of flattened curvilinear needles.U. cornuta yields d-usnic and usnaric acids the latter in larger quantity. U. ceyatina obtained from the pine trees of the Black Forest a t an altitude of 700-800 metres furnishes only barbatic acid and a trace of usnic acid ; this result is contrary to that of Hesse (Abstr. 1895 i 298) the latter observer stating that barbatin and a large quantity of usnic acid are obtainable from the lichen. U. dasypoga accompanies the preceding species and yields barbatic d-usnic and usnaric acids but not alectoric acid (compare Hesse Abstr.; 1900 i 149). Parmelia sinuosa contains dusnic acid and probably usnaric acid. Thamnolic acid a substance isolated from Tharnnolia uermicularis when heated a t 50-60' with concentrated hydrochloric acid yields thamnolin a reddish-brown microcrystalline substance dissolving in hot water alcohol chloroform or glacial acetic acid to a red solution.This product is also sparingly soluble in ether or benzene and develops a reddish-brown coloration with ammoniacal or alkaline solutions ; it is reprecipitated by hydrochloric acid but not by carbon dioxide. Cladina uncialis contains d-usnic and thamnolic acids the former being identified by conversion into usnolic acid and the latter by the thamnolin reaction. Squamatic acid hitherto only obtained by Hesse from Cladonia spuamsa has also been isolated from C'. glauca. The presence of patellaric acid in Urceolaria scruposa has been con- firmed; it crystallises from 50 per cent. alcohol in flattened plates and decomposes at 165'. This acid gives a bluish-red coloration with19 0 ABSTRACTS OF CHEMICAL PAPERS.bleaching powder and also develops an intense blue coloration with a solution of barium hydroxide or hydrated barium peroxide. Lecanoric acid has the same melting point and develops a similar coloration with bleaching powder but not with barium hydroxide or peroxide. Olivetoric acid develops a bluish-green coloration with the latter of these reagents but not with the former. Patellaric acid dissolves in sodium hydrogen carbonate and cold barium hydroxide solutions without decomposition and acids regenerate the unaltered substance ; when heated with dilute potassium hydroxide solution it develops a yellow coloration which then becomes red and on adding a few drops of chloroform the liquid acquires a deep green fluorescence which is rendered more distinct by cooling and diluting.Lecanoric and atranoric acids could not be detected in the extracts from U. scruposa. G. T. M. Reduction of Carboxylic Derivatives to Aldehydes and their Derivatives and to Amines. By FRANZ HENLE (Ber. 1902 35 3039-3044).-The hydrochlorides of the imino-ethers are readily reduced by sodium amalgam and dilute acids t o the corresponding aldehydes. If the redyction be carried on in presence of phenyl- hydrazine or semicarbazide the corresponding hydrazone or semicarb- azone is obtained. Benzimino-ethyl ether hydrochloride is readily converted in this way into benzaldehyde the yield amounting to 23.5 per cent. of the theoretical.In the presence of phenylhydrazine the yield of benzylidenehydrazone is quantitative and this reaction can readily be demonstrated a voluminous precipitate of the hydrazone being formed. I n the presence of semicarbazide a yield of 52 per cent. of the theoretical amount of semicarbazone is obtained. I n a similar manner acetimino-ethyl ether hydrochloride yields 40 per cent. of the theoretical amount of ethylidenephenylhydrazone. I n the absence of phenylhydrazine the chief reaction is the hydrolysis of the imino-ether but a certain amount of acetaldehyde is also produced. Since phenylhydrazones can be reduced to amines this reaction affords a new method of passing from the nitriles to the primary amines all the operations being carried out at low temperatures.Benzamidine hydrochloride is reduced by sodium amalgam and hydrochloric acid to benzylamine the yield amounting to 38 per cent. of the theoretical. A. H. up-Dinitrobenzaldehyde. By PAUL FRIEDLBNDER and PAUL CORN (Monatsh. 1902 23 543-562).-op-Dinitrobenzpl chloride is obtained in an almost quantitative yield when pnitrobenzyl chloride is nitrtited with a slight excess of nitric acid in concentrated sulphuric acid (compare Krassusky J. Russ. Phys. Chem. Soc. 1895 27 335). It forms rhombic crystals melts a t 34" is insoluble in water spar- ingly soluble in light petroleum but easily so in other ordinary solvents. It has little odour and is only slightly volatile with steam op-Dinit~o6enxyZaniEine formed from op-dinitrobenzyl chloride and aniline in alcoholic solution crystallises from benzene in orange-red crystals melts at 132" and forms a hydrochloride which crystallises inORGANIC CHEMISTRY.701 colourless needles or leaflets and is dissociated by water and a pkutinichZol.icle which is easily soluble in water. op-Dinitrobenxyl-p- toluidine crystallises from alcohol in delicate red needles and melts a t 93'. op-Dinitrobenxyl-a-nu~J~tl~ylunaine crystallises from glacial acetic acid in dark red scales and melts at 164'. op-Binitrobenxylaniline-p- sulphonic m i d crystallises in yellow needles is moderately soluble in water and less readily so in alcohol; the bwium and silver salts are described. op-Dindp*obenzyZ acetate crystallises in glistening four-sided thick plates melts at 96-97'? is easily soluble in .alcohol benzene or glacial acetic acid but insoluble in light petroleum and is hydrolysed by dilute sulphuric acid t o op-dinitrobenxpl alcohol which crystallises from alcohol in glistening lemon-yellow needles melts at 114-115" and is easily soluble in alcohol benzene or glacial acetic acid but insoluble in light petroleum.The action of nitric acid on p-nitrobenzyl alcohol dissolved in sulphuric acid leads to the formation of p-nitrobenzyl nitrate and not of dinitrobenzyl alcohol. p-Nitrobenxyl hydrogen sulpliute is formed when the alcohol is dissolved in concentrated sulphuric acid. op-DinitrobenxaldeJhyde formed by oxidation of dinitrobenzylaniline- sulphonic acid with sodium dichromate in sulphuric acid solution crystal- lises from a mixture of benzene and light petroleum in glistening plates which become matt on exposure to light melts a t 68-69' is easily soluble in most solvents but sparingly so in water or light petroleum and is only slightly volatile with steam.When warmed with sodium carbonate solution the aldehyde is decomposed with formation of a brown substance ; with scdium hydrogen sulphite it forms a crystalline compound easily soluble in water an$ with phenylhydrazine in alcoholic solution i t forms a phenyliqdraxone which crystallises in reddish- brown hair-like needles melts a t 227-228" and is sparingly soluble in the usual solvents. op-Dinitrobenz~liden~aniZine formed from dinitro- benzaldehyde and aniline crystallises from glacial acetic acid in thick glistening orange-yellow needles melts a t 131-132" .and is easily soluble in benzene or acetic acid more sparingly so in alcohol.op-Di- nitrobenx~lidene-p-tol~id~ne crystallises from glacial acetic acid in yellow needles and melts a t I 5 1'. op-Dinitrobenxylidene-a-naphthyl- arnine crystallises in orange-red needles melts a t 202" and is sparingly soluble in alcohol or glacial acetic acid. op-Dinitrobenxaldoxirne crystallises from hot water in glistening silky needles melts a t 127-128° and is easily soluble in benzene with a slight green colour in the usual solvents and in sodium hydroxide solution. The benxoyl derivative crystallises from glacial acetic acid in small slightly yellow needles sintcrs and melts at 165-166'. On prolonged boiling with acetic anhydride the aldoxime is converted into dinitrobenzonitrile which crystallises from alcohol in glistening slightly brownish-yellow rhombic plates melts at 104-105" and is easily soluble in ether alcohol or benzene but less readily so in carbon disulphide.op-Dinitrobenxarnide formed from the nitrile by the action of warm concentrated sul2huric acid crystallises from water in long glistening slightly green needles melts at 203-204' and is converted by nitrous acid in 50 per cent. sulphuric acid solution info dinitrobenaoic acid which is also formed792 ABSTRACTS OF CHEMICAL PAPERS when dinitrobenzaldehyde is boiled with silver acetate in acetic acid solution. o-Xitroso-p-nitrobenzoic acid is formed from dinitrobenzaldehyde when i t s solution in benzene is exposed to direct sunlight. The nitroso-compound crystallises from ethyl acetate in glistening slightly greenish-yellow leaflets melts above 300° and is sparingly soluble in the usual solvents forming grass-green solutions when warmed.With aniline i t forms a yellowish-red azo-compound and with methyl sulphate a methyl ester which crystallises from dilute acetic acid in glistening yellow silky needles melts .at 137-138" and is more soluble than the acid. G. Y. Condensation of Methyl Propyl Ketone with Benzaldehyde. By CARL D. HARRIES and P. BROMBEBGER (Her. 1902,35 3088-3090). -When these substances react in presence of dilute sodium hydroxide solution beneylidenemethyl propyl ketone CHPh:CH*UOPr is formed as a yellowish oil which boils a t 275" and has a sp. gr. 0.9979 a t 17" ; its phenylhydraxone melts at 99-100° i t s semicaybaxone a t 150° and its oxime at 97".The oxime gives a dibromo-compound (m. p. 158') when treated with bromine. On reductlon i t yields the corresponding saturated ketone as a colourless oil which boils at 130" under 18 mm. pressure and has R sp. gr. 0.9614 at 17". In presence of hydrochloric acid the condensation takes place to benxylidenepropyl methyl ketone CH,Me*C(CHPh)*COMe a yellow oil which distils a t I2O-13O0 under 18 mm. pressure and has a sp. gr. 1.0216 at 17". I t s oxime melts at 8 5 O its phenplhydraxone at 86") and its semicarbuxone at 207". J. McC. [Derivatives of] Hydroxybenzophenone. By FRITZ ULLMANN and IRMA GOLDBERG (Ber. 1902 35 2811-2814. Compare Graebe and Ullmann Abstr. 1896 i 440).-o-Hydroxyphenyl p-tolyl ketone OH*C,H,*CO*C,H,Me produced by condensing o-methoxybenzoyl chloride with toluene in the presence of aluminium chloride separates from alcohol in large crystals melting at 61.5" and dissolving in sodium hydroxide solution t o form a yellow sodium derivative; the benxoyl derivative melts at 80' ; the phenylhydraxone and the dibrorno- compound form yellow crystals melting at 145" and 132.5' respectively; the oxime is a white substance melting at 175".3 -Methoxybenzophenone OMe- C,H,* COPh prepared from m-methoxybenzoyl chloride and benzene boils at 342-343O under 730 mm. pressure and solidifies to a crystalline mass melting at 37"; it is hydrolysed to 3-hydroxybenzophenone by hydrobromic acid. 4-Methoxy benzophenone OMe*C,H,*COPh obtained by employing .p-methoxybenzoyl chloride in the preceding condensations boils at 354-355" under 729 mm.pressure (compare Gattermann Abstr. 1890 962). G. T. LM. Synthesis of Two Benzoylxylenols. By PIETRO BARTOLOTTI and ADOLFO LINARI (Gaxxetta 1902 32 i 494-503).-6-Benxoyl- 1 4 2-xylenoZ C H * C O * C 9 ~ ~ ~ ~ ~ ~ ~ ~ C H was prepared by firstORGANIC CHEMlSTRY. 793 behzoylating 1 ; 4 2-xylenol by Baumann's method then heating the benzoyl compound with benzoyl chloride and zinc chloride by which means benzoylxylenyl benzoate was obtained ; the latter compound was then hydrolysed with aqueous alcoholic sodium hydroxide. Benzoyl- 1 4 2-xylenol is deposited from alcohol in yellowish shining scales melting a t 166-167' ; it is soluble in alkali hydroxides giving a yellow coloration but in dilute alcoholic solution i t gives no coloration with ferric chloride.I t s acetyl derivative C17H1h03 separates from aqueous alcohol in large tabular colourless crystals melting at 62-62.5'. The methylether is a dense colourless liquid which boils at 194-195' under about 10 mm. pressure and is soluble in the ordinary solvents. Benxoyl-1 2 4-xyZenoZ C,H5*CO* C<gg:iig>CH prepared in a similar manner t o its isomeride separates from alcohol in yellow crystals which melt at 110-111' and are soluble i n the ordinary solvents ; it colours the alkali hydroxides yellow and i n . aqueous alcoholic solution gives a n intense black coloration with ferric chloride. I t s benxoyl derivative C,,H,,O is deposited from alcohol in colourless crystals which melt at 110' and a r e soluble in the ordinary solvents.The acety2 compound Cl7HI6O3 crystallises from dilute alcohol i n shining colourless scales melting a t 74-74.5'. The inethyl ether C,,H,,O separates from alcohol in colourless crystals melting a t 82.5-83". T. H. P. Hydroxy-derivatives of a-Naphthaquinone. By PAUL FRTED- LANDER and L. SILBERSTERN (Monatsh. 1902 23 513-533).- 1 8-AminonaphthoI formed by melting 1 S-aminonaphthalene- sulphonic acid with sodium hydroxide (D.R.-P. 55404) crystallises from light petroleum in white needles becomes grey on exposure t o air and melts and blackens at 94-97'. The sulphate (CloH,ON),,H,SO separates from hot water i n very slightly soluble crystals; the hydrochloride is sparingly soluble in concentrated hydrochloric acid and forms colourless crystals which become grey on exposure to air.The ucetyl derivative OH*C,,H,*NHAc is soluble in .aqueous alkalis forins colourless crystals and melts at 138'. With diazotised sulphanilic acid in acetic acid solution aminonaphthol forms a red precipitate which on reduction with zinc dust and dilute hydrochloric acid and treatment with ferric chloride yields jugloe (8-hydroxy- a-naphthaquinone). Naphthazitrin (Will Abstr. 1895 i 668) is formed from 1 8-di- aminonaphthalene 1 8-dihydroxynaphthalene or 1 8-aminonaphthol by condensation with 2 mols. of diazotised sulphanilic acid and reduction and oxidation of the product. With sodium hydroxide and 1 mol. of methyl sulphate 2 3-dihydroxynaphthaleue yields a mixture of the mono- and dimethyl ethers. The dimethyl ether is formed quan- titatively by the action of 2 mols.of methyl sulphate. The monomethyl ether forms colourless needles melts at 108' has an odour resembling that of guaiacol is easily soluble in the usual solvents gives a green coloration with feri ic chloride in alcoholic solution and is volatile with steam. The dimethyl ether crystallises in colourless needles melts at 115-1 16" has a n intense odour and is slightly volatile with794 ABSTRACTS OF CHEMICAL PAPBRS. steam. The monoethyl ether melts at 109-110° the dietlql ether a t 96-97O. Genxeneuaodihydroxynaphthalene formed from 2 3-dihydroxynaph- thalene and 1 mol. of benzenediazonium chloride crystallises from alcohol in glistening needles and dissolves in alkalis t o a yellowish-brown solution which becomes bright yellowish-red on addition of acid.1-Amino-2 3-dilqdrox?jnapht?iuZene formed by addikion of 1 mol. of diazotised sulphanilic acid t o 2 3-dihydroxynaphthalene and reduction of the .product with stannous chloride and hydrochloric acid separates from hot water in small white crystals decomposes at about 230° and is soluble in aqueous alkalis and in acids. Oxidation of the amino- dihydroxynaphthalene by ferric chloride leads to the formation of a quinone C20H1007 (?) which decomposes at about 260° does not sublime dissolves in alkalis with a n intense bluish-violet colour is reprecipitated unchanged by acids and yields a tarry reduction product from which the quinone is re-formed by action of ferric chloride. The action of 2 mols. of diazotised sulphanilic acid on 2 3-dihydr- oxynaphthalene leads to the formation of a dye which gives greyish- violet solutions in acids reddish-violet in alkalis and is reduced by stannous chloride and hydrochloric acid to 1 4-diasnino-2 3-dihydroxy- nuplu9kdene which is unstable when free but forms a sulphate crystallising in glistening leaflets and yielding a n intensely blue precipitate when warmed in aqueous solution in contact with air.Oxidation of the diamino-base with ferric chloride leads to the formation of isonaphthazarin. Fusion of P-naphthol-3 6 8-trisulphonic acid (Abstr. 1883 737) with sodium hydroxide leads t o the formation of two dihydroxynaph- thalenedisulphonic acids. The one which forms a sparingly soluble sodium salt crystallising in delicate needles gives a rapidly fading blue coloration with ferric chloride and reduces silver nitrate must be 2 8-dihydroxynaphthalene-3 6-disu-lphonic acid as in dilute solution it gives an intense bluish-violet coloration and forms a dark blue pre- cipitate on addition of formaldehyde and concentrated hydrochloric acid.This reaction is found to be general for 2 8-dihydroxynaph- thalenes. 2 3-Dihydroxynaphthalene-6 8-disulphonic acid forms a solu'ble sodium salt and a sparingly soluble barium salt but gives a stable violet coloration with ferric chloride but yields no characteristic reaction with formaldehyde and concentrated hydrochloric acid. Prolonged fusion of the trisulphonic acid with sodium hydroxide results in the formation of 2 3 S-trihydroxynaphthalene-6-sulphonic acid; this reduces silver nitrate gives with ferric chloride a green coloration and with formaldehyde and Concentrated hydrochloric acid a deep violet coloration and precipitate.2 3 8-Trihydroxynaphthalene (D.R.-P. 1 l209S) formed by heating the sulphonic acid with sulphuric acid at 180° crystallises from xylene i n yellow needles melts at 176" is easily soluble in water alcohol or ether sparingly so in benzene or light petroleum gives a dark blue coloration with ferric chloride in aqueous solution and on warming with formaldehyde and hydrochloric acid forms a greyish-green precipitate. The triacetyl derivative forms green crystals melts at 143-144' and is easily soluble in benzene glacial acetic acid or alcohol more sparingly soORGANIC CHEMISTRY.795 in water ether or light petroleum. The trimethyl ether prepared by the action of methyl sulphate and sodium hydroxide crystallises from light petroleum in small prisms melts a t 127-12S0 is insoluble in alkalis and has on warming an odour resembling thymol. When coupled with diazotised sulphanilic acid in dilute acetic acid solution trihydroxynaphthalen6 forms an orange-red dye which in solution is changed to reddish-violet by sodium carbonate or ammonia t o bluish-violet by sodium hydroxide. On reduction of the dye with stannous chloride and hydrochloric acid a base is obtained which forms a sparingly soluble colourless crystalline szclphccte rapidly oxidised on exposure to air. Oxidation of the base with ferric chloride leads to the formation of a pzcinone C,,H,(OH),O which crystallises from dilute alcohol in small brownish-red crossed needles decomposes without melting a t a high temperature sublimes to a slight extent gives with sodium carbonate a violet coloration with sodium hydroxide a green coloration which disappears on warming and forms a diacetyl derivative which crystallises from dilute acetic acid in golden-yellow leaflets darkens a t 5 5 O and melts at 65-67'. Anthraquinone.By K. DAMMANN and LUDWIG GATTERMANN (Chem. Centr. 1902 ii 368; from Zeit. Fad. Textilchem. 1902 1 325-326).-The basic compounds formed by the action of dehydrat- ing agents on a-arylaminoanthraquinones have been regarded as acridine derivatives. This view is confirmed by the fact that the acridine derivative prepared from o-acridylbenzoic acid is identical with the compound obtained by the action of phosphoric acid on a-anilinoanthraquinone. This acridine derivative C,oH,,ON prepared in the one case by boiling a solution of o-acridylbenzoic chloride in carbon disulphide with aluminium chloride crystallises from a mix- ture of pyridine and methyl alcohol in orange-red leaflets and melts at 206'.E. W. W. By JAKOB MEISEN- HEIMER (Anncclen 1902,323,205-246),-Anthraqu~noneoxirnedimeth~Z- acetal C( O;Me),<:62>CXOH is prepared by heating nitroanthra- cene with a solution of potassium hydroxide in methyl alcohol dilut- ing the product with water and precipitating the oxime with carbon dioxide ; it crystallises from benzene or methyl alcohol in pale yellow needles melts at 171' and dissolves in the ordinary organic solvents but not in water ; the acetpZ derivative decomposes at 114'; the methyl ether separates in colourless crystals melting at 96' the benxyl ether crystallises in yellow needles and melts a t 69-70'.Anthra- quinoneoximediethylacetaZ obtained by the action of an alcoholic pot- assium hydroxide solution on nitroethoxydihydroanthracene OEt*CH<C6H4>CH*N02 CH separates from benzene in granular crystals and decomposes a t 112-1 73' AntiLra~zciiaoneoximemet~ylethylacetaZ is produced either by treating nnthracene ethyl nitrate with potassium hydroxide dissolved in methyl alcohol or by the action of an alcoholic solution of the alkali hydroxide on nitromethovydihydroanthracene ; it forms colourless crystals and decomposes a t 134-135'.G. Y. Reactions of A r o m a t i c Nitro-compounds. 6 4 6 4796 ABSTRACTS OF CHEMICAL PAPERS. CH Anthruptcinonedimethykccetal C(OMe)2<CGH4>C0 results from the oxidation of anthraquinoneoximedimethylacetal with a n alkaline solu- tion of potassium ferricyanide ; i t crystallises in transparent prisms melts at 1 2 9 O and is readily soluble in the ordinary organic solvents. When treated in methyl alcohol solution with a trace of dilute sul- phuric acid the preceding acetal yields anthraquinone. Anthraquinoneoxime results when the product of the action of methyl alcohol and potassium hydroxide on nitroanthracene is acidified with a mineral acid instead of carbon dioxide. Nitromethoxydihydroanthracene OMe*CH<C6H4>CH*N02 C H which is readily prepared by adding concentrated nitric acid t o anthracene suspended in benzene and methyl alcohol yields a n unstable pot- assium derivative cry stallising i n colourless lustrous needles ; this substance dissolves in water or methyl alcohol but on prolonged heat- ing with these solvents it decomposes yielding nitroanthracene ; it may also be crystallised from benzene.This derivative is also ob- tained by shaking together powdered nitroanthracene and a methyl alcohol solution of potassium hydroxide. When treated with pot- assium hypobromite the potassium derivative yields bromonitro- methoxydihydroanthracene OMe*CH<CGH4>CBr*N0 C H a mbstance separating from ether i n well-defined colourless crystals decomposing at 93'; this product when boiled with methyl alcohol and potassium hydroxide gives rise to nitromethoxyanthracene G 4 6 4 G 4 which crgstallises in yellow needle; a i d melts at 156'.also gives rise to a certain amount of nitroanthrsnol. This reaction B~.omonitroanthronedimetl~ylacetccZ C(OMe)2<:G3>CBr*N02 is produced by boiling nitromethoxyanthrscene with a methyl alcohol solution of potassium hydroxide diluting the liquid with water and adding sodium hypobromite solution ; it crystallises from methyl alcohol in white leaflets and clecomposc!s at 139-140". This acetal unlike those previously described) is not affected by mineral acids. 6 4 Oxanthramyl methyl ether O&Te*CH<C6114>C0 CH prepared by acidi- 6 4 fying an ice-cold aqueous solution of the potassium derivative of nitro- methoxydihydroanthracene with very dilute sulphuric acid is separated from the nitroanthracene also produced in this reaction by successive crystallisation from chloroform and benzene ; it crystallises from these solvents o r from the alcohols in colourless prisms melting at 102*5O and is probably identical with the substance described by Liebermann as melting at 98" (compare Abstr.1889 715). isoNitromethoxydihydroant?wacerne OMe CH<CGH4>C NO OH is obtained from the preceding experiment when the first chloroform ex- tract is evaporated at 20-30' under diminished pressure instead of C H G 4ORGANIC CHEMISTRY 797 at 100'; on adding light petroleum to its chloroform solution i t separates in colourless rhombic plates decomposing a t 125'. Potassium 3 5-dinitro-4-methoxy-4-ethoxyquinol-l-nitrolate produced either by the action 'of {itassiurn hydroxide on a solution of ethyl picrate in methyl alcohol or one of methyl picrate in ethyl alcohol when decomposed by dilute sulphuric acid regenerates a mix- ture of the two alkyl picrates.Potassium 3 5-dinitro-4-ethoxy-4-isobutylquinolnitrolate produced by the action of potassium hydroxide on isobutyl picrate and ethyl alcohol or ethyl picrate and isobutyl alcohol also yields a mixture of the two alkyl picrates on treatment with dilute sulphuric acid. G. T. M. Nitro-derivatives of Phenanthraquinone and of Phenan- thraquinol. By JULIUS SCHMIDT and ADOLF K;~MPF (Uer. 1902 35 31 17- 31 as).- 3-Nitrophenanthraquinone is most readily prepared by the oxidation of 3-nitrophenanthrene (this vol.i 29) with an acetic acid solution of chromic acid. It melts and decomposes a t 279-28O0 (compare Schwabacher and Werner this vol. i 440) and may be crys- tallised from concentrated nitric acid. The nitro-derivative described by G. A. Schmidt as melting a t 263' is undoubtedly impure (Abstr. 1879 i 941). 3-Nitrophennnthraquinonemono-oxime crystallises from benzene in yellow needles melting a t 240'. Nitrodiphenylenequin- oxaline >C,H obtained by the action of o-phenyl- enediamine hydrochloride on 3-nitrophenanthraquinone crystallises in greenish-yellow needles melting a t 252-253'. Anschutz's 10-bromo- nitrophenanthrene (Ber. 1878 11 1218) does not contain the nitro- group in position 3. Hot fuming nitric acid converts phenanthraquinone into 2 7-dinitro- phenanthraquinone melting at about 300' and an isomeric dinitro-deriva- tive melting a t 215-217' and more readily soluble in acetic acid than the 2 '7-dinitro-compound. Phenanthraquinone and its nitro-derivatives are readily reduced t o the corresponding quinols by the action of an alcoholic solution of phenylhydrazine acetate or of hydrogen sulphide.Phenanthraquinol (9 10-dihydroxyphenanthrene) melts sharply at 147-148' after sintering at 130' and yields a diacetyE derivative melting at 202'. 3-Nitro-9 1 O-dihydrox?/p~enanthrene crystallises in rose-red needles with a bluish lustre melts at 222-223' and dissolves in alkalis t o deep indigo-blue solutions which rapidly absorb atmospheric oxygen. Its monoacetyl derivative crystallises in yellow needles meking and decomposing a t 234- 235'.2 7-Dinitro-9 10-dihydroxyphenanthrene crystallises from alcohol in minute brick-red needles melting and decomposing a t 274'. It dissolves in sodium hydroxide yielding a green solution which absorbs oxygen but slowly. The monobenxoyl derivative U,,H,,07N2 forms a yellow powder which sinters a t 260' and is completely melted a t 271". The diacetyl derivative CI8H1,O8N2 crystallises in pale yellow ?,H** y:N NO,* C,H; C N VOL. LXXXIJ. i. 3 7;798 ABSTRACTS OF CHEMICAL PAPERS. needles melting and decomposing a t 285'; on reduction it yields a stable diamino-compound which after diazotising can be used for the preparation of sparingly soluble azo-dyes. An isomeric dinitro-9 10-dihydroxyphenanthrene. may be obtained by reducing the dinitrophenanthraquinone of unknown constitution with hydrogen sulphide ; it crystallises in glistening pale-red plates melting a t 301'.Its dibenxoyl derivative melts a t about 210' and its diacetyl derivative at 2589 J. J. S. Enantiomorphic Structure of some Compounds of Cam- phor revealed by Etching. Resolution of Racemic Benzyl- idene Camphor. Isomorphism of its Active Components. By JULES MINGUIN (BUZZ. Xoc. Chim. 1902 [iii] 27 888-892).-The crystals of the camphor compounds have a completely symmetrical form although in solution they are optically active. The author demonstrates in the case of benzylidenecamphor and p-bromobenzyl- idenecamphor that the corrosion figures obtained by means of benzene exhibit enantiomorphism. The author has also found that the enantio- morphic forms of benzylidenecamphor can give mixed crystals so that the crystals of the one form can induce the crystallisation of the other.The author puts forward the idea that; pseudo-racemism and even true racemism may be due entirely to the relative arrangement of the crystalline molecules of the oppositely active forms. By OTTO WALLACH (AnnaZen Compare Abstr. 1901 i 155-157).-[With A. F. Terpenes and the Ethereal Oils. 1902,323 135-160. HANS BOTTICHER. ' 5-Dih~tdro-m-toZ~Zac~tic acid resulting from the hydrolysiiof its ethyl ester with sodium methoxide crystallises from alcohol in needles melting at 170-172'; the tcnzide melts at 146-14'7O. The ester itself was not obtained pure but is produced by condensing methylcyclohexenone with ethyl bromoacetnte in the presence of zinc.The unsaturated acid yields dihydro-xylene when heated for 5 hours at 160'. Ethyl A1 '5-dihyd~o-3 5-xylyl-1-acetate (or 3 ; 5-dimethyZ-Al' 5-diihydro- phenyZacetat4 CH2<CJ3Me.CH CMe= CH>C*CH2*C0,Et prepared by con- densing 3 5-dimethylcyclohexenone with ethyl bromoacetate boils at 136-137' under 18 mm. pressure ; the acid produced by hydrolysing the ester with sodium ethoxide and acidifying the product crystallises from acetone o r methyl alcohol in yellow flakes melts at 150-152' and boils at 170' under 15 mm. pressure; the arnide melts at 126-127'. The two unsaturated acids are also characterised by their silver salts. 3 5-Dimethyl-hl 5-dihydrophenylacetic acid when heated in closed tubes at 200° yields Al '5-dihydromesityZene which boils at 147' under the ordinary pressure and has a sp.gr. 0.826 at 1 8 O . When the un- saturated acid is distilled with soda-lime it yields a mixture of this hydrocarbon and mesitylene. Ethyl propylidenebisacetoacetate prepared by mixing propaldehyde with ethyl acetoacetate and slowly adding diethylamine to the mixture,ORGANIC CHEMISTRY. 709 crystallises from alcohol in silky needles melting at 76-78' ; when heated with potassium hydroxide solution it gives rise to 3-methyl-5-ethyl- A2-cyclohexenone a substance boiling at 102' under 14 mm. pressure and 232' under the ordinarv Dressure. This ketone when condensed with ethyl bromoacetate,* 5elds ethyl 5-rnethyZ-3-ethyZ-hl:5-diilydvo- plbenylacetate C H 2 < ~ ~ ~ ~ ~ > C * C H 2 * C O 2 E t from which the free unsaturated acid is obtained by hydrolysis with alkalis ; the ester boils a t 145-147' under diminished pressure the acid melts at 141-143' and yields a silver salt and an arnide the latter melting a t 123'.When heated in closed tubes at 200° the acid yields a mixture of s-dimethyl- ethylbenzene and a hydvocuvbon Cl0Hl6 boiling at 166-172' and having a sp. gr. 0.0834 at 20' ; the latter substance is unsaturated but does not furnish a solid nitrosochloride or nitrosite. 3-Methyl-5-isopropyl-A2-cycZohexenone is most conveniently condensed with ethyl bromoacetate by adding zinc turnings to the warm mixture diluted with benzene; the ester C,,H,,O thus produced boils at 154-158' under 16 mm. pressure and has the composition of an aromatic derivative ; the corresponding acid Cl,Hl,02 does not melt sharply one portion fusing a t 111-114' and another a t 135-140'.The two fractions however have the same percentage composition. When heated a t 200° the acid yields a hydrocarbon boiling a t 186-1 94' and having the properties of a dirnethyZisoprop$bennxene Cl H,. IWith FRITZ THOLKE.] -Ethyl menthozacetccte CH2<~~2M~&~~~>C(OH)CH2*C0,Et produced by condensing menthone with ethyl bromoacetate boils a t 150-152' under 14 mm.pressure and possesses an odour of cedar oil; the corresponding acid yields a well-defined silver salt. The unsatu~ated ester C H 2 < ~ ~ ~ ~ ~ ~ ~ > C C H * C 0 2 E t results from the action of potassium hydrogen sulphate on the preceding. ester a t 140-150° ; it boils a t 140-142' under 14 mm.pressure ; the unsaturated acid boils a t 158-163' under 10 mm. pressure and is characterised by means of its silver salt. Bomomenthene CllH20 obtained by heating the un- saturated acid under pressure a t 270-280' boils a t 1S6-187' under the ordinary pressure and has a sp. gr. 0.8215 and nD 1.4579 at 23'. The hydrocarbon is probably 1 5-dimethyZ-2-ethyLA1-tetrahydrobenxene. Ethyl cccruornenthoZc6cetcde CH2<CHPra~cH CH2* CHMe>C(OH)*CH2*C0,Et produced from carvomenthone by the general method boils a t 162-164' under 16 mm. pressure and possesses the odour of cedar oil; the corresponding acid yields a silver salt Cl,H,lO,Ag; the unsaturated ester boils a t 150-152' under 13 mm. pressure and the corresponding acid at 166-172" under 11 mm.pressure. Homocaruomenthene CllH20 obtained by heating the unsaturated acid boils a t 194-196' under the ordinary pressure and has a sp. gr. 0.8300 and n 1,46187 a t 20'. The condensation of carvenone with ethyl bromoacetate leads to the 3 k 2800 ABSTRACTS OF CHEMICAL PAPERS. formation of an unsaturated esteil C,,H,,O boiling at 135-137' under 16 mm. pressure the wnsaturated acid boils at 175-180' under 17 mm. pressure with slight decomposition; it yields a silver salt Cl,H170,Ag. A hydrocarbon CllH18 produced on heating the un- saturated acid at 250-260° boils at 194-197O under the ordinary pressure and has a sp. gr. 0.851 and m 1,4821 at 22'. Homolimonene is analogous with the preceding compound and is obtained in the ordinary way from ethyl dihydrocarveolacetate (Abstr.1901 i 156) ; i t boils a t 191-192' and has a sp. gr. 0,8465 and n 1.4771 at 20'. [With NICOLAI S P E R A N S K I . ] - ~ ~ ~ ~ condensed with ethyl bromo- acetate pentanone yields a n oily product boiling at 105-107' under 11 mm. pressure which although not obtained in a state of purity is - - considerid to be ethyl cyclopentanolacetate 2>C(OHj CH,. C0,Et. $!H,.CH CH;CH Y O The unsaturuted ester 8 ~ ~ ~ > C * C H 2 * C 0 E t or CH,*CH CH2'cH2>C I CH* CO,EG z x produced b i heatkg the preceding compound with potassium hydrogen sulphate at 130° is a n oil boiling at 82-84' under 11 mm. pressure ; the corresponding acid C7HZ002 boils at 122' under this pressure and melts at 49-50'; its dibTomide C7H1002Br2 melts a t 88' and i t s amide C,H,*CO*NH at 144'.On oxidation with chromic acid in glacial acetic acid solution the preceding acid yields a small amount of pentanone. G. T. M. Terpenes and Ethereal Oils. Tetrahydrocarvoneisooxime. By OTTO WALLACH (Annalen 1902 323 323-333. Compare Abstr. 1900 i 590).-[With L. F~~s~~~~~.]-~etrahydrocarvoneisooxime (m. p. 104') obtained by the transformation of tetrahydrocarvone- oxime yields a crystalline hydrochloride Cl,HISNO,HC1 ; this sub- stance is however only produced in ethereal solution and is dissociated by water. The amino-acid (m. p. 201-202O) produced from the isooxime by ring fission is now shown t o be ~-ccmino-~-isopropylheptoic acid NH,*CHMe*CH,*CH2*CHPrP*CH2*C02H ; its ethyl ester is a colourless odourless liquid boiling at 149' under 20 mm.pressure; the methyl ester boils at 133-134' under 18 mm. pressure. When treated with sodium nitrite and acetic acid the preceding ethyl ester gives rise t o a mixture of ethyl decenoate CHMe:CH*CH,*CHPr@*CH,*CO,Et and etlzgl E-hydroxy-P-isoiuro~yl~~~ptoate OH*CH,Me*C H2*CH,-CHP~ 8- CH,*CO,Et the former of these boiling at 108-111° and the latter at 152-155' under 13 mm. pressure. Ethyl E-amino-P-isopropylheptoate combines with methyl iodide yielding the quaternary iodide Cl,H1802Et*NMe,I ; the substance when treated with silver chloride. forms a hvgroscopic chloride which is identified in the form of its 'pZatinichZo&& C,oH6,0,N,,H,PtCl,. The corresponding betaine CHMe< obtained by CH,-CH,*yHPrP NMe,*C0,*CH2ORGANIC CHEMISTRY. so1 treating the quaternary iodide with silver oxide is an amorphous hygroscopic substance which yields a platinichlorz'de ( c10H1702N'1e3)2 H2P cl,.The €-amino-acid when treated with nitrous acid yields a mixture of three substances a lactone an unsaturated acid and a hydroxy-acid. The first two only are volatile in steam. The non-volatile product is a viscid non-crystallisable substance which yields a ketonic acid probably P-isopropyl-4-ketoheptoic acid CH2Ac*CH2*CHPr@*CH2*C02H ; this compound melts at 37-38O and forms a semicarbazone melting at 151-152" (compare Baeyer and Villiger Abstr. 1900 i 133). On further oxidation the hydroxy-acid gives rise to isopropylglutaric acid. The lactone CHMe<o,G.o.CH CH -CH2>CHPrP is identical with the substance obtained by oxidisini tetrahydrocarvone (Baeyer and Villiger Zoc.cit.). The unsaturated compound is a decenoic acid (Abstr. 1901 i 590) having the formula CHMe:CH*CH2*CHPrfl*CH2eC02H ; the amide melts at 63-64O and on treatment with phosphoric oxide yields the nitrile C,H,,CN a substance boiling at 99-100' under 12 mm. pres- sure. A base boiling a t 89-90' under 12 mm. pressure is obtained by reducing the nitrile with sodium and alcohol; it yields a n alcohol on treatment with nitrous acid. G. T. M. Terpenes and Ethereal Oils. Compounds of the Thujone Series. By OTTO WALLACH (Annalen 1902 323 333-373. Com- pare Abstr. 1895 i 619; 1897 i 246).-isoThujone when oxidised with potassium permanganate solution gives rise to a ketolactone and two acids. The ketolactone ClOH,,O melts at 43-44' and yields a semi- curbaxone C,oH1,02:N*N H*CO*NH melting a t 188-189'.The oxime C,,H,,O,:NOH separates from dilute methyl alcohol in transparent prismatic crystals melting at 155-156' ; the phenyl- hydraxone forms snow-white crystals and melts at 144-146". The ketolactone is not identical with that obtained from thuja- menthone. The acidic products of the oxidation of isothujone are ketonic acids having the formulae C,H,,O and C,H,,O and are separated by the fractional crystallisation of their semicarbazones in alcohol. The semicarbazone of the former acid melts at 1S8-1S9°; and acid regenerated from this derivative melts at 73-74' boils at 145' under 10 mm. pressure and when oxidised with sodium hypobromite decom- poses into bromoform and isopropylsuccinic acid.This result indicates that the C acid is an isopropyllcevulic acid having one of the following forrnulz CH2Ac*CHPr@*C02H or CHAcPr@*CH2*C02H. This acid yields an-oxime CSHl3O2:NOH melting a t 119-120" and a phenylhydraxone melting a t 100-1 0 1 O . The other ketonic acid C,H,,O is a n odourless liquid boiling a t 158' under 11 mm. pressure ; its semicas.6nxone is readily soluble in hot alcohol and boils at 154-156' ; the oxime melts a t 77". On oxidationso2 ABSTRACTS OF CHEMICAL PAPERS with potassium hypobromite the ketonic acid yields a lactone and a dibasic acid melting at 106-1 08' which is probably isopropylsuccinic acid. The ketolactone when oxidised with permanganate nitric acid or sodium hypobromite gives rise t o a n acid CgHl4O4 which is isomeric with homoterpenylic acid and resembles this substance by crystallising with lH,O; it crystallises from dilute methyl alcohol in plates melt- ing at 52.5-535O and boils at 205-206' under 12 mm.pressure; its silver salt O,H,,O,Ag is soluble. When the oxidation is carried further by means of chromic acid the preceding acid yields isopropyl- lavulic acid. Benxylideneisothujone C,,H140 CHPh results from the interact ion of benzaldehyde and isothujone in the presence of a n alcoholic solution of sodium ethoxide ; i t boils at 210-212O under 12 mm. pressure and melts at 83'. Since isothujone can be ultimately oxidised t o an isopropyllaevulic acid its constitution must be represented either as according as to whether the isopropyl group in the oxidation product is in an a- or a P-position.Assuming that Wagner's rule for the oxidation of ethylene derivatives holds in this case the ketolactone must have one or other of the following formulae 111. C H P r B e M ; g 2 > C 0 . IV. CHPrP<gg20>CMeAc. The condensation with benzaldehyde indicates that isothujono con- tains the residue CO*CH and accordingly formula I is to be preferred for the ketone. From this. the ketolactone should be remesented by formula 111 the acid C,H,,O being therefore represbted by co-0 CH,<C HprB>CMe C o p The constitution of the acid C,H,,O is still uncertain. Thujamenthylamine ClOHlR*NH2 the base obtained by reducing the oxime of thujamenthone boils at 198-200' under the ordinary pressure and has a sp. gr. 0.8095 and n 1.4531. It yields acetyl and benxoyl derivatives and a carbamide and p?~elzyZt?~iocarbamide these substances melting at 128-129' 106-107' 205-206° and 112' respectively ; the plmwJcar6amide is amorphous and the hydrochloride is crystalline. Benxylidenethujumenthone C,,H,,O:CHPh produced by condensing isothujone with benzaldehyde boils at 180-182' under 11 mm.pres- sure but does not crystallise. Thujamenthoketonic acid C,,H,,O the oxidation product of thuja- menthone yields a silver salt and a semicarbaxone C,,H,,O,N which melts somewhat indefinitely at 170-175° and is soluble in ammonia. The ketonic acid on oxidation with sodium hypobromite gives rise to a dibasic acid C,H1,O which melts at 137-138' and crystallises from ether in transparent prisms; the silver salt has the composition The oxidation of thujamenthone also results in the formation of a ketolactone C,,H,,O ; this product crgstallises from ether melts at 42" and boils at 130-132' under 10 mm.pressure ; the oxime melts at C9H1404Ag2*ORGANIC CHEMISTRY. 803 158-15(3°. The senlricccrbaxo9be crystallises in needles and melts at 179-180" ; the p?tmay/l?ujdraxom forms white leaflets melting at 144-146". The ketolactone closely resembles the corresponding sub- stance derived from isothujone and the two compounds yield semi- carbazones oximes and phenylhydrazones which are very similar. The greatest difference is observed in their products of oxidation ; the ketolactone from isothujone gives a di basic acid crystallising with 1H,O and melting at 52-53" whilst the ketolactone from thuja- menthone yields an isomeric lactone-acid C9Hl4O4 which is anhydrous and melts at 94O; the product on further oxidation gives rise to iso- Drotnllsvulic acid.The following formulix A L d CHPrs<CH2. CMeAc- Co>O C H < ~ ~ ~ > C M e * C O H are suggested for thn jamenthone the ketolactone and the lactone-acid respectively. Thujamenthoketonic acid and the dibasic acid (a-methyl-P-isopropyl- glutaric acid P) are regarded as having the constitutions CHMeAc*CHPrS*CH,*CO,H and C0,€I*CHMe*CHPrS*CH2*C02H respectively. The formula for thujone suggested by Semmler (compare hbstr. 1893 107 ; 1896 330 ; 1897 i 247) is confirmed by the observation t h a t this ket,one when saturated with hydrogen chloride and heated at 120-150' gives rise t o a considerable quantity of cymene the reaction being explained in the following manner CH,*CHMe>C.*H + CH~<~~+CH,>CO + CH,<CprSCI-CH CH*CHMe The substance dihydrocarvacrol represented by the third formula is probably produced by the action of ferric chloride on thujone and under these conditions becomes oxidised to carvacrol. The above formula for thujone does not however explain the forma- tion of tanacetogenic acid and camphoric acid (m.p. 146') from this ketone by the action of sodium hypobromite. By OTTO WALLACH and 0. RAHN (Annalen 1902 324 79-97. Compare Abstr. 1895 i 547 ; Tiemann and Semmler ibid i 548)-1 :8 9-Tvibromoterpane CI\Ie&r<~~~:~~~>CHCllleBr.CH,Br prepared by adding succes- sively bromine and hydrogen bromide to a glacial acetic acid solution of Helle and Stephan's terpineol (compare 'this vol.i 64l) crystaliises from dilute alcohol and melts at 67". When treated with 1 mol. of bromine the tribromide yields dipentene tetrabromide melting at 123". The monobromide CIOHIBBr produced by treating the tribromide with sodium methoxide in methyl alcohol solution is a n oily substance boiling at 105-1 10" under 10 mm. pressure and yielding with bromine a pentabromide which separates from alcohol or ethyl acetate in white crystals and melts at 137O. Assuming t h a t the removal of bromine G. T. M. Terpenes and Ethereal Oils Terpineol.804 ABSTRACTS OF CHEMICAL PAPERS. by sodium methoxide takes place in the same way as in the case of dipentene tetrabromide the monobromide may be represented by the formula C M e < z ~ ~ g ~ ~ > C H * C M e C H B r whilst the pentabromide has a constitution corresponding with CMeBr<C€€o-CHn cH Br cIH2>CH CMeBr*CH2Br.Helle and Stephan's ter$neol y:elds 1 8 9-trihydroxyterpane (m. p. llSo) and this in turn gives rise to the ketone CgH1202. When warmed with dilute sulphuric acid the latter product loses water and becomes converted into an unsaturated ketone. isomeric with phorone which YboilGat 205-206' and has a sp. gr. 0.940 and nD 1.4719 a t 19'. The semicarbaxone crystallises from alcohol in lustrous leaflets melting a t 164-165' the oxirne melts a t 51" and on treatment with bromine yields the dibromo-oxinte decomposing at 150". The unsaturated ketone is a p-acetyltetrahydrotoluene for when heated with concentrated sulphuric acid it loses hydrogen and furnishes pacetyltoluene.The terpineol melting at 32' and dihydro- carveol are isomeric substances represented respectively by the form ul s OH CMe<CHo. CH2*cH2>CH*CMe:CH CHn and 1 L CHMe<CH(OH).~~>cHMe:cH CH2- ; the latter compound yields successively a trihydroxyterpane the hydroxyket One CHMe<CH( OH,- OH). CH2>CH*COM~ CH and the above- 1 0 mentioned p-acetyltetrahydrotoluene ; the final product when re- duced with sodium in dilutealcoholic or ethereal solution gives rise to the terpineol C M e < z ~ ~ ~ ~ > C H * C H N e * O H which boils a t 212-213' and has a sp. gr. 0.942 and n 1.4836 a t 19'; its phenyl- urethane crystallises from dilute methyl alcohol and melts at 69'. This alcohol which is a lower homologue of the terpineol melting a t 35' when heated either with dilute solutions of oxalic or sulphuric acid or with sodium hydrogen sulphate a t 180-1990" becomes converted into a lower homologue of cineol ; this product boils at 168-172' has a sp.gr. 0.92 and shows the characters of a saturated oxide CgHl,O being stable towards potassium permanganate solution. A hydyocarbon CMe<EE>g2>C:CHMe or is obtained from the secondLry aliohol by saturating its chloroform solution with hydrogen chloride and adding phosphorus pentachloride ; it boils at 160-1634 and has a sp. gr. 0.843 and n 1.47586 at 22". The action of hydrogen chloride and phosphorus pentachloride probably results in the formation of the saturated dichloride,ORGANIC CHEMISTRY.805 this product by the loss of hydrogen chloride would furnish a hydro- carbon having one or other of the formulze just given. G. T. M. Terpenes and Ethereal Oils Trimethylcyclohexenone Tri- methylcyclohexanone and 3 3-Dimethylcyclopentanone. By OTTO WALLACH and A. SCHEUNERT (Anncden 1902,324,97-112).-cz-cycZo- Geraniolene the chief product of the transformation of geraniolene yieldsa nitrosochloride melting a t 100-1 20'and a nitrosate C,H,,O,N melting a t 102-104O. and nitrolebenz~lumine C,H,,ON*NH*CHPh melt respectively a t 136-138" and 106'. 2 4 4-Tri.met~~yZcyclo-A2-~~exenoneox~m~ resulting from the action of alcoholic alkali hydroxides on the nitrosochloride or the nitrosate boils at 131-132' under 15 mm. pressure and crystallises in prisms melting a t 128-129'.The corresponding mitrolepiperidide C,H,,ON*C,NH,o v 2 4 4-T~imethyZeyclo-A2-Aercenone CMe2<CH,.CH CH CMe>CO produced by hydrolysing the preceding compound with dilite klphuric acid is a colourless liquid boiling a t 195-196' and having an odour resem- bling that of tanacetol; i t has a sp. gr. 0.9245 and n 1.4749 at 25'; the molecular refraction deduced from experimenh is 42.02 whilst the calculated value for an unsaturated alcohol containing two ethylene linkings is 42-16 Accordingly the ketone appears to exist in the e n o h form. The semicarbaxone C,H,,N*NH*CO*NH melts a t 158-159' ; the benxylidene derivative C H P h C < ~ ~ ~ ~ $ > C H obtained by con- densing the ketone with benzaldehyde in the presence of sodium ethoxide melts a t 54-55'.2 4 4-~ri~net~yZcyclohex~no2 C M e 2 < ~ ~ ~ ~ ~ ~ > C H * OH results from the reduction of bhe unsaturated ketone with sodium in ethereal or alcoholic solution ; in the former case a considerable amount of pinacone is produced. The saturated alcohol is a viscid colourless oil boiling a t 192-193' and has a camphor-like odour. 2 4 4-TrimethyZcyclohexanone CMep<CH2-CH2 CH,*CHMe >CO obtained by oxidising the preceding alcohol with chromic acid boils a t 191' and has a sp. gr. 0.902 and n 1.4545 a t 19O; its semicacl.bcczone C,H,,N*NH*CO*NH and oxime melt respectively a t 164-1 65' and 108-109'. The latter derivative when treated with moderately concentrated sulphuric acid becomes transformed into the isooxime melting a t 115- 116' ; this product when saturated with hydrogen chloride in ethereal solution yields a stable AydrocMoride.The isooxime should have one or other of the formule CH,*CMe,-CH L and CHMe<NH-CO-bH2 and accordingly the aminocarboxylic806 ABSTRACTS OF CHEMICAL PAPERS wid obtained by its hydrolysis with 20 per cent. hydrochloric acid a t 150" is either r-ainino-ayy-trimeth?/Z~~ezunoic acid NH,*CH,*CH,*CMe,*CH,*CHMe*(IO,H or €-ctmino-yy-climethyl~~e~tanoic mid NH,*CHMe*CH,*CMe,* CH,*CH,*CO,H. This acid separates from dilute alcohol in colourless crystals melting at 160-161". The constitution of 2 4 4-trimethylcpZohexanone is determined by studying the products of its oxidation. isoGeronic acid results from the action of potassium permanganate and is identified by means of its semicarbazone.The ketonic acid on treatment with potassium hypo- bromite yields PP-dimethyludipic acid which melts a t 85-86' and is characterised by its silver salt and by conversion into 3 3-dimethyl- cyclopentcmone C O < ~ ~ ~ x ~ ~ through the agency of its calcium salt. This cyclic ketone regenerated from its semicnrbuxoize (m. p. 174-175°) boils at 154-155' and has the odour of menthone. The production -of dibenxylidene-3 3 -dimethyZcyclopentanone C( :CHPh)* YH Co<C(:CHPh)*CMe,' by the action of 2 mols. O€ benzaldehyde 0 the ketone in the pre- sence of sodium ethoxide proves that the methyl groups are not in an a-position with respect to the carbonyl radicle. The dibenzylidene derivative crystallises from ethyl acetate in brilliant yellow needles and melts at 138-139'.Benzylidene-PP-di- rnetlzylcyclopentanone obtained from the ketone by the action of 1 mol. of benzaldehyde is very soluble in alcohol or ether and separates from a mixture of the latter solvent and light petroleum in pale yellow crystals melting a t 66 - 67". Terpenes and Ethereal Oils. Transformation of Cyclic Hydrocarbons and Ketones. By OTTO WALLACH and .M FRANKE (AnnuZen 1902 324 112-1 1'7. Compare preceding abstract).-Di- hydroisophorone derived from isophorone (compare Knoevenagel Abstr. 1897 i 611) has a constitution corresponding with the formula C H M e < ~ ~ ~ ~ ~ ~ > C H and is therefore 3 5 5-trimethyl- cyclohexanone differing only from 2 4 4-trimethylcyclohexunone pro- duced from cyclogeraniolene in the position of its carbonyl group The first of these isomerides can be transformed into the second by the following series of changes.The crystalline trans-dihydroisophorol C,H,,*OH on treatment with phosphoric oxide or anhydrous zinc chloride yields a-cyclogeraniol- ene and this hydrocarbon when treated in the manner indicated in the preceding abstract gives 2 4 4-trimethylcyclohexanone. 3-MethylcycZohexanol when dehydrated with zinc chloride gives rise to a tetrahydrotoluene C7H12 which is isomeric with the hydro- carbon derived from methylcyclohexyl chloride The new hydrocarbon yields a nitrosate which in turn furnishes a methylcyclohexenone C7H100 differing in properties from 3-methylcyclohexanone (Knoe- venagel Abstr. 1897 i 606). G. T. M. G. T. M.ORGANIC CHEMISTRY SO7 Isomeric Changbs in the Thujyl Series Constitution of Thujone.By IWAN L. KONDAKOPF (Chem. Zeit. 1902,26,720-724). -Thujyl alcohol which is probably a dicyclic compound is converted by phosphorus pentachloride into an unstable thujyl chloride of in- constant composition (compare Semmler Abstr. 1893 i l?8) ; it con- sists mainly of a tertiary compound which with moist silver oxide gives a tertiary alcohol with bromine evolves hydrogen bromide and with alcoholic potassium hydroxide forms a *mixture of at least two hydrocarbons ; these in their properties resemble on the one hand dicyclic thujene (Tschugaeff Abstr. 1901 i 38) and the sabinenes and on the other monocyclic tanacetene (Semmler Zoc. cit.) and Wallach's thujene (Abstr. 1893 i 105).From the hydrocarbon frac- tion (b. p. 160-175') dipentene dihydrochloride can be obtained by treatment with hydrochloric acid. Thujyl chloride and hydrogen chloride yield two hydrochlorides one of which is dipentene dihydro- chloride. Thujone does not form an additive product with hydrogen chloride but with hydrogen bromide gives a substance which boils a t 105-117° under 11 mm. pressure ; by moist silver oxide it is con- verted into a n optically inactive ketonic alcohol which boils at 229-231' under the ordinary pressure and a t 105-106° under 11 mm. pressure and has a sp. gr. 0.9314 a t ZOO and m 1,4841 ; its oxime melts at 11 4.5-1 15'. By prolonged treatment or by warming with hydrochloric acid thujyl chloride is converted into a dichloride which boils a t 116-130' utlder 12 mm.pressure and is heavier than water; it is perhaps identical with the dichloride of dihydrocarveol. ThujgZ bromide is prepared by the action of hydrogen bromide on thujyl alcohol ; it boils a t 110-117' under 11 mm. pressure and has a sp. gr. 1.007 a t 20' and [aID + 23'5' ; it appears to be a secondary compound. The author believes that thujone is best repreeented by the formula CMe2<(5H.CH2.(30 * K. J. P. 0. By FRANK D. DODGE (J. Amer. Chern. Xoc. 1902 24 649).-When pinene ,and camphene are treated with acetic acid containing 1 per cent. of sulphuric acid they are converted to the extent of 43 and 77 per cent. into terpincol and isobornyl acetates respectively whilst limonene terpiuolene and terpinene are under the same conditions esterified to the extent only of 4 11 and 8 per cent To account for this similarity in reaction of camphene and pinene it is suggested that the former must contain like the latter a 3- or 4-carbon ring leading to one of the follow- ing formulz for this hydrocarbon 1.CMe-C(yH,)Me-CH CH*CH,*yHMe The Constitution of Camphene. /CH2-H2\ '- CH*CH2 / /CH,*CH2\ I \CH-CH,/ 2. UH2*C-CMe,--CH. The second of these would lead to a formula for camphenilone identical with that proposed by Wallach for808 ABSTRACTS OF CHEMICAL PAPERS. fenchocamphorone and is therefore improbable. The first formuIa represents camphene as a saturated substance which is in harmony with its behaviour to bromine and permanganate. It affords further an explanation of the formation of isobornyl acetate by the opening of the 4-carbon ring; the position of the latter however precludes any further rearrangement of the rest of the molecule such as occurs in the corresponding reaction with pinene and so accounts for the possi- bili ty of reobtaining camphene from isoborneol.Whilst the new formula is in agreement with the constitution assigned to camphoric acid camphenylic acid and camphene glycol it is not in harmony with Jagelki's formula for camphenilone (Abstr. 1900 i 627). This since it assumes the presence of an oxidised 4-carbon ring is improbable and it is proposed to substitute for it the following formula /CH2*CJ32\ CMe-CHMe-TCH \CO-UH2/ representing camphenilone as a true lower homologue of camphor and satisfactorily accounting for its principal reactions.If the presence of a 4-carbon ring in camphene be admitted the symmetry of the camphor molecule suggests the possible occurrence of such 4-carbon rings in other positions and the reactions of camphenone would be satisfactorily accounted for by the following formula CH-C(C)H,)Me-CMe whilst fenchene which reacts like pinene and camphene with acetic acid would be represented thus CH-C(~H,)Me-CH. This formula however is not in harmony with Wallach's representation of fenchocamphorone (Abstr. 1900 i 241). By LUIGI BALBIANO and VINCENZO PAOLINI (Ber. 1902 35 2994-2998; Atti 22. Accad. Lincei 1902 [v] 11 ii 65-69. Compare Abstr. 1902 ii 109)- Mercuric acetate reacts with olefines at the ordinary temperature insoluble mercurous acetate being formed along with acetic acid and oxidation products of the olefine.EPinene is thus converted into dioxypinene C,,H,,O which is a viscid oil of sp. gr. 1.069 a t O" boils a t 145' under 4 mm. and a t l7O-17l0 under 20 mm. pressure and is optically inactive. This substance behaves RS a ketonic alcohol containing an ethylene linking ; i t combines with two atomic proportions of bromine and yields an oxime melting a t 1 3 8 * 5 O which also unites with bromine and a semicarbazone which crystallises in needles melting at 180'. The compound with phenylcarbimide crystallises in prisms melting at 125". Oxidation with permanganate converts i t into terpenylic acid 0-CMe \ /CH2-CH2 '-CH-CO' 2\ /CH,-CH '-CH*CHMe / T. A. H. Oxidations with Mercuric Acetate. Qo* C H 2 > ~ ~ * ~ ~ 2 - ~ ~ 2 ~ .[With A. NA~~accI.]-Anethole is converted by mercuric acetate into a glycol OMe*C,H,-C,H,(OH) which crystallises in mnmmillaryORGANIC CHEMISTRY. 809 groups of needles and melts a t 98'. The diacetyl derivative is an oil which boils at 210' under 41 mm. pressure. The glycol is oxidised by chromic acid to anisic acid. [With E. Luzz1.1-isoSafrole which contains the propenyl group is readily oxidised by mercuric acetate but the corresponding glycol has not yet been obtained pure. Safrole on the other hand which contains the ally1 group is not oxidised but when treated with the acetate for four months yields a compound C H 2 O,:C,H,* C,H,( 0 H)*Hg*OAc which forms crystalline crusts. An isomeric compound is obtained as a pale yellow syrup by the action of mercuric acetate for only 8-10 days.Both compounds when treated with acids yield safrole. Cam- phene behaves in a similar manner to safrole yielding a crystalline mercury compound of complex constitution. Essential Oil of Asarum Arifolium. By EMERSON R. MILLER (Arch. PlLarm. 1902 240 371-385).-By distilling the roots of Asarum nrifolium with steam shaking the oil with aqueous potassium hydroxide fractionating the residual oil and examining the various fractions the following constituents were detected I-pinene eugenol a phenol of unknown composition methyleugenol methylisoeugenol safrole (the chief constituent) asarone and probably a sesquiterpene. A. H. C. F. B Constituents of Calamus Oil. I. By HERMANN THOMS and R. BECKSTROEM (Ber. 1902 35 3187-3195. Compare Abstr.1901 i 396).-The fraction of oil used had a sp. gr. 1,0254 at 20° a - 0.68' at 26' in a 2 em. tube and distilled between 272' and 340' uncier the ordinary pressure. It contained free n-heptoic acid and palmitic acid eugenol asarylaldehyde of which the oxime was also prepared and analysed and esters of acetic and paImitic acids. From the fractions of high boiling point of the saponified oil a solid substance was isolated which separated in needle-shaped crystals was crystallised from alcohol and melted a t 168'; for this substance which has been observed by Schimmel & Co. (Schimmel's Ber. Oct. 1899 8) and by Soden and Rojahn (Abstr. 1901 i 395) the name calameon is proposed. Subsequent addition to the oils of moist ether or light petroleum caused the separation of a considerable quantity of asarone from which asarylaldehyde and asaronic acid were prepared ; the amount of asarone in the oil can be directly deduced from the Zeisel methy! number for none of the other constituents contains a methoxy- group.By the action of arsenic acid on the fractionated oil a solid arsenate was produced from which after removing the arsenic a polymeride of asarone was isolated ; this was obtained as a white powder consisting of minute clear transparent prisms which melts a t 203' and distils with much decomposition between 175' and 225' under 16 mm. pres- sure; it can be prepared directly from pure asarone by the action of arsenic acid. It yields the same oxidation products as and is partially reconverted into asarone when distilled ; its molecular weight corre- sponds with that required for the formula (C12H1603)3 and the name paru-asarone is suggested for the compound.After removing the whole of the asarone by this method or by means of sulphuric acid a residue810 ABSTRACTS OF CHEMICAL PAPERS. of hydrocarbon was left ; the fractions of high boiling point contained a laevorotatory hydrocarbon Cl5H2 which had a sp. gr. 0,9336 at B' and [a]D-13'38' at 22' whilst the fractions of low boiling point gave a dextrorotatory hydrocarbon which had a sp. gr. 0.9330 a t 18' and [.ID+ 13983' at 18'; the hydrocarbon could also be directly isolated by dissolving the fraction of the oil in light petroleum treating with dry hydrogen chloride which precipitates the asarone and converts the hydrocarbon into the hydrochloride C,,H,,,HCl which remains in solution and is left as a liquid on evaporating the solution ; from this the hydrogen chloride is removed by distillation in a vacuum. By HERMANN THOMS and R.BECKSTROEM (Ber. 1902 35 3195-3200).-Calameon C,,H,,O separated from the fractions of high boiling point of calamus oil forms glistening hemihedral orthorhombic crystals melts a t 16S0 dissolves in 22 parts of cold alcohol sublimes in glistening needles when heated and has [a] -8.94' at 26' in alcohol; it is not an acid phenol aldehyde ketone ester alcohol or phenol ether is not attacked by sodium in alcoholic solution but in ethereal solution yields a sodium derivative C,,H,,O,Na which forms a white sandy precipitate decomposes and becomes brown a t 168' and when boiled with water is reconverted into calameon.Calameonic acid C15H2404,H20 prepared by oxidising calameon with permanganate crystallises from much ether in stout prisms and melts with liberation of gas at 153" ; the anhydrous substance crystallises from ether and melts a t 138". The ammonium salt Cl,H,,O,NH,,l~H,O melts at 180'. The calcium salt with 6H,O crystallises in glistening flakes. Carbon dioxide and acetic and oxalic acids are also formed in small quantities in the oxidation. Calsmeon combines additively with two atomic proportions of bromine but the compound is not stable loses water and hydrogen bromide leaving an oil of the formula Cl5H,,Br. By passing dry hydrogen chloride into an ethereal solution of calameon a hydro- chloride Ci,H,60,,HC1 is formed which separates in white needle- shaped crystals melts a t 119" and is reconverted into calameon when boiled with alcohol.When warmed with 80 per cent. sulphuric acid acetyl chloride or banzoyl chloride calameon loses 2H,O and leaves a hydrocarbon cukamene C,,H ; this is a clear refractive liquid boils at 144' under 15.5 mm. pressure has a sp. gr. 0.9324 a t 23" and [aIn - 11.31' at 26' is not reduced by metallic sodium but combines with water when warmed with a mixture of sulphuric and acetic acids. By the action of bromine a substitution product C,,H,,Br is obtained as a pale- yellow oil. Calamene gives a crystalline hydrochloride which melts at 108'. On oxidation i t is converted completely into acetic and oxalic acids T. M. L. By A. B. AUBERT (J.Amer. Chem. Soc. 1902 24 778-780).-This essential oil is of a dark bluish-green colour and possesses a pleasant odour. It has a sp. gr. 0.9217 a t 22' mD 1.506 at ZOO is miscible with absolute alcohol ether xylene or chloroform but only partially Eoluble in 95 per cent. alcohol. It was separated T. M. L. Calameon from Calamus Oil. Oil of Milfoil.ORGANIC CHEMISTRY 811 by distillation under reduced pressure into the following fractions 170-190' (7 per cent.) 190-210' (17 per cent.) 210-220' (50 per cent.) 220-235' (9 per cent.) and above 235' (3 per cent.) leaving 14 per cent. of a dark coloured waxy residue. The first fraction was slightly acid ; it gave indications of the presence of a small amount of cineol (1) and of an aldehyde with an odour of cedar-wood.The fraction 210-220' had a t first a deep blue colour but became light yellow when left in the dark. It consists principally of a substance having the composition C12H20 which is optically active having a rota- tion - 14.2' in a 100 mm. tube n 1.492 and boils at 254' (uncorr.) under 754.8 mm. pressure. When treated with bromine it evolves hydrogen bromide and is converted into a pitch-like resin. T. A. H. By JOHN C. UMINEY and C. T. BENNETT (Phccrm. J. 1902 [iv] 15 146-147).-A sample of Chinese oil of neroli said to have been obtained from Citrus triptera had a yellowish- brown colour with a slight blue fluorescence sp. gr. 0.850 at 15' and optical rotation + 3 5 O in a 10 cm. tube. It contained 4.79 per cent. of esters (calculated as linalyl acetate) and 21.41 per cent of free alcohols (calculated as linalool).By distillation under the ordinary pressute the following fractions were obtained 170-175' 30 per cent. ; 175-180° 14 per cent. ; 180-185' 21 per cent. ; 185-190' 7 per cent. ; above 190" 28 per cent. The chief constituents of the oil are limonene camphene (?) linalool linalyl acetate (traces) methyl anthranilate and a paraffin hydrocarbon. By CARL D. HARRIES (Ber. 1902 35 3256-3266).-When gaseous nitrous acid is passed through a benzene solution of Para rubber a green colloidal precipitate of the nitrosite (CloH1603N2)~ separates which is insoluble in all the common solvents except pyridine and aniline which appear to decompose it. When this is further treated in suspension in be~zene with nitrous acid it changes to a yellow nitrosite (niti*osite 6) which is soluble in ethyl acetate acetone or alkali solution reduces Fehling's solution and decomposes when heated at 130' ; from ebullioscopic measure- ments in acetone solution its molecular weight has been found to be about 600 and its formula is C,,H,,O1,N,. When oxidised with nitric acid this nitrosite gives a dark yellow powder of the formula C,,H,,O,,N~ oxalic acid and an oil which appears to contain an aliphatic nitro-acid.When oxidised with permanganate nitrosite b gives a mixture of fatty acids principally oxalic and succinic. When Pararubber is dissolved in moist benzene and a rapid current of unwashed nitrous acid is passed through the solution another yellow powder is obtained which has the formula C20H30014N6 and is termed nitrosite c.This decomposes a t about 160' and on oxidation gives products similar to those obtained from nitrosite 6. Myrcene (from Bay oil) polymerises to a thick greenish oil when heated for 4 hours at 300'. On subjecting the product to fractional distillation a t a pressure of 13 mm. about a third passed over between 160' and 200° and this was found to be dimyrcene. The undistilled residue consists of poZ$naywe?ae which is soluble in benzene. By the action of nitrous acid on dimyrcene a nitrosite is produced which is Chinese Oil of Neroli. E. G. Chemistry of India-rubber.812 ABSTRACTS OF CHEMICAL PAPERS. apparently identical with nitrosite c obtained from rubber. From the polymyrcene a nitrosite of the formula C,,HB,Ol,N was formed.The author has examined the products of the direct oxidation of Para rubber with nitric acid and confirms the observations made by Dittmar (this vol. i 386). The " dipentene fraction" of rubber oil has been distilled under reduced pressure and the fractions examined as to density and refractive power ; the results indicate the presence of a new hydrocarbon. The results of the investigation tend to confirm R7eber's opinion (Abstr. 1900 i 353) that rubber is a derivative of an aliphatic terpene that is it is an unsaturated open-chain hydrocarbon. - J. McC. Elemi. By ALEXANDER TSCHIRCH and J. CRERIER (Arch. Pharm. 1902 240 293-324).-Forty-six specimens of elemi were examined some partly crystalline others amorphous. They were all derived from Bursaraceae or Rzctaceue and may be referred to three main types derived from Canwium Amyris and Protium respectively. A sample of each of these types was examined chemically.Nanila elemi from Cunarium commune.-A specimen of soft resin was examined first; i t had an acid number 21 and a saponification number 31.5. One per cent. aqueous ammonium and sodium carbon- ate solutions extract nothing from an ethereal solution of the resin. One per cent. aqueous potaPsium carbonate solution extracts acids and a-manelemic acid C37H5604 (Buri Abstr. 1878 439) crys- tallises from a solution of these in alcohol. This melts a t also has a specific rotation [a]= 15*0° acid number 104.5 corresponding with monobasicity and " saponification " number 197 ; the last number really indicates the formation of a dipotassium salt and is not a true saponification number for mineral acids precipitate the original acid from the alkaline solution.The (mono) potassium and silver salts were analysed ; (mono) acetyl and benxoyl derivatives were prepared melting a t 205' and 210' respectively ; no methoxyl group is present ; concentrated nitric acid oxidises the acid forming a substance with the composition C35H54020 together with some picric acid. From the mother liquor of the a-acid amorphous p-manelemic acid C,,H,,O was isolated ; i t melts a t 75-76' is optically inactive and has an acid number 93 corresponding with monobasicity and a saponification number 115. Manamyrin C,,H5,0 (Vesterberg Abstr. 1887 733 ; 1891 165) was obtained from the resin freed from acid by digesting it with alcohol and crystallising the residue from a mixture of alcohol and ether.This was benzoylated and the product sepuated by means of hot 80 per cent. alcohol into a soluble and an insoluble portion melting at 191-192' and 228-229' respectively ; by hydrolysis of these a- and P-amyrin were prepared respectively the latter with more difficulty ; they melt a t 181' and 192' and have the specific rotations 91.6' and 99.6'. Bryoidin C21H4203 melting a t 135*5' was pre- pared by digesting the elemi with dilute alcohol a t a gentle heat and evaporating the extract to crystallisation (Fluckiger Buchner's Rep. Pharm. 224); from the mother liquor a bitter substance and sodium chloride were obtained the latter originating presumably fromORGANIC CHEMISTRY.S13 melting of the resin when gathered with boiling sea-water. By distilling the resin with steam an essenticd oil was obtained and fractionated ; one fraction boiled a t 170-175' and had sp. gr. 0,955 another boiled a t 175-210' and eventually deposited a fern crystals melting at 170'. Mumeleyesen C,,H,,O remains after the removal of the other constituents of the resin; it is amorphous and melts a t 63-65' I n 100 parts of the drug there are contained manamyrin 20-25 ; essential oil 20-25 ; bryoidin 0*8-1 ; a-manelemic acid 5-6 ; P-manelemic acid 8-10 ; maneleresen 30-35 ; inorganic con- stituents and bitter substance 1-2 ; impurities 5-6. A specimen of hard resin was then examined. It had an acid number 24 and a saponification number 34 and resembled the soft resin except that it contained more impurities and much less e~;ential oil; the amount of a-manelemic acid slightly exceeded that of the P-acid.A third specimen collected from Cccnariuna commune was examined finally ; it contained the same constitaents as %he other specimens. Yucutan elerni from Amyris eZemiJercc.-The acid number of the specimen examined was 15 the saponification number 33. The con- stituents were much the same as in the Manila specimens except that no acids were present. I n 100 parts of the drug there were con- tained yucamyrin (melting at 179' and containing about equal parts of the a- and P-modifications) 10-15 ; essential oil 8-10 ; yuceleresen (melting a t 75-77') 60-70 ; bitter substance and impurities 4-5. The very large proportion which this resin contains of substances which resist the action of alkalis (resen and amyrin) makes it peculiarly suitable for the basis of a lacquer.African (Cameroon) elemi possibly from C'anarium Schzueinfwt1zii.- The acid number of the specimen examined was 21 the saponification number 38.. Only an amorphous cfelemic acid C,,H9,0 was ob- tained i t melted a t 97-98' and had an acid number S 5 correspond- ing with monobasicity and a saponification number 102. Afcmyrin meIted a t 170' and was not separated into constituents. No bryoidin was found. I n 100 parts of the drug there were contained afamyrin 20-25 ; essential oil 15-20 ; afelemic acid 8-10 ; afeleresen Braxiliccn Protiurn-Elenti (Alntessegoc- Elenai) f rom Almessega 6rc~nchc~- A small specimen of this rare elemi was examined ; it had an acid number 32 and a saponification number 54-5.The resin contained one-fourth of its weight of impurities ; when freed from these it was found to con- tain in 100 parts protamyrin C,,H,oO (melting a t 170-171') 30 ; amorphous protelemic cccid 25 ; poteleresen 37.5. Only traces of essential oil and of bitter substance were present and bryoidin could not be detected. It is noteworthy that all the five samples of elemi examined although they were not derived from the same genus of plants oreven from the same family yet contained an amyrin-that is a mixture of two isomeric alcohols with the composition C,,H,,O. In the future Tschirch proposes to regard as elemis proper only those which contain amyrin or an allied substance 40-45.C. F. B. VOL LXXXII. 1. 3 1814 ABSTRACTS OF CHEMICAL PAPERS. Soluble Hydroxyanthraquinone-glucoside contained in Bar- badoes Aloes. By EUGEN AWENG (Chem. Cvntr. 1902 ii 368-369 ; from Apoth.-Zeit. 17 432).-A large quantity of a double glucoside which resembles that contained in Frangula and Xagrada (Abstr. 1901 i 39) has been isolated from the aqueous extract of Barbadoes aloes. This compound gives the reactions of hydroxyanthraquinone and when boiled with hydrochloric acid forms sugar and a substance similar to the $-emodin obtained from Franguln. A considerable quantity of $-emodin may also be extracted from the aloes by treating the portion insoluble in water with 95 per cent. alcohol. By the action of bromine or by boiling this $-emodin with alcohol and acid for a long time emodin and a compound which gives the reactions of rhamnetin are formed.By FRIEDR~CH KRAFT (C'hem. Centr. 1902 ii 533-534 ; from 8chweix. Woch. Pharrn. 40 322-326. Compare Abstr. 1898 i 40 ; 1899 i 32 ; 1900 i 49).-Good extracts prepared from the roots of Aspidium FiZix-mas. contained on the aveiage 3.5 per cent. of filicic acid 2.5 of flavaspidic acid 0.05 of albaspidin 0.1 of aspidinol 0.1 of flavaspidin 5 of amorphous acid and 6 of filicinigrin. Flavaspidic acid may be extracted from crude filicic acid by means of carbon disulphide; it dissolves in 30 parts of hot disulphide and on cooling 85 per cent. crystallises out. Flavaspidin resembles flavaspidic acid very closely and a small quantity is generally contained in the acid. It is however less soluble in carbon disulphide than the acid crystallises from ethyl acetate in colourless prisms melts at 199O and is readily soluble in benzene chloroform acetone or amyl alcohol; it dissolves in alkalis and decomposes carbonates of alkalis or alkaline earths.Filicinigrins consist of decomposition products of the other six components of the extract and form a brown to black amorphous powder ; they are distinguished from the other acids by their insolubility in light petroleum and their physiological inactivity ; their solubility is variable and sometimes the powder is infusible. The chief componeDtof the extractis the amorphous acid andon this its pharmacological effect depends. It forms a brownish-yellow amorphous powder melts at about 6OC is very readily soluble in acetone chloroform ethyl acetate ether benzene carbon disulphide carbon tetrachloride or glacial acetic acid.The slight reduction effected by boiling the acid with ammoniacal silver solutions or with Fehling's solution is probably due to the presence of decomposition products. Ferric chloride pre- cipitates an amorphous reddish-brown substance from the akoholic solution. When melted with alkalis the acid yields the same products as filicic acid (Boehm) together with methylphloroglucinol methyl ether melting a t 118-119" and an acid melting at 137". The amorphous acid must therefore possess a more complicated structure than filicic acid and may possibly be a homologue containing four butanone rings. Reduction of Artemisin by means of Stannous Chloride. By P.BERTOLO ,(Atti R. Accad. Lincei 1902 [v] 11 i 486-492. Compare Abstr. 1901 i 718).-1n order further to study the analogy 3. w. w. Extractum Filicis. E. W. W.ORGANlC CHEMISTRY 81 5 in behaviour existing between santonin and artemisin the author has investigated the reduction of the latter by means of stannous chloride in hydrochloric acid solution. Instead however of yielding a compound analogous with santonous acid this reduction furnishes a product possessing a lactonic structure and having the composition C15H180 the same as that of santonin. This compound crystallises from alcohol or acetic acid in small white needles which melt at 269-270' and are slightly soluble in ebher chloroform benzene or aqueous alkalis; when suspended in water and treated with ferric chloride or sulphuric acid it is turned brown but remains undissolved.On boiling with solutions of the alkalis or alkaline earths the compound yields salts of a monobasic hydroxy-acid ; the barium (C,,H,,O,),Ba silver lead and copper salts were prepared ; when treated with hydrochloric or sulphuric acid these salts are slowly converted into the original lactonic compound The acetyl derivative of the latter C15Hlt03Ac crystallises from alcohol or from a mixture of chloroform or benzene with light petroleum in white shining leaflets or needles which melt at 205-206'; on boiling with potassium hydroxide solution and acidifying with hydrochloric acid the original lactone is re-formed. These results show that in place of the carbonyl group present in artemisin the reduction product of the latter contains a hydroxyl group of a phenolic nature.When fused with alkali the compound yields 1 4-dimethyl-p-naphthol ; this compound is not obtained either from santonin or artemisin and the author concludes that the ketonic groups in the molecules of these two substances occupy corresponding positions. On reducing artemisin by means of zinc dust and acetic acid a dextrorotatory compound of a lactonic nature melting a t 275' is obtained. When artemisin is treated with sodium carbonate and the solution acidified with dilute sulphuric acid a compound is obtained crystal- lising from water in long silky needles which melt at 121-122' and in alcoholic solution are dextrorotatory . T. H. P Degradation of Brazilin. By WILLIAM H.PERKIN jun. (Ber. 1902 35 2946-2947).-A claim of priority (see Proc. 1902 18 147) over Kostanecki and Paul (this vol. i 686). Dyeing of Animal Fibres by Acid Colouring Matters. By PAUL SISLEY (BUZZ. Soc. Chim. 1902 [iii] 2'7 901-914).-The author determines the partition coefficient of picric acid between water and toluene water and ether and water and amyl alcohol and shows that in all these cases the partition coefficient depends on the con- centration. Similar results were obtained with various acid colouring matters. Experiments were also carried out on the extraction of picric acid both in neutral and in acid solution by silk amyl alcohol and toluene when it was found that the amount of picric acid extracted was much greater in acid solution than in neutral This the author explains by the diminution of the dissociation of picric acid by the acid added.R. H. P. 3 1 2816 ABSTRACTS OF CHEMICAL PAPERS. [No reference is made t o the work of Walker and Appleyard (Trans. 1896 69 1334) on this subject.] A. F. Composition of the Tanning Material 'Taran.' By F. SAROSEK (J. Rzcss. Phys. Chem. Xoc. 1902 34 504).-Taran is a root used for tanning in the native tanneries of Central Asia ; i t contains 17 per cent. of tannin which is taken up by leather; ellagic acid is also present. '1. H. P. Action of Hydroxylamine on Ethyl Dimethylpyronedicarb- oxylate. By CARLO PALAZZO (Atti R. Accacl. Lincei 1902; [v] 11 i 562-565).-The action of hydroxylamine on the ethyl di- methyl pyronedicar boxylate prepared by Conrad and Guthzeit (Abstr.1856 333) in presence of sodium carbonate yields a compound which - has probably the constitution CMe< I and separates from C *CO,Et' L water in shining white needles containing water of crystallisation ; it is soluble in acetone hydrochloric acid or acetic acid and in acetic acid soIution gives the normal depression of freezing point The anhydrous compound melts at 164' and immediately afterwards undergoes vigorous decomposition. It decolorises permanganate in the cold and in acetic acid solution absorbs bromine whilst when hested with hydriodic acid it evolves ethyl iodide. With silver nitrate it gives a white precipitate which has the composition C,H,P,NAg,ZH,O and is rapidly turned violet by the action of direct sunlight. T. H. P. Chromone.By R. HEYWANG and STANISLAUS VON KOSTANECKI (Be?* 1902 35 2887-2891. Compare Abstr. 1901 i 735 ; and this vol. i 303 GgO).-Chromone derivatives have been prepared (Zoc. cit.) by condensing derivatives of o-hydroxyacetophenone and ethyl oxalate. Ruhemann and Stapleton (Trans. 1900 77 1179) prepared chromone itself from phenoxyf umaric acid. Chromone-2-carboxylic acid ~ 6 ~ 4 < ~ ~ @ ~ 0 2 H has now been prepared from o-hydroxyaceto- phenone ethyl oxalate and sodium ; the ethyl o-hydroxybenzoyl- pyruvate first formed was not purified but converted into chromone- 2-carboxylic acid by treatment with hydrogen chloride in alcoholic solution ; the acid crystallised in needles decomposing at 252' (com- pare Ruhemann and Stapleton) with evolution of carbon dioxide and formation of chromone.Chromone is decomposed by boiling with alcoholic sodium ethoxide into o-hydroxyacetophenone and formic acid. The melting point of a-naphthachromone (t'his vol. i 303) which has not been previously recorded is 125'. The paper contains a list of the chromone derivatives which u p t o the present time have been prepared. K. J. P. 0. 3 3' 5'-Trihydroxyflavone. By STANISLAUS VON KOSTANECKI and PETER WEINSTOCK (Bey-. 1902 35 2885-2887).-2 4-Diethoxy-3' 5'- dirnethoxybenxo?$acetophenone C,H,(OEt),~CO*CH,*CO*C6H3(OMe) is prepared by heating 2 4-diet3hoxyacetophenone and ethyl 3 6-di-ORGANIC CHEMISTRY. 817 methoxybenzoate with sodium at 130° it crystallises in needles melt- ing at 139-5" and gives a dirty red coloration with ferric chloride.When the P-diketone is boiled with hydriodic acid i t is converted into trihydroxyflavone which for purposes of purification is methylated by means of methyl sulphate and potassium hydroxide. lises in needles melting at 181-182' and by prolonged boiling with hydriodic ezid is converted into 3 3' 5'-trihydroxyJZccvone the latter forms crusts of microscopic needles melting a t 329' dissolves in sodium hydroxide with a greenish-yellow coloration and in con- centrated sulphuric acid with a yellow coloration and a greenish fluorescence 3 3' 5'-Tric~cet0x~JZ~v0ne CI5H7O2( OAc) crystallises in white needles melting a t 187'. Hyoscine and Atroscine. By OSWALD HESSE (J. p ~ . Chenz. 1902 [ii] 66 194-205. Compare this vol. i 51).-Freshly pre- pared hyoscine hydrobromide has [.ID - 27.7" at 15' ; after four weeks the rotation has diminished to [..ID - 25.9".This is probably due to the existence of a labile modification of hyoscine. The latter is obtained on separation of the alkaloid from its salts or from the crystalline form when placed over concentrated sulphuric mid or phosphoric acid. Atroscine monohydrate and dihydrate crystallise together on addition of a crystal of each to the syrupy atroscine at 5-So. At 0" the dihydrate at 15-20' the monohydrate is formed. I n presence of a trace of the monohydrate at 20" the dihydrate changes slowly t o the monohydrate; the change takes place more quickly iu contact with ether a t 15". When pure the dihydrate is not less stable than the monohydrate (compare Gadamer this vol. i 173 ; Kunz-Krause this vol.i 174). When molecular proportions of tropine platinichloride and oscine platinichloride (m. p. 2 10-2 1 2') are dissolved toget her in hot water dark orange-red crystals (C,Hl,Ollr',C,Hl3O,N),,HzPtCl6 separate which contain no water of crystallisation melt and decompose at 202-204' and are probably identical with Ladenburg's $-tropine platinichloride (this vol. i 390). The remainder of the paper is a reply to E. Schmidt's note t o Gadamer's paper. fl-Methylmorphirnethine. By LUDWIG KNORR and SAMUEL SMILES (Ber. 1903 35 3009-3010. Compare Abstr. 1894 i 430)- P-Methylmorphimethine is formed when the a-compound is boiled with acetic anhydride water or 50 per cent. alcohol but not with absolute alcohol. It is best prepared by boiling the a-compound with 60 per cent.alcohol containing 10 per cent. of potassium hydroxide and crystallises in prisms melting at 134-135' ; [ a ] D + 438' (c = 1) in solution in 97 per ceht. alcohol. The base forms a violet solution in sulphuric acid which becomes blue and then green when ice-water is added. The methiodide melts at about 300" and has [.ID + 233' (c = 0.6) in solution in 97 per cent. alcohol The benzoate crystallises in small C15H,02(0H)3 ; K. J. P. 0. Atroscine occurs in a crystalline and an amorphous form. G. Y.818 ABSTRACTS OF CHEMICAL PAPERS. needIee melting at 1 5 7 O and has [a] + 254O (o= I) in aqueous solu- tion. The oily base as obtained by theaction of acetic anhydride on the a-compound can be readily purified by means of the benzoate. A. H.A Fourth Methyhorphimethine. By LUDWIG KNORR and JOHN HAWTHORNE (Ber. 1902 35 3010-3013. Compare the preceding abstract).-y-Methylmorphimethine (Schryver and Lees Trans. 1901 79 563) is converted by boiling alcoholic potash into 8-methylmorphi- methine which crystallises in prisms melting a t 111-113" and has [.ID + 256%' (c= 1.243) in solution in methyl alcohol. The base is as a rule more readily soluble than the y-isomeride. The methiodide of s-mtlthylmorp~~imethine crystallises in rectangular plates which melt and decompose at about 282-284O ; [.ID + 150.7' (c = 1 *003) in abso- lute alcohol. This substance can also be obtained by heating the methiodide of the y-base with dilute aqueous potash. The benzoate crystallises in slender needles melts indefinitely at 99-108O and has [.ID + 181*L0 (c = 0.6315) in solution in 99 per cent.alcohol. y-Methyl- morphimethine benzoate also melts indefinitely at about loo' is more readily soluble in water than the y-derivative and has [ a] + 41.3' (c = 0,8685) in solution in 99 per cent. alcohol. A. H. Morphigenine and Epiosine. By ERNST VAHLEN (Ber. 1902 35 3044-3047. Compare Arch. Path. Pharm. 48 368).-In reply t o the criticism of Pschorr (this vol. i 672) the author maintains that the physiological action of epiosine resembles that of morphine and is not due to the formation of methai?moglobin in the blood of the ttnirnals experimented on. A. H. Addition of Sulphurous Acid on Quinidine. By WILEELM KONIGS and HANS SCHONEWALD (Ber. 1902 35 2980-2991).-An aqueous solution of quinidine which has been saturated with sulphur dioxide deposits after some weeks the monobasic mid C,,H2,07N2S2 ; this crystallises with 4H,O and decomposes a t about 260'.I t s solu- tions in dilute sulphuric acid exhibit a blue fluorescence and give the colorations with chlorine water and ammonia characteristic of quinine and quinidine. The hydrobromide and hydrochlos*ide are both crystal- line salts. The ammonium salt with 4H,O is amorphous and has [a] 160'42' at 19.5'. The 6arium and silver salts were obtained as yellow amorphous precipitates and the monobp*omo-derivative C:,,H,,07N,BrS as a pale yellow crystalline precipitate. When oxidised with chromic acid the acid yields quininic acid and when oxidised with permanganate in the cold the sulphonic acid C20H2,0,N2S2 which crystallises with 4H20 in beautiful white six- sided leaflets and forms a pale yellow amorphous hygroscopic ammonium salt.Quinine yields the analogous additive produc5 C,,H2,O7N,S,,H,O only in small quantities. R. H. P. Pipecoline Derivatives. By G. VON OSTOJA BALICKI (Ber. 1902 35 2780-2782).-NitrosopipecoZine i s an oil boiling at 123" underOBGANIC CHEMISTRY. 819 31 mm. pressure ; it is prepared by treating a solution of pipecoline in cold dilute sulphuric acid with sodium nitrite. On reduction with zinc dust and water the nitrosoarnine yields pipecolylhydranine (1. amino- pipecoline) ; this product is a coloiirless oil boiling at 156-160' which has a sp. gr. 0.90058 a t 1go/4O. The 8-hydrazine solidifies on cooling in solid carbon dioxide and yields uncrystallisable salts with halogen hydr- acids ; the picm!de crystallises from alcohol in orange-yellow needles and melts a t 143O.A crystalline hydrazone C,.H~,N*N:CH*C,H,*NO melting a t 63' was obtained from the hydrazine and m-nitrobenzaldehyde but benz- aldehyde piperonaldehyde acetone and acetophenone yield oily hydr- azones and dextrose furnishes only an uncrystallisable osazone. G. T. M. Condensation of Aldehydes with Ethyl Cyanoacetate. I. By ICILIO GUARESCHI (Atti R. Accad. Sci. Torino 1901-1902 37 593-611. Compare Abstr. 1900 i 52 and Ill).-The author has shown (loc. cit.) that the reaction between an aldehyde ethyl cyanoacetate and ammonia leads not to a piperidine derivative as was to be expected but to a pyridine compound there being an apparent disappearance of hydrogen.The latter the author has now traced and he finds that it is used up in converting some of the cyanoacetamide derivative which is an intermediate product in the above reaction into the corresponding saturated compound. These reactions are expressed by the equations (1) R*CHO + CN*CH,*CO,Et + NH = Et*OH + H,O + R*CH:C(CN)*CO=NH,. (2) R*CH:C(CN)*CO*NH + H =.R*CH,*CH(CN)*CO*NH,. This reaction may also be employed to obtain not only dicyanodioxypyridinzs but also monoalkylcyanoacet- amides. The reactions of certain other aldehydes with ammonia and ethyl cyanoacetate have been studied the results being as follows m-Tolualdehyde ammonia and ethyl cyanoacetate give rise to three products ( 1) The ammonium derivative of rn-to~y~d~cyanog~utacon~m~de C,H,Me*C<CH(CN).Co C(CN)-co>N*NH4 the main product of the reaction \ I crystallises from water in colourless anhydrous needles which are soluble in pyridine and do not melt even at 290' ; when heated with 60 per cent.sulphuric acid it yields na-tolyl-y-cyanovinylacetic acid C,H,Me*C( :CH*CN)*CHB*CO,H t o be described in a later communica- tion ; the silver and copper ( + 6H,O) salts were prepared. (2) m-ToZyZ- cyanoacetamide C,H,Me*CH,*CH( CN)*CO*NH crystallises from water in broad nacreous lamin2 which melt a t 108.5-109*5° and are soluble in alcohol ether or pyridine. (3) A compound almost insoluble in water and melting in the crude condition at 194-198O. Cuminaldehyde ammonia and ethyl cyanoacetate yield two pro- ducts (1) The ammonium derivative of propylphenyl-PP-dicyano- glutaconimide C H P r * C < ~ ~ ~ ~ ~ ~ > N * N H crystallising from water in yellowish slender needles dissolving in alcohol or pyridine and remaining unfused at 290' ; when heated with 60 per cent.sulph- uric acid it yields P-propylphenyl-y-cyanovinylacetic (cumyl-y-cyano- viuylacetic acid) to be described in another communication. The copper520 ABSTRACTS OF CHEMICAL PAPERS. (+ 8H,O) and silver salts were prepared and analysed. The coniime derivative C,,H,,O,N,,C,H,,N is precipitated either in prisms or needles melting at 251-252'; the micotine salt forms a minutely crystalline precipitate melting a t about 300'. (2) Cumylcyanoucet- amide (a-cyanopropylphenylhydrocinnamamide) C,H,Pr*CH,*CH( CN) *CO*NH separates from water in long colourless silky needles which are soluble in alcohol or pyridine and melt at 144-145'; it sublimes but with partial decomposition. Its solution is neutral and develops ammonia when heated with potassium hydroxide.%-Butaldehyde ammonia and methyl (or ethyl) cyanoacetate inter- act with the formation of (1) The ammonium derivative of prop$ dicyunogZu,tuconimide CH2Et*C<CH(CN),Co c(cN)-co>N*N€€4 which separ- ates from water in slender silky needles soluble in pyridine ; it has a bitter taste recalling those of quinine and magnesium sulphate. When heated with 60 per cent. sulphuric acid it yields P-propyl-y.cyano- vinylacetic acid to be described later ; the silver salt was prepared. (2) But ylcyamoacetczmide (/I-pr opy 1-a-c y anopr opionamide) CHPr-CH(CN)*CO*NH which crystallises from water in thin nacreous lamin= melting at 125-5-126.5' and subliming in iridescent plates ; it gives a neutral aqueous solution is soluble in pyridine and yields ammonia when heated with potassium hydroxide solution.Benzaldehyde ammonia and ethyl cyanoacetate yield (1) benzy 1- cyanoacetamide (2) phenyldicyanodioxypyridine (Zoo. cit.) and (3) a wmpound insoluble in wator and probably identical with that of Carrick. Anisaldehyde ammonia and ethyl cyanoacetate yield anisylcpano- ucetumide OMe-CI,H,*CH,W€(CN)*CO*NH2 which crystallises from ether in slender silky needles soluble in water or alcohol and melting a t 172'. From heptaldehyde ammonia and ethyl cyanoacetate are obtained -the two products (1) the ammonium derivative of y-hexyl-PP-dicyano- dioxypyridine and (2) heptyl-a-cyanoacetamide which will be described in a later communication.T. H. P. Action of Sulphuryl Chloride on Pyrrole. By GIROLAMO MAZZARA (Gaxzetta 1902 32 i 510-514).-The interaction of 1 mol. of sulphuryl chloride and 1 mol. of pyrrole yields an unstable monochZoi.o-derivative of the latter which is a heavy yellow liquid and decomposes explosively whilst with 2 mols. of the chloride a dichloyo- compound is obtained which when repeatedly distilled in a current of steam is converted first into a white buttery mass and afterwards into carbonaceous matter. Both these compounds are volatile in a current of steam and colour sulphuric acid green whilst pine shavings moistened with hydrochloric acid are turned red by them.Tetrachloropgrrole C,NHCI is obtained in good yield by the inheraction at 0' of an absolute alcoholic solution of pyrrole with sulphuryl chloride (4 mds.) and is identical with Ciamician and Silber's (Abstr. 1885 1077) compoundp T. H. P,ORGANIC CHEMISTRY. 821 Formation of Pyrrole Derivatives from isoNitrosoketones. By LUDWIG KNORR and H. LANGE (Bey. 1902,35 2998-300s. Com- pare AnnuZen 1886,236 296).-Pyrrole derivatives have hitherto been obtained from three different isonitroso-derivatives by reduction in presence of a ketone or ketonic ester and the reaction has now been extended t o four additional isonitroso-compounds. The intermediate formation of amino-ketones is rendered probable by the fact that in many cases the substitution of aminoacetophenone for isonitrosoaceto- phenone was accompanied by a considerable increase in the yield whilst in certain cases pyrrole derivatives were obtained from tho amino-ketone but not from the isonitroso-ketone I n the new series of syntheses the following results were obtained.isoNitrosoacetophenone yields pyrrole derivatives with ethyl acetoacetate (the yield being 56 per cent.) acetylacetone (40 per cent.) ethyl acetonedicarboxylate ( 3 per cent.) benzoylacetone (4.5 per cent.) but does not yield them with ethyl oxalacetate ethyl acetoneoxalate dibenzoylmethane formyl- acetone phenylacetone diphenylacetone or acetophenone. Amino- acetophenone gives pyrrole derivatives with ethyl acetoacetate (almost 100 per cent.) acetylacetone (100 per cent.) ethyl acetone- dicarboxylate ( 9 per cent.) benzoylacetone (38 per cent.) and in traces with ethyl acetoneoxalate formylacetone and phenylacetone whilst i t does not yield them with ethyl oxalacetate dibenzoylmethane benzoylaldehyde diphenylacetone and deoxybenzoin.isoNitrosodeoxybenzoin yields pyrrole derivatives with ethyl aceto- acetate (25 per cent.) and with acetylacetone (50 per cent.) but not with deoxybenzoin. isoNitrosoacetone yields pyrrole derivatives with ethyl acetoacetate (50 per cent.) acetylacetone (33 per cent.) and in traces with benzoyl- acetone. Finally dimethyl isonitrosoacetonedicarboxylate yields ;t pyrrole derivative with dimethyl acetonedicarboxylate. Acetone and methyl ethyl ketone wi t.h isonitrosoacetone and acetolle with isonitrosoacetophenone give products which only yield the reac- tions of pyrrole derivatives after treatment with strong sulphuric acid.These cases seem to indicate that t h e reaction proceeds in two stages The following new compounds have been obtained by this method. is Ethy Z 3-phenyZ-5-methy Zpywole-4-car.Eoxy Zccte N H< prepared from ethyl acetoacetate and isonitrosoacetophenone or amino- acetophenone melts a t 1 0 5 O and gradually becomes yellow in the air. The corresponding cccid melts and loses carbon dioxide at 115". Bi- CMe ?* C0,Et C H I CPh methy Z 3-pheny ZpGrole-4 -carboxylo-Fi -metate C( CH,* C0,Me) ?*CO,Me NH<CH==Iz==Cph ' prepared from met.hy1 acetonedicarboxylate and isonitrosoacetophenone me1 t s at 1 2 6'. 4- A cet y l - 3-phen y l-5 -me t h y Zp yrrole CMe Y-COMe NH<CH=CPh ' prepared from isonitrosoacetophenone and acetylncetone melts a t 15 la and is converted by the action of benznldehyde and aqueous potash into 4-cinnccmoyl-3-phenyl-5-nzet~~~lp~~~~~o~e melting at 16T.s22 ABSTRACTS OF CHEMICAL PAPERS.CMe QBz prepared from 4-Benzo yl-3-phen yZ-5-methyZpyrrole NH< CH= CPh isonitrosoacetophenone and benzoylacetone melts at 231'. E t h d prepared CMe :$WO,Et CPh-CPh 2 3-diphenyZ-5-~~eth~Z~y~~~~o~cccrboxylate NH< from ethyl acetoacetate and isonitrosodeoxybenzoin is a colourless crystalline substance. CMe:~Ac is prepared CPh CPh' 4- Acetyl-2 3 -diphen yl-5-meth ylpyrro Ze NH< from acetylacetone and isonitrosodeoxybenzoin and is converted by benzaldehyde into 4-cinnamoyl-2 3-diphen?/l-5-methyl~yr~ole which melts a t 215'.The reaction product obtained from acetone and isonitrosoacetone does not contain a pyrrole derivative but one is formed when it is mixed with sulphuric acid. The expected dimethylpyrrole could not be obtained pure a large proportion of dimethylpyrazine being simultaneously formed. A. H. . [Double Salts of Thallium and Alkaloids with Hydracids.] By CARL RENZ (Ber. 1902 35 2768-2774. Compare R. J. Meyer Abstr. 1900 ii 655 and this vol. i 393).-ThaZlic bromide pyridine hydrobromide (TIBr,),(C,NH,,HBr) obtained by dissolving the corre- sponding double chloride in hot concentrated potassium bromide solu- tion crystallises on cooling in pale yellow needles melting a t 174'. Thccllic chloride piperidine hydrochloride TlCl,( C5NHll,HCl)3 unlike the other organic double salts of the type is extremely soluble and separates from a concentrated solution of its generators only after further evaporation under reduced pressure ; it forms long prismatic crystals soluble in alcohol but not in ether.Thallic iodide hyoscyamine hydriodide T11,,C17H,,0,N,HI separates in red crystals from a concentrated solution of potassium iodide and the corresponding double chloride and melts a t 200'. Tl~allic iodide atropine hydriodide T113,C 7H230aN HI resembles the preceding compound and melts a t 192'. Thullic chloride cocaine hydrochloride TlCI,,(C,7H,,0,N,HC1) re- sulting from the interaction of its generators in concentrated solu- tions crystallises in white needles. Thu Zlic chloride styy chnine hydrochloride TlCl,,( C2,H,,02N,,HC1) obtained like the preceding double salt crystallises from a mixture of alcohol and dilute hydrochloric acid in iridescent leaflets decomposing at 240'.Thullic chloride cinchonine hydrochloride TlCl,,( C,,H,,ON,,HC1),,4I3[,0 crystallises from hot dilute hydrochloric acid in aggregates of silky needlqs. T'halZic chloride quinine hydrochloride T1C13,C2,H,,02N,,HC1,2H,0 closely resembles the preceding compound. Thallic chloride yields less stable double salts with coniine nicotine and 2 6-lutidine ; with morphine it gives rise to an insoluble yellow- ish-white powder (T1C13),,C17H,90,N.ORGANIC CHEMISTRY. 823 Dimethylaniline interacts with thallic chloride giving rise t o a violet colouring matter resembling crystal-violet ; dimethyl-o-toluidine furnishes a similar dye of redder shade.Methyldiphenylamine when left in contact with a n alcoholic solu- tion of thallic chloride becomes oxidised to a blue colouring matter which is probably identical with diphenylamine-blue. The Three Isomeric Cyanides of Pyridine. G. T. M. By RUDOLF CAMPS (BYc~. Pharm. 1902 240 366-3$0).-811 three cyanopyridines can be obtained by distilling under diminished pressure a mixture of phosphoric oxide with the amide of the corresponding pyridine- carboxylic acids (this vol. i 824). In the case of the 4-compound it was found also that the cyanide can be obtained by distilling a mixture of the acid with lead thiocyanate. 2-Cyanopyridine is not reduced to pyridylmethylamine by 3 per cent. sodium amalgam ; pyridine and hydrocyanic acid are formed and at the Game time a certain amount of hydrolysis to the amide and the acid takes place.Nor ca.9 4-cyanopyridine be reduced with aluminium amalgam ; the acid is formed. Cyanopyridines (pyridyl cyanides) c,NH,.CN.-The %compound (picolinonitde) melts at 29'. The 4-isomeride (isonicotinonitde) melts at 79" ; its hydrochloride platiniddoride and atwicldoride melt and decompose at 199') 293' and 185' respectively ; the mercurichloride C,NH,*CN,HgCl was analysed. C. F. B. E thy1 2 6-Dimethyl-4-chloronicotinate. By AUGUST MICHAELIS and R. HANISH (Ber. 1902 35 3156-3161).-The compound previously described as 2 6-dimethylchloroethoxylutidine (Abstr. 1901 i 609) is now shown to be ethyl 2 6-dimethyl-4-chloronicotinate (compare Collie Trans. 1891 59 176). The aurichlovide of the ester melts at 116-117' and the picrccte at 129'.Methyl iodide at 95-100° transforms the ester into ethyl 2 6-dimethyl-4-iodonicotinute methiodicle C,,H,,O,NI,MeI melting at 194'. Methyl bromide yields the methobromide C,oH,,O,NCl,MeBr melting at 198'. Concentrated hydrochloric acid at 150' converts the ester into y-lutidone melting at 224-225'. Aniline yields Conrad and Epstein's phenylaminolubidine (Abstr. 1887 50 1). 4-chloro-2 6- dimethylnicotinic acid melts at 168-170' and when heated at 175" loses carbon dioxide and yields chlorolutidine. 4-Fthozy-2 6-dimethyl- nicotinic ucid crystallises from hot water in coloiirless needles contain- ing 3H,O; when anhydrous it melts at 200-201'. The sodium salt silvei. salt and the hydrochloyide melting at 127O have been prepared.J. J. S. Derivatives of 2 6-Dichloroisonicotinic Acid. By KARL BITTNER (Ber. 1902 35 2933-2936).-2 6-Dianilinopy~idine-4-carb- oxyanilide C,NH2(NHPh),*CO*NMPh prepared by heating dichloro- isonicotinic acid with aniline crystallises from alcohol in olive-green glistening hexagonal plates and me1t.s at 140-141'. The mid C,NH,(NHPh),*CO,H crystallises from alcohol in yellow micro-824 ABSTRACTS OF CHEMICAL PAPERS. scopic needles and does not melt at 300". The methyl ester C,NH,(NHPh),*CO,Me crystallises from alcohol and melts at 142'. 2 6-D~thiol~y~iJi~~e-Li-carboxyZic acid C,NH2(SH)2*C0,H forms small reddish-yellow needles and melts at 230'. The potassium salt KS*C,NH,( SH)*CO,K,EtOH separates from alcohol in insoluble glistening golden flakes and does not lose i t s alcohol of crystallisation by long drying at 110'.The methyl ester C,NH,(SH);CO,Me separates from dilute methyl alcohol in microscopic cinnabar-red needles melts at 156O and has a characteristic odour. The acid appeals to be oxidised by nitric acid to the corresponding disulphonic acid. T. M. L. Some Carbamides Thiocarbamides and Ethyl Carbamates of Pyridine. By RUDOLF CAMPS ( A ~ L Pharm. 1902 240 345-365).-isoNicotinic acid was found to melt at 315". The carboxylic acids C,NH,*CO,H were converted into the esters C,NH,*CO,Et by heating them on the water-bath with a mixture of equal weights of alcohol and sulphuric acid; the 4-esterr. boiling at 218O takes up ethyl iodide and when the additive compound is treated with moist silver oxide it forms a silver salt from which by treat- ment with hydrogen sulphide and evaporation of the filtered liquid /,CH*CH\\ the ethylbetaine of isonicotinic acid C%O-0-NEt \\ melting and de- \CH:CH/ composing a t 241° was obtained. The esters were converted into the amides C,NH,*CO*NH by pouring concentrated ammonia over them and allowing the mixture t o remain at the ordinary temperature ; the 4-acmide melts a t 155" when anhydrous at 117-120" when crystallised with water.The amides were converted into the aminopyridines C,NH,*NH2 by treatment with a solution of bromine in aqueous potassium hydroxide ; at the same time clibrontonn2iiaopyridines C5NH2Br2*NH2 melting at 137" 148' and 167" in the case of the % 3- and 4-compounds respectively were formed in small amount and also some bl.onzo-2-rcmino;llyridine C,NH,Br.NH melting a t 106-107° Rnd crystallising in slender lustrous needles and a sub- stance melting a t 196" probably a complex carbamide derivative (compare Pollak Abstr.lS95 i 391) in the cases of the 2- and 3-compounds respectively. The amines condense with acetic an- hydride t o form the ucetylumi~zo~yridines C,NH,*NH Ac or '' anti- febrines " of the pyridine series which melt respectively at 71" 133" and 150" (when anhydrous; the last a t 124" when crystallised with water). The amines are all converted into hydroxy pyridines (pyridones) when diazotised in cold sulphuric acid solution (conipare Marckwald Abstr. 1894 i 381 who obtained chloropyridine only when diazo- tisin g in hydrochloric acid solution) With ethyl chloroforma6e in ethereal solution they form ethyl py~idinecurbamates (urethanes) CO,Et*NH*C,NH melting respec- tively a t 105") go" and 129" and sometimes also a little of the di- py~id?/Zcarbunzides CO(NH.C,NH,) which can always be obtained byORGANIC CITEMHTRT' 825 the further action of the amine on the carbamate and melt at 1754 225" and 208' respectively ; with aniline the 2-carbamate forms 2-pyridylphenylcarbamida NHPh*CO*NH*C,NH crystallising in slender needles and melting at 180'.With phenylthiocarbimide the aminopyridines condense to pyridylphenylthiocarbamides NHPh*CS*NH*C,NH which melt a t 171' 164' and 148' respectively. When heated with carbon disulphide in alcoholic solution 2-aminopyridine forms di- p?/ridylt~~iocurbumide CS(NH*C,NH,) crystallising in lustrous highly refractive long needles or prisms and melting at 163' along with small quantities of substunces melting at 147' and 85' respectively ; the 4-amine forms ethyl 4-p?/rid?lZthiocarbamc~te OEt*CS*NH*C,NH crystallising in needles and melting a t 110' when anhydrous at 92-93' when crystallised with water together with a yellow sub- stance probably 4-ccrninopyidine 4-;u?lridyldithiocclrbc~~7~~te? C,NH,*NH,,SH*CS*NH*C,NH which melts and decomposes at 152". C.F. B. Condensation of 2 4-Lutidine with p-Nitrobenzaldehyde. Compare Bialon this By R. KNICK (Be?.. 1902 35 2790-2793. vol i 828).-p-~its.opl~enyl-2 ; 4-lutidykulkine NO,*C,H,*CH(OH) CH,*C,NH,Ne produced by heating 2 4-lutidine and p-nitrobenzaldehyde at 130-135' crystallises from alcohol in yellow plates melting at 168-169' ; the base is insoluble in water and dissolves only sparingly i n the other organic solvents.The hydi*ocMoride separates i n fern- like crystals and melts at 242' ; the picmte crystallises from water in golden spangles containing lH,O the anhydrous salt melts at 171'; the benxoute C2113,s04N2 forms white flakes decomposing at 214'; the plutilzichloride melts a t 2 19'. The preceding base yields p-ccmiiaophenyl-2 4-ZutidpZuclkine on reduc- tion with tin and hydrochloric acid; this melts at 130' and yields a platinichloride crystallising in orange-red needles and decomposing at 222'; the mercurichloi*ide separates in needles and melbs at 836'. p-Nitro-4-nzet7~yZsti~6u~oZe? NO,*CsH,*CH:CH*C,NH,Rlc is a bye- product in the preceding condensation ; i t crystallises in pale yellow lustrous leaflets and rnelts at 134' ; the hydrochloride separates in yellow needles melting a t 234-235' ; the plutinicldoTide and mes.curi- chloride melt respectively a t 23'1' and 187' respectively ; the base also yields a dibromide.p- Ainino-4-met?~ylst~l~~czoZe produced by reducing the preceding base melts at 119' and yields a hydrochloride and a dibromide separating in white crystals and decomposing respectively at 208' and 157"; the pEutinicl&wide and rnercurichloride form yellow needles ; the former darkens at 280' without melting the latter decomposes at 176'. G. T. IT. Reduction Products of U- and y-Benzylpyridines. By A. E. TSCHITSCIIIBABIN (J. Buss. Phys. Chem. Xoc.1902 34 508-5 14).- By the reduction of 2- and 4-benzylpyridines with sodium in alcoholic826 ABSTRACTS OF CHEMICAL PAPERS. solution yields of 60-70 per cent. of the corresponding benzyl piperidines are obtained. i-2-BenxyZpiperidi.ne CH,Ph*C,NHlo boils a t 267-268' and crystal- lises in needles melting at 32'; it has a faint odour resembling that of piperidine and is soluble in alcohol or ether; the hydrochloride forms hydrated acicular crystals which melt a t 58' whilst the anhydrous salt melts at 137' ; the platinichloride crystallises from water in yellow needles which melt with incipient blackening at 210" ; the aurichloride separates as golden-yellow flattened needles melting at 168-170'; the picrate crystallises from alcohol or acetone in short thick prisms which melt at 156-157' and are slightly soluble also in water or benzene.4-BenxyZpipe~idine CH,Ph*C,NHlo is a liquid having a faint odour of piperidine and boiling a t 279'; when strongly cooled i t yields a crystalline mass melting a t 6-7'. It is soluble in alcohol or ether and has a sp. gr. 0.9972 at 20"/0'. The hydrochloride froms white scales melting at 172-173' ; from aqueous solutions the platinichloride separates in large shining plates melting at 197' the aurichloride in plates melting at 145-146' and the picrate in long thin shining prisms melting at 184'. 4-Benzyltetrahydrop y r idine (4-benxylpiperidine) CH,Ph* C,NH which is also obtained from the reduction of 4-benzylpyridineY is a viscoixs liquid having a n odour resembling that of sperm oil and boiling at 280-282'; its sp.gr. is 1.018 at 20'/Oo. Its picrate separates from alcohol in thick prisms melting at 129-131'; the plathichloride separates from water in yellow prisms melting at 193-195'. The mother liquor from the reduction of the 2-compound also yields a small quantity of a liquid boiling at 270-272' but there was not suflicient t o allow of its investigation. T. H. P. Nitro- and Amino-stilbazoles. By ERNST SCHMIDT (Arch. Pharm. 1902 240 390).-The meta-compounds lately described (Feist this vol. i 642) had been obtained already by Bchuftan (Abstr. 1890 1438). C. F. B. Action of p-Tolualdehyde on 2-Picoline and 2-Methyl-6- phenylpyridine. By WOLFGANG DIERIG (Rer. 1902,35 2774-2779). -p-Meth y I- 2-stilbaxole C5NH4*C H CH * C,H,Me produced by condens- ing 2-picoline and p-tolualdehyde with zinc chloride a t lSO' separates from dilute alcohol in colourless felted crystals and melts a t 82' ; it is insoluble in water but dissolves in the ordinary organic solvents and forms a hydrocidoride C14H1,N,HCl,H20 crystallising from water or alcohol in pale yellow needles sintering at 170" and melting at 190-1 9 1'.The platinichloride ( Cl,H,,N)2,H2PtCI,,H20 decomposes at 194-1 95' ; the aurichloride crystallises in flattened red needles decomposing at 180-181' ; the rnercurichloride forms yellow needles blackening at 219' and decomposing at 225'; the picrats separates in yellow needles and melts a t 193-194'. A bromine additive product C14H,,NBr,,HBr is obtained i n the form of its hydrobromide byORGANIC CHEMISTRY. 827 mixing bromine and the base in carbon disulphide solution ; i t decom- poses a t 170'.p-Methyldihydro-2-stilbazole C,NH,*CH,*CH,*C,H,Me prepared by heating the preceding base with concentrated hydriodic acid at 140-150° is a colourless oil boiling a t 294-296' under the ordinary pressure; it has a neutral reaction and is darkened by exposure t o light. The platinichloride and aurichloride crystallise in yellow needles and melt respectively a t 180' and 138-140'. p-MethyL2-stilbaxoZine C14H21N resulting from the action of sodium and alcohol on p-methyl-2-stilbazole is an oil boiling at 145-14s' under 11 mm. pressure and having a characteristic disagreeable odour. The platinichloride aurichloride and picrate crystallise in yellow needles melting respectively at 182' 136' and 125'.p-~olyl-Z-picolyZaZk~ne C,NH,*CH,-CH(OH)*C,H,Me resulting from the action of ptolualdehyde on 2-picoline a t 140' crystallises from alcohol in lustrous needles melting a t 93'; the pkutinichloride is a red crystalline substance sintering a t 140' and melting at 150'; the auri- chloride forms golden-yellow needles soluble in water or alcohol but not in ether ; it melts a t 131'. 6-Phenyl-p-methyl-2-stilbaxole C,NH,Ph*CH:CH*C,H,Me prepared by condensing 6-phenyl-2-methylpyridine and p-tolualdehyde with zinc chloride a t 180-190° crystallises from alcohol in needles and from ether in thick spicules ; it melts at 113'. The hydrochloside C,,H,7N,HCl,H,0 separates in yellow needles from water or alcohol ; it sinters at 195' and melts at 202'.the awrichloride and the mercuk&loyide crystallise in needles and the last of these salts melts at 183'. The picrate crystallises with 3H,o and melts at 196'; the bromine additive compound separates from alcohol in transparent leaflets and melts at 173'. 6-PhenyLp-methyZ-2-stilbccxoline produced by reducing the preceding base with sodium and alcohol is a pale yellow oil having a disagreeable odour and boiling a t 245" under 20 mm. pressure which solidifies to a glistening mass in a freezing mixture The hydrochloride separates in white crystals soluble in water or alcohol ; it sinters at 230' and melts at 250'; the picrate crystallises in needles sintering at 180' and melting at 197'. Theplatinichloride (%.OH- 7N >z 9 H P C 1 ,H,O G. T. M. Action of Aldehydes on 6-Phenyl-2-methylpyridine. By OTTO OLLENDORFF (Ber.1902 35 2782-2786. Compare Abstr 1901 i 165 ; this V O ~ . i 234 and 818).-6-Phenyl-2-picolyZ-p-nitro- phenykalkine C5NH3Ph*CH,*CH(OH)~C6H,*N0 produced by con- densing 6-phenyl-2-methylpyridine p-nitrobenzaldehyde and a small quantity of water at 140° crystallises from alcohol in white needles and melts at 112' ; the hydrochloride C,,H,,O,N,,HCl,H,O separates in tabular crystals from its alcoholic solution on adding hydro- chloric acid; it melts a t 126'. The platinichloride forms yellow prisms and melts a t 212'. 6- PhenyL2-p-nitrostilbaxoZe C,NH,Ph * CH CH*C,H,*NO crystallises from alcohol in lustrous plates melting at 142'; i t is obtained in small quantity by condensing 6-phenyl-2-methylpyridine and paitrobenz-828 ABSTRACTS OF CHEMICAL PAPERS.aldehyde at 150' in the presence of zinc chloride. The hydrochlorz'de crystallises in white needles and melts a t 135'. 6-Phenyl-2-p-methoxystiZbaxole C5NH,Ph* CH:CH* C6H4* OMe prepared in a similar manner from the substituted pyridine base and anis- aldehyde crystallises in white needles and melts a t 129' ; the hydro- chloride separates in yellow needles melting a t ZOO' the hydrobromide is obtained in fan-shaped aggregates ; the double thallic salt TlC13,( C,,H170N,HC1) (compare Renz this vol. i 822) crystallises from dilute alcohol in yellow leaflets melting at 98' ; the platinichloride crystallises in prisms melting a t 245' and the mercurichloride in yellow needles melting a t 221'. The preceding stilbazole derivative when reduced with sodium and alcohol yields an oily base which is characterised by its hpdro- chloride C2,H2,0N,HCl a " substarice crystallising in needles melting at 229'.2- o- 17ricl~loro-~-l~yd?~oxypropyk 6 -phen ylpyridine C,NH,Ph*CH,*CH(OH)*CCl produced by heating 6-phenyl-2-methylpyridine with chloral on the water-bath crystallises in triclinic plates melting a t 65' and con- t aining 1 &H,O ; it s platinichloride (C,~H,,ONCI,) H,Pt Cl 2 H,O crystal- lises in red needles and melts a t 201 . 6-Phenyl-2~yi~idylncryl~c acid C,NH,Ph*CH:CH*CO,H results from the action of alcoholic potassium hydroxide on the preceding base and is isolated in the form of its hydrochloride; the platinichloride (C1411110~N),,H2PtCl crystallises from alcohol in yellow leaflets and melts at 604".G. 1'. M. Action of Anisaldehyde on Quinaldine 2-Picoline and 2- Methyl-5-ethylpyridine. By 0. BIALON (Ber. 1902 35 2786 -2790. Compare preceding abstracts).-Anisylidenequinaldi~ie OMe*C,H;CH:CH*C,NH produced by condensing quinaldine and anisaldehyde at 180' in the presence of zinc chloride crystallises from alcohol in white lustrous leaflets melting a t 126' ; the hydrocldoride separates from water iu yellow needles and melts at.208" ; the pZntinichlo&de is a yellow in- soluble substance melting a t 254' ; the auricldoride is also yellow crystallises from dilute hydrochloric acid and melts a t 199'; the yicrate crystallises from acetone in yellow needles. When reduced with sodium and alcohol the preceding base gives rise to p-methoxy- benxyltetraT~ydropuinaldine OMe*C,H,*CH,*CH,*C,NH, a secondary amine crystallising from alcohol in white silky needles melting a t 71' ; the benxoyl derivative prepared by the Schotten-Baumann reaction crystallises in white needles and melts a t 97'; the IqdrochZo&ie separates in yellow feathery crystals and melts a t 21S0 the auri- chloride and platinichloride are unstable.p-Methoxy-2-stilbazole OMe*C6H,.CH:CH*C5NH obtained in a poor yield by heating a-picoline and anisaldehyde at 180-190' for 36 hours in the presence of zinc chloride crystallises from alcohol in lustrous silvery leaflets melting at 75' ; the hydrochloride separates from hot water in yellow needles and melts at 200-201°; the azcri-ORGANIC CHEMISTRY. 820 chloride and platinichloride melt respectively a t 178' and 225' (com- pare Scliuftan Abstr.1889 1437). On reduction with sodium and alcohol the preceding base yields an oily amine the hydrochloride of which crystallises in white needles and melts a t 173" ; the double salts with platinum gold and mercury are unstable oily products. p-Meth,oxy-5-eth,yZ-2 -stiZbaxoZe OMe* C,H; C H CH*C,NH,Et result- ing from the interaction of 2-methyl-5-ethylpyridine and anisalde- hyde was only isolated in the form of aurichloyide and platinichloride these salts melting respectively at 137" and 201"; the latter crystallises in yellow needles. Compounds of Quinoline and isoQuinoline with Cupric and Cuprous Thiocyanates. By FRANZ M. LITTERSCHEID (Arch. Pharm. 1902 240 386-390. Compare Abstr. 1901 i 635 ; this vol.i 308).-Quinoline and isoquinoline unite with dry cupric thio- cyanate forming green substances of the composition Cu(C,NH7*CNS),. With cuprous thiocyanate they unite t o form golden-yellow crystsls with the composition Cu,(C,NH7*CNS),,2C,NH7. When dried at 1 OO" these leave first lemon-yellow substances with the composition Cu2( C,NH7*CNS) and finally cuprous thiocyanate. With cuprosocupric thiocyanate the golden-yellow crystals mentioned above were obtained. G. T. M. C. F. B. Preparation and Properties of some Quinoline Bases of Fluorene and Fluorenone. 11. By OTTO DIELS and OTTO STAEHLIN (Bey. 1902 35 3275-3284. Compare Abstr. 1901 i 521).-2- Aminofluorene (Zoc. cit.) when boiled with glycerol arsenic acid and concentrated sulphuric acid gives Juoreneqzcinoline YH2->C,NH which crystallises in white plates melts at 134.5' (corr.) boils at 390-400° and is almost insoluble in water or cold alcohol but soluble in hot alcohol methyl alcohol benzene or acetone; it is only when fresh that i t dissolves in ether but it easily dissolves in chloroform.The hydrochloride forms yellow needles containing 2H20 and melting at l l O o or when anhydrous at 241" (corr.). The salts are in general fairly insoluble. The methiodide C,,H,,NI,H,O when anhydrous de- composes a t 241" (corr.) without melting. When reduced with zinc and hydrochloric acid the quinoline base gives Jhorenetetrahydro- quinoline C,,H,,N which forms white needles melts at 143" (corr.) is insoluble in cold water slightly soluble in alcohol to a blue fluorescent solution and easily so in ether acetone benzene or chloroform.Its hydrochloride crystallises well as do also the sulphate nitrate and platinichloride. With oxidising agents the tetrahydro-compound gives an indigo-blue coloration which becomes violet then brown; it reduces an ammoniacal silver solution . Nitrous acid converts i t into a nitroso- compound of the formula C16H,40N2. This nitrosoamine melts at 162' (corr.) and is insoluble in water but soluble in chloroform acetone or benzene or in concentrated sulphuric acid to a greenish solution ; it responds to the Liebermann nitroso-reaction. The phenylcarbimide of the tetrahydro-base C,,H,,ON melts at 208'. Fluorenequinoline when oxidised with sodium dichromste and acetic C6*4 VOL. LXXXII. i. 3 m830 ABSTRACTS OF CHEMICAL PAPERS.acid gives a new base which forms yellow crystals melts at 191' (corr.) and has the formula C,,H90N. This is insoluble in cold water or alcohol but easily soluble in benzene or chloroform. I t s hydrochloyide sulphate and nitrate have been prepared. 2-Aminofluorenone when boiled with glycerol arsenic acid and con- centrated sulphuric acid gives jluorenonequinoline which crystallises in yellow needles and melts at 188'. The methiodide C,7H,,0NI,H,0 is insoluble in all organic solvents and decomposes when heated at 240'. When fluorenonequinoline is fused with potassium hydroxide the potassium salt of a carboxylic acid of the formula C,,H,,N*CO2H is obtained. The free acid can be crystallised from hot alcohol melts at 264-265' (corr,) and is insoluble in water ether chloroform or acetone but is soluble in solutions of acids or bases.J. McC. Some Ammonium Compounds. X Hydroxyphenylmethyl- dihydroacridine By HERMAN DECKER TH. HOCK and C. DJIWONSKY (Be?.. 1902 35 3068-3079. Compare Abstr. 1893 i 115 ; this vol. i 691),-The methyl ether of 5-hydroxy-5-phenyl-10-methyl-5 10-di- hydroacridine is formed when the carbinol base is boiled with methyl alcohol. It forms colourless needles which melt at 152-153' and become red. The corresponding isobutyl ether also forms colourless crystals which melt at 108.5O. Halogens act on hydroxyphenylmethyl- dihydroacridine and with iodine the di-iodide of phenylacridine meth- iodide is produced which crystallises from chloroform in dark six- sided plates and melts at 148-150'.With excess of iodine a poly- iodide is formed. The action of methyl iodide on the carbinol base is t o reproduce pheny1acridin.e methiodide. From a consideration of the work of Werner Kehrmann and others the authors deduce support for the theories which Decker has already advanced for the constitution and mode of formation of these am- monium compounds. J. McC. Oxidation Products of o-Aminophenol. By EMIL DIEPOLDER (Bey. 1902 35 281 6-2823).-When o-aminophenol hydrochloride is oxidised with potassium ferricyanide or ferric chloride a mixture of triphenodioxazine and 3-hydroxybenzeneazoxindone is obtained. 3- Hydroxybenxeneaxoxindone CGH4<~>C,H,0*OH which is the tautomeric form of phenoxazine-2 3-quinone crystallises from xylene in beautiful brown needles with a blue iridescence blackens at 240-250° and decomposes at 278'; i t is soluble in ammonia and when treated with sodium hydroxide yields o-aminophenol and di- hydroxyquinone. The acetyl derivative crystallises in clusters of golden lustrous leaflets and melts a t 225-226O.An insoluble bye- product which decomposed at 268' obtained in the above oxidation was proved to be a double compound of 3-hydroxybenzeneazoxindone and 3-aminobenzeneazoxindone. 7-PhenyZtriphenccxineoxaxine,ORGANIC CHEMISTRY. 83 I (Abstr. 1898 i 93) crystallises from nitrobenzene and is identical with the compound wrongly described as N-methyltriphenazinoxazine- carbazole (Abstr. 1901 i 618). A red coloration with ferric chloride which is converted into blue or green with reducing agents such as stannous chloride seems to be characteristic for those o-aminophenols which have two free para- positions and not more than one alkyl in the amino-group.R. H. P. Aminohydroxydiphenylamine and Analogous Compounds. By ROBERT GNEHM [with H. BOTS and G. WEBER] (Be?*. 1902 35 3085-3088).-By the condensation of dimethylp-phenylenediarnine with quinol or by the reduction of phenol-blue dimethgl-p-amino-p- hydi*oxydiphenylurnine is obtained in the form of white needles which melt a t 161'. I t s diucetyl derivative melts at 131' and its clibenxogl derivative a t 210'. When treated with concentrated nitric acid the diacetyl compound loses the acetyl groups and a tetranitro-compound melting at 228' is formed. With methyl iodide or ethyl iodide direct addition takes place and well crystallised products melting a t 818' and 206' respectively are obtained.When resorcinol is used in place of quinol dimetliyk-p-amino-m- hydroxycli~~~enylamine is formed ; this is easily soluble in the common organic solvents or in hot water and melts at 99'. It forms a diucetyl compound which melts a t 101' and a dibenxoyl derivative which melts a t 112'. With nitrous acid i t gives a nitrosournine which separates from dilute alcohol in brownish needles and melts a t 125.5'. By the reduction of indamine dimethyl-p-diaminodiphenykcmine is formed. 2-p-D imet~~?llanilino-7-hydrox?lnaphthalene NMe,. C,H,-NH* C,,H,*OH is produced from dimethyl-p-phenylenediamine and 2 7-dihydroxy- naphthalene; i t crystallises in white plates and melts a t 126-127'.J. McC. It is soluble in hot water and melts a t 116'. Benzylidenehydrazine. By THEODOR CURTIUS and H. FRANZEN (Ber. 1902 35 3234-3239). -Benzylidenehydrazine CHPh:N*NH (Curtius and PAug Abstr. 1892 456) is best prepared by the action of hydrazine on henzaldazine CHPh:N*N:CHPh. The picrate CHPh:NgNH2,C61-f2(N02),*oH separates as a thick yellow precipi- tate and is sparingly soluble in all solvents. It condenses with phenylthiocarbimide to form benzylidenephenylthiosemicarbazide CHPii N*NH*CS*NHPh (Pulvermacher Abstr. 1894 i 304) and with acetic anhydride gives acetylbenzylidenehydrazine (Curtius and Schafer Abstr. 1895 i 263) whilst ethyl bromide converts it into hydrazine hydrobromide and benzaldazine. o-Hydroxybenzylidenehydrazine (Cajar Abstr.1899 i 146) can be prepsred in a similar manner from the azine; the picrate forms a yellow slightly soluble crystalline powder. o-Hydroxybenxylidenephenyl- thiosemicarbuxide OH *C,H;C H N*NH*CS*NHPh separates from alcohol in white flakes or needles. 2 4 5-Trimethylbenxylidenehydraxine C,H,Me,*CH:N*NH from 2 4 5-trimethylbenzaldazine (Graf Diss. Heidelberg lS99) boils 3 m 2832 ABSTRACTS OF CHEMICAL PAPERS at 165-166' under 14 mm. pressure solidifies in the receiver melts at 70° and dissolves readily in organic solvents; the picrate is a yellow slightly soluble crystalline powder and melts a t 170-1'71'; 2 4 5-t.limetl~yZbenxylidenebenxylideneT~ydruxine C,H,Me,* CH:N*N:CHPh separates from alcohol in yellow needles ; the o-hydroxybenzylidene- hydrazine C,H,Me3*CH MoN:CH *C,H,*OH crystallises from alcohol in yellow needles.p-I~ethylbenxylidenehydraxine C,H,Me*CH:N*NH2 is a white crystal- line substance boils at 148' under 12 mm. pressure and melts a t 56'; the picrute is a yellow crystalline powder and melts a t 175-176O. p-Methy tbenxyliclereben~~ lidenehydruxine C6H,Me CH N *N CHPh separates from alcohol in yellow needles. m-Chlorobenxy lidenehydruxine C,H,Cl*CH N*NH is a white crys- talline substance and boils a t 163-164' under 20 mm. pressure ; the beizxylidenahydruaine C,H,Cl*CH:N*N:CHPh separates from alcohol in yellow needles. T. M. L. I Preparation of Hydrazides from Diammonium Salts. By THEODOR CURTIUS and H. FRANZEN (Ber. 1902 35 3239-3241)- Hydrazides can be prepared in good yield by directly heating the hydrazine salts of the acids ; the preparation of acetyl- propionyl- lactyl- and benzoyl-hy drazines by this method is described.Hydruxine p-bromobenxoate C,H4Br*C02H,N2H4 separates from alcohol in colourless needles softens at 165O melts at 1 70° and dis- solves readily in alcohol or water. When heated it is converted into di-p-brornobenxoylhydrux~ne N,H,(CO*C,H,Br) which crystallises from alcohol in minute colourless needles and melts a t 280' ; p-bromo- benzoylhydrazine was not produced. Hydyaxine p-toluate C,H,Me*CO,H,N,H forms colourless soluble needles and when heated is converted into a mixture of p-toluoylhydr- azine and p-ditoluoy lhydrazine. Constitution of the Alkyl Derivatives of Methyluracil and &Methyluric Acid. By ROBERT BEHREND and RICHARD THURW (AnnuZen 1902 323 160-178.Compare Abstr. 1900 i 63).-The dimethyluracils are most conveniently prepared by methylating 4-methyluracil with less than the calculated quantities of methyl iodide and potassium hydroxide ; under these conditions the mixture of di- methyl derivatives contains 60 per cent. of the @compound and 40 per cent. of the a-isomeride the formation of trimethyluracil being reduced to a minimum. Both these compounds on further methylation yield the same tri- methyl derivative namely 1 3 4-trimethylurucil ; this compound separates in rhombic crystals' melting at 110-112' ; like the mono- methyl compound it may be sublimed without decomposition. The two dimethyl derivatives on oxidation give rise to the same methyloxaluric acid the products of the two reactions being shown to be crystsllographically identical.The following results indicate that a-dimethyluracil is 3 4-dimethyl-2 6-dioxypyrimidine whilst i t s p-iso- meride is 1 4-dimethyl-2 6-dioxypyrimidine. 3 4-Dimethyl-1-eth~turacil (3 4-dimethyZ-1-ethyl-2 6-dioxypyrimidine T. M. L.ORGANIC CHEMISTRY. 833 NEt<EgG!E>CMe produced by ethylating a-dimethyluracil with ethyl iodide or bromide crystallises from benzene in lustrous leaflets melting a t 11 2-1 14d. 1 4-0 dmet hy 1-3 -et hy Zurucil( 1 4-dime thy 1-3- e th y 2-2 ; 6-dioxypyrinaid ine) NMe<:g:;>CMe prepared in a similar manner from P-dimethyl- uracil crystallises from alcohol in prisms and melts a t 110-1 12'. l-,Wethyl-2 ; 6-d~oxy-5-nitropyr~mid~ne-4-carboxyl~c acid (@net?hyhiti*o- urc6ci~carboxy~ic acid) NMe<CO-NH co*c(No2)>C*C0,H is produced by oxi- dising /3-dimethyluracil with a mixture of sulphuric and nitric acids the latter being saturated with nitrous fumes; it separates from water in light yellow crystals containing 2H,O.The water of crystal- lisatio-n is evolved a t 200°,and carbon dioxide is eliminated a t 140-150O. The double salt 2C,H,0,N3K,KN0 2 H20 separates in feathery crys- tals when the crude product of oxidation is neutralised with potassium hydroxide. The simple salt C',H,06N3K,H,0 separates in yellow crystals from an aqueous solubion of the preceding compound. The crude acid also contains a less soluble substance C,H,0,N4 which dissolves in hot water yielding an acid solution which develops an intense yellow coloration with the alkalis 1 -MetkyZ-2 6-dioxy-5-nitropyrimidine (P-n~ethylnitrouracil~ NMe<CO'C(N02)>CfJ CO-NH ' produced on heating the preceding acid crystallises from water in colourless needles and melts at 263O with partial decomposition ; its potassium derivative is obtained by heating the potassium salt of the preceding acid.1 - Methy I- 3 -ethyl- 2 . 6 -dioxy-5 -nitrop yrimidine ( 1 -meth&3 -et hy lnit ro- uracil) NMe<:gzy$$.3H obtained by heating the silver deriv- ative of the preceding compound with ethyl iodide a t loo' crystallises from water in prismatic needles and melts a t 105-106O ; this substance is identical with the product formed by successively ethylating and methylating the potassium derivative of nitrouracil.(3-methyl- 1 -ethylnitro- uracil) 9 "Et<CO co'C(No,)>CH --*Me prepared from a-methylnitrouracil crystallises from water in needles melting a t 124'; it is decomposed on prolonged heating in aqueous or alcoholic solution ; Lehmann who first obtained the two preceding dialkylated nitrouracils gave the melting point of the former as 70-73' and that of the latter as 106-109' (compare Abstr. lS90 33). a-Dimethyluracil can be successively converted into 3-methylnitro- uracil 3-methylisobarhituric acid 3-methylisodialuric acid and &methyluric acid. If therefore the original substance is 3 4-di- methyl-2 6-&oxypyrimidine the final product must contain its methyl group in position 3 of the pyrimidine ring and this cycle of changes supplies confirmatory evidence in support of Fischer's view t h a t the acid in question is 3-methyluric acid.3 -Methyl - 1 -ethyl-2 6-dioxy-5 -nitropyrimidine G. T. M.834 ABSTRACTS OF CHEMICAL PAPERS. Oxidation of Methyluracil. By ROBERT BEHREND and RICHARD GRUNEWALD (Annulen 1902 323 178-204. Compare preceding abstract).-When methyluracil is oxidised with an amount of potassium permanganate equivalent to three atoms of oxygen acetylcarbamide and oxaluric acid are produced the relative proportion of these sub- stances depending on the temperature; in the cold the former com- pound is the chief product at the boiling point the latter predominates whilst the two are formed in approximately equal amounts at 40-50". This result is obtained however only in alkaline solutions ; if the mixture becomes neutral or acid the proportion of acetylcarbamide increases and predominates even at high temperatures. 3-lIydroxy-4-nzet?tylurucil NH<Eg3%2>CMe is produced when 4-methyluracil is oxidised with one atomic proportion of oxygen by means of permaoganate solution the maximum yield being obtained at 20-40° when the solution is rendered neutral by the addition of an equivalent amount of acetic acid. The substance is sparingly solu- ble in water or alcohol but readily dissolves in alkaline or ammoniacal solutions ; it forms prismatic anisotropic crystals having either pyramidal or truncated ends ; with neutral ferric chloride i t develops a n intense blue coloration which disappears after a time or more rapidly on warming or treating with acids or alkalis.The compound was not obtained in a state of purity the percentage of carbon being somewhat too high. 3-Acetoxy-4-methyZuraciZ produced by treating the preceding sub- stance with acetic anhydcide crystallises from water in felted needles decomposing at 238-241° ; i t regenerates the hydroxy-compound by alkaline hydrolysis. 3-Hydroxy-4-methyluracil on further oxidation gives rise to acetylcarbamide and oxaluric acid. Although a compound intermediate between 3-hydroxy-4-methyl- uracil and its oxidation products could not be isolated yet the soluble product obtained by treating 3 3-dibromo-4-hydroxy-4-rnethylnracil NH<CO*CBr CO-K~>CIMe*OH with potassium hydroxide solution appears t o contain such a substance namely 3 3 4-trihydroxy-4- CO*C(OH) > met?~yEdi?~ydrouraciZ NH<Co-N$ ;' CMe*OH for on reduction it yields 3-hydroxy-4-methyluraci1 whilst on oxidation acetylcsrbamide and oxaluric acid are produced.Acetylallanturic acid is probably an intermediate product of the latter process b u t it has not been isolated. This supposition derives support from the fact that in acid or neutral solutions oxidation by chromic or permanganic acid leads to the formation of parabanic acid a substance whicb should readily result + o = CO* $3 (OH)*CO* CH CO'NH from the hypothetical compound NH< co*co NH<Co,&H + CH,*CO,H. The production of the same methyloxaluric acid from a- and p- dimethyluracils may be explained by supposing that the oxidation follows a course similar to that just indicated the two isomeridesORGANIC CHEMISTRY.835 giving rise successively to methyl derivatives of trihydroxymethyl- dihydrouracil and acetylallanturic acid the latter substances yielding CO*NH ' by further oxidation the same methylparabanic acid NMe< from which methyloxaluric acid is finally obtained. Action of Mucobromic and Mucochloric Acids on Benz- amidine. By FRANZ KUNCKELL and LEO ZUMBUSCH (Bey. 1902 35 3164-3168. Compare Abstr. 1901 i 759).-Bertxamidine 5-bromo- Z - ~ h e n y l p ~ r i n i i d i 1 ~ e - 6 - c c c r b o z y l a t e N C * CO,H,NH,*CPh:NH is obtained when a chloroform solution of mucobrornic acid is left in contact with an excess of a-benzamidine for some time or more readily when the mixture is warmed. It is sparingly soluble in water and crystallises in colourless needles melting at 22SO.The acid crystallises in needles melts a t 159' and yields a barium salt C2,Hi20,N,Br2Bn crystallising in long colourless needles. Bromine converts the acid into a compound Ct,H602N2Br2 and ammonia into 5-umino-2-pl~enylp~rimidine-6-carboxylac acad melting at 196". The hydrochloride melts a t 183'. When heated at 165-170° the acid readily ioses carbon dioxide and yields 5-bromo-2-phenyl- pyrimidine melting at 104". Miicochloric acid and bemamidine yield bemamidine 5-cl~loro-2-phenylpyrimidine-6-carboxylate melting at 230-231'; the ucid melts a t 164O and the bavium salt crystallises in long needles. 5-Chloro-2-phenylpyrimidine me1 ts a t 96". J. J. S. Action of Benzamidine on @-Bromo-o-benzylacetophenone. By FRANZ KUNCKELL and 0.SARFERT (Be?.. 1902 35 3169)-2 4 6- Triphen$3 4-clilLydro~yyinzidine N<CPh CH>CHPh is obtained when a chloroform solution of bemamidine is warmed with P-bromo- o-benzylacetophenone (Rupe and Schneider Abstr. 1895 i 361) ; it melts at 186-187" is readily soluble in chloroform alcohol or ether and as a feeble base combines with hydrogen chloride in the absence of water. J. J. S. Cyclic Diammonium Compounds. By MAX SCHOLTZ (Ber. 1902 35 3047-3055).-The stability of cyclic compounds containing nitrogen in the ring is discussed and the author has prepared the following compounds containing two nitrogen atoms from dipiperidyl- ethane and dipiperidylpropane by the action of methylene iodide ethyl- ene bromide trimethylene bromide and 0- m- and p-xylylene bromides.With the exception of nzethylene iodide these dihalogen compounds give diammonium derivatives as has been proved by the analysis of the platinichlorides and aurichlorides. Ethyleneti.imethyle?~edipiperidyZiunz bromide C H N B r < ~ ~ ~ ~ ~ ~ ~ > N B r C K obtained by the action of trimethylene bromide on dipiperidglethane is easily goluble in water and crystallises in rhombic plates. Ditrinaeth ylenedipiper id!yZiurn bromide co*vo G. T. M. CPh*NH - - 4 5 H 10' * N B ~ < ~ ~ ~ * ~ CH,* C H,* H 2 * C H 2 > ~ ~ r CH c~H~,,,836 ABSTRACTS OF CHEMICAL PAPERS. obtained from dipiperidylpropane and trimethylene bromide at the ordinary temperature as a flaky mass volatilises a t 100'. The platini- chloride C16H,oN2,H2PtC16 melts at 259' and the nurichloride at 214O.C16H30N,,2HAuC14j Etl~ylene-o-xylylenedipiperidyliun~ bromide C,H,,:NBr<E2* c6H4*CH2>NBr:C5HI0 which is obtained from dipiperidylethane and o-xylylene bromide in chloroform solution can be separated from alcoholic solution by means of ether as a hygroscopic crystalline powder. The platinichloride does not melt but decomposes at 300"; the aurichloride melts at 243'. The corresponding meta- and para-compounds are simi€arly obtained. The platinichloride of the meta-compound melts at 262' the aurichloride at 182' ; the platinichloride of the para-compound melts a t 235O the aurichloride a t 210'. From di piperidylpropane and the xylylene bromides trimethylene- xyl3 lenedipiperidylium bromides CH2 c5H10'NBr<CH2-CH2-CH:>NBr'C,H~0 CH,*C6H4*CH are formed.The platinichloride of the ortho-compound melts at 242-243' and the azirichloride at 141'. The platinichloride of the para-compound melts at 2 5 2 O and the csurichloride becomes dark at 140' and melts a t 200'. By the action o€ methylene iodide on dipiperidylethane and dipiper- idylpropane two mols. of the iodide combine with one mol. of the base with formation of dipipel.idylethanebisiodornet?~yl iodide and dipiperidylpropanebisiodomethyl iodide [ C,Hlo NI( CH,I)*CH,],CH ; the former crystallises in yellow plates is insoluble in ether and melts at 1 8 2 O ; the latter forms yellow crystals melts at 195-196O and is sparingly soluble in alcohol or water and insoluble in ether. [ C~H~O N I(CH$)] 2CzH4 J. McC. Synthesis of Xanthine Derivatives by means of pNitropheno1. By WALTHER BORSCHE (Chem.Centr. 1902 ii 284-285 ; from Nachr. k. Ges. Wiss. Gottingen 1902 141-145. Compare Stormer Abstr. 190 1 i 726).-Dinitrodihydroxymethylxanthine C15H1207N2 obtained in almost theoretical quantity by the actioii of formaldehyde on p-nitrophenol in presence of dilute sulphuric acid at 40° separates from alcohol in colourless crystals melts at 1 4 8 O is insoluble in alkalis and when warmed with nitric acid yields picric acid. By the action of potassium permanganate and chromic acid nitrosalicylic acid and 2 7-dinitroxanthine-4 5-dicarboxylic acid ClqH,0,N2 are formed respec- tively. The latter crgstallises from alcohol in slightly yellow needles melts at l l O o and is dissolved and decomposed by alkali hydroxides or carbonates with formation of formaldehyde and the alkali salt of 5-nitrosalicylic acid ; 3-nitro-6-hydroxybenzyl alcohol is probably an intermediate product of the reaction. o-Nitrophenol is not attacked by formaldehyde.E. W. W.ORGANIC CHEMISTRY. 837 Triketones. 11. ,@$-Triketo-&phenylbutane. By FRANZ SACHS and ALFRED R~HMER (Ber. 1902 35 3307-3319. Compare Abstr. 1901 i 670).-The preparation of pya-triketopentane has been improved and is described in detail. It gives a yellowish-red to brown coloration with sulphuric acid and benzene containing thiophen ; further it does not form insoluble compounds with sodium sulphite or hydrogen sulphite; both i t and its hydrate have a bitter burning taste and colour the human skin brown. The free keto-group in the bisphenyl- hydrazone (Zoc.cit.) does not react with phenylhydrazine in alcoholic solution or with semicarbazide. The constitution of the 2-acetyl- 3-methylquinoxaline previously obtained from the txiketopentsne and 0-phenylenediamine hydrochloride is confirmed by the formation of the phenylhydraaone CGHb<N:CMe N:?*CMe:N*NHPh which crystallises in small lemon-coloured needles and melts a t 178' of the oxime which melts at 194*5' of the p-nityophenylhydrumne which melts at 264' and of the semicarbnxone which crystallises from glacial acetic acid and melts at 267-268". The auinoxaline condenses with benzalde- hyde in the presence of' sodiirn ethoxide forming 2 3-cinnamoyl- . The bis-semicarb- methylquinoxaline CGH,< N:?*CO*CH:CHPh N:CMe uxone of the triketopentane crystallises from glacial acetic acid melts at 32l0 dissolves in alkalis and is reprecipitated by acids. Hydr- azine hydrate reacts violently with triketopentane with the evolution of nitrogen and the formation of 4-hydroxg-3 5-dimethyZpyrcixoZe which crystallises in colourless needles and melts a t 173.5".py&Triketo-&phenylbutane can be prepared by analogous methods t o those described (Zoc. cit.). The condensation pwduct of benzoyl- acetone and p-nitrosodimethylaniline crystallises from alcohol in red- dish-brown needles and melts at 99'. The triketone COMe*CO*COPh is a reddish-yellow oil i s insoluble in water but miscible with all organic solvents and is hygroscopic ; it gives a violet coloration with sulphuric acid and benzene containing thiophen and reduces Fehling's solution. The hydrate COMe*C(OH),*COPh forms colourless rhombic crystals melts at 54-58" and is much more stable in air than the triketopentane.The P-phenyZhydrccxme crystalliscs in dark red rhom- bic prisms melts a t 167' and condenses with o-phenylenediamine forming a compound C,,H!,N which melts at 183'. The triketone reacts with a n excess ot phenylhydrazine forming 1 5-diphenyl- 3- naethylpyraxo Ze-4-azo benzene Y P h N>CMe which crystal- lises from alcohol and melts at 136.5'. The /3-monosemicarbaxone of the triketone crystallises in felted needles and melts at 190'. 2-AcetyZ-3-pl~enyZpuinoxaZine crystallises in colourless needles melts at 99*5' and forms a semicarbazone melting at 243' and a p'henyl- hydrazone which melts at 183' and is identical with the product ob- tained from the phenylhydrazone of the ketone and o-phenylene- diamine ; the condensation product of benzaldehyde and the quin- oxaline melts at 164'.4-Hydroxy-5-phen~Z-3-met~yZ~~ruxole crystallises in white needles and melts at 188'. An undetermined compound C P h :C(N :NPh)838 ABSTRACTS OF CHEMICAL PAPERS obtained by the polymerisation of the ketone in the presence of piper- idine crystallised in broad needles and melted at 202". R. H. P. Preparation of Aromatic Guanidines. By FREDERICK J. ALWAY and CAREY E. TAIL (Amer. Chena. J. 1902 28 158-164)- Aromatic guanidineo are best prepared by Hofmsnn's met hod (Ber. 1869 2 458). The thiocarbamide and arnine in molecular pro- portion are dissolved in alcohol and the solution is heated until i t boils; an excess of lead hydroxide is then added and heating is continued until desulphurisntion is complete.On the addition of nitric acid to the filtered solution the nitrate slowly separates and may be collected and recrystallised. I n the preparation of phenyldi-o-tolyl- gnanidine a small quantity of tri-o-tolylguanidine i s simult>aneously formed The yield of the nitrate (or mixture of nitrates) amounts to 75-90 per cent. of the theoretical. The nitrates of the following bases have been obtained by the method described diphenyl-m-tolyl- phenyldiq-tolyl- o-tolyldi-p-tolyl- m-tolyldi-p-tolyl- di-o-tolyl-p-tolyl- di-o-tolyl-m-tolyl- and phenyl-o-tolyl-p-tolyl-guanidine. Diphenyl-p-tolylguanidine nitmte is obtained in equally good yield from diphenylthiocarbamide and p-toluidine and from phenyl-p-tolyl- thiocarbamide and aniline.It forms small colourless plates and melts at 196-197'. E. G. Dyes of the Capri-blue Group. By RICHARD MOHLAU K. KLIM- MER and EDMUND KAHL (Chem. Centr. 1902 ii 377-378 ; 458-459 ; from Zeit. Pcwb. Textilehem. 1902 1 313-324 354-356).-The following compounds are used in the preparation of dyes of the capri- blue or diaminophenazo-oxonium chloride yH:CH* E*SJ--S*CH :?H NH2*C= CH*C* C(OCl)*C*CH:C*NH,' group. 4-Nitro-2-dimethyZa?ninotoZuene NO,*C,H,Me*NMe prepared by nitrating 2-diir~ethylaminotoluene in concentrated sulphuric acid boils a t 280' with partial decomposition and is readily soluble in acetic acid mineral acids or most organic solvents. 4-Amino-2-dimethyl- uminotoluene NH,*C,H,Me*NMe obtained by reducing the preceding compound with tin and hydrochloric acid is an pil boils at 248' (uncorr.) is volatile in steam and readily soluble in acids or organic solvents.The sulphnte CgH1,N2,H,S0 separates from alcohol in lustrous crystals and melts at 209'; the hydrochloride melts a t 20So. The ncetyl derivative NHAc*C,H,Me*NMe crystallises from light petroleum in needles is readily soluble and melts at 103'. 2-Di- meth~Z~nzino-4-l~ydroxytoluene NMe,*C,H,Me*OH prepared from 4-amino-2-dimethylaminotoluene or by melting potassium 2-dimethyl- amino-4-sulphonic acid with potassium hydroxide melts at 46' boils at 2 5 3 O and is readily soluble in acids alkalis or organic solvents. The hydrochloride CgHl,ON,HCl forms rhombohedra1 crystals and melts at 213".The ucetyl derivative NMe,*C,H,Me*OAc is a readily soluble liquid and boils at 195" under 60 mm. pressure. The benxoyl derivative crystallises from alcohol in four-sided plates and melts at 46'. By the action of nitrous acid on 2-dimethylamino-4-hydroxytoluene inORGANIC CHEMISTRY. 839 aqueous solution in presence of excess of hydrochloric acid dimethyl- amine and Kostanecki's 3 5-dinitrosocresorcinol C,HMeO,( NOH) (Abstr. 1888 263) are formed. On the other hand by the action of a n aqueous solution of sodium nitrite on crystalline Z-dimethylarnino- 4-hydroxytoluene hydrochloride a theoretical yield of 5-nityoso-2- dirvzetkyZcimino-4-hydroxytoZuene NMe,*C,H,Me(NO)*OH is obhained ; it crystallises from benzene in reddish-brown needles melts at 102" and is readily soluble in alcohol benzene acetic acid pyridine or chloroform and slightly so in water or ether.The hydrochloride C,H,,O,N,,HCl melts at 170° and the sodium salt C,H,,O,N,Na forms a blood-red solution in water or alcohol The following compounds are prepared from 2-diethylaminotoluene o r its derivatives 4-~2Titro-2-diethylaminotoZuene is a n oil boils at 283' (uncorr.) and is volatile in steam. 4-Amino-2-diethyZaminotoluene is a yellow oil which can be distilled at 259' in an atmosphere of carbon dioxide ; the hydrochloride C,,H,,N 2 HCl,H,O me1 t s and decomposes at 213-215'. 2-DiethyZamwao-4-hydroxytoZuene is a slightly yellow oil becomes red on exposure t o air distils at 259-261' (uncorr.) in an atmosphere of carbon dioxide,and is volatile in steain ; by allowing its solution in benzene to evaporate at the ordinary temperature it separates in crystals which melt at 46'.The hydrochloride C,,H,,ON,HCl crystallises from alcohol in rhombohedra1 crystals and melts at 187'. The benxoyl derivative crystallises from alcohol i n rhombic prisms and melts at 36'. 2-DiethyZaminotoZuene-4-suZpJ~onic acid NEt,*C6H Me*SO,H,H,O crystallises from water in hexagonal rhombic plates and is slightly soluble in cold water or alcohol. The potassium salt separates from 95 per cent. alcohol in crystals contain- iug water of crystallisation. 17et~~~meth~ldiaminop~enoto~axo-oxonizcsn chloride C17H,,0N,CI is prepared by treating 2-dimethylamino-4-hydroxytoluene with nitroso- dimethylaniline in boiling glacid acetic acid.The corresponding iodide crystallises from alcohol in violet needles is slightly soluble in water and more readily so in alcohol acetone or chloroform form- ing greenish-blue solutions. By boiling a n aqueous solution with alkalis a blue precipitate is formed and the liquid acquires the odour of dimethylamine. 17~t~~ametl~~icEiamino)lilenc7toloxaxine yH:CH*13;'*C(NH):s*CH:QRle NMe,* C= CH*C.CO--C*CH:C*NMe ' prepared by reduction with zinc and hydrochloric acid is a greyish- white crystalline powder and is easily reconverted into the dye. Di- metJ~yZd~ethyldiccna~~~o~~~~enoto~~~o-oxonium iodide C,,H,,ON,I prepared from 2-dimethylamino-4-hydroxytoluene and nitxosodiethylaniline crystallises from alcohol in violet-blue crystals ; its solution in water akohol or glacial acetic acid has a more reddish-blue colour than that of the tetramethyl derivative. The isomeric dirnethyZdiethyZdiaminopheno- tolazo-oxonium iodide prepared from 2-diethy lamino-4-hydroxytoluene and nitrosodimethylaniline forms greenish-blue solutions in water alcohol acetone or glacial acetic acid ; it is more soluble in water than the preceding compound and its solution in concentrated sulphuric acid is reddish-violet whilst t h a t of the isomcride is reddish-brown. Capri-blue G.O.N.is the corresponding zinc chloride double salt.840 ABSTRACTS OF CHEMICAL PAPERS. Pheny7dinaethyldiaminop?~enotolaxo-oxoniu~ chloride C,,H,,ON,Cl prepared from dimethylaminocresol and p-nitrosodiphenylamine hydrochloride is a crystalline indigo-blue powder soluble in alcohol acetone or glacial acetic acid forming blue solutions but only very sparingly so in water.I t s solution in concentrated sulphuric acid is green and on dilution becomes violet. as-DimetlLyldiumino~?~eno- toluxo-oxonium c?Lloride C,,H,,ON,Cl obtained by the action of di- methy laminocresol on quinonedichlorodi-imide in alcohol at 40' crys- tallises with lH,O is readily soluble in water alco-hol acetone or glacial acetic acid and forms a very dark violet solution in concen- trated sulphuric acid which on dilution becomes successively red violet and blue. Sodium hydroxide precipitates the free base from aqueous solutions of the chloride as a reddish-brown substance which is soluble in ether. as-Dimethyldiaminotolona~htha-czo -oxoniwm chloride Cl,H180N,CI prepared from a-naphthylamine and nitrosodimethyl- aminocresol hydrochloride crystallises from water containing hydro- chloric acid in green needles and is readily soluble in water alcohol acetone or pyridine,' forming blue solutions tinged slightly with red.Its solution in concentrated sulphuric acid is red and on dilution becomes yellow. The free base dimetfL~~luminotolc~minonu~?~thuxo- oxonium hydyide Cl9HZ7O4N3 crystallises f;om alcohol in orange-red needles E. w. w. Antipyrylcarbamide a Product of the Metabolism of Pyramidone. By MAX JAFFE (Ber. 1902 35 2891-2895. Com- pare Abstr. 1901 i 672).-From the urine after administration of CO-E*NH*CO*NH pyramidone antipyrylcarbamide NPh< NMe*CMe (m. P* 247-248' Knorr Abstr. 1897 i 112) has been isolated and identi- fied by conversion into 4-aminoantipyrine ; the carbamide gives a violet coloration in aqueous solution with ferric chloride K.J. P. 0. Triethyltrirnethylenetriamine. By ALFRED EINHORN and AUGUST PRETTNER (Ber. 1902 35 2942-2944).-Triethyltrimethyl- enetriamine combines with methyl iodide forming the methiodide C H 2 < ~ ~ ~ ~ ~ > N E t M e I which is obtained as a white precipitate melting at 97-98' on adding ethyl acetate to its solution in chloro- form. The triamine yields a hydriodide C,H,,N,I which crystallises from alcohol in needles melts at 121' and when treated with alkalis is reconverted into the base If this hydriodide is heated for three- quarters of a n hour at 80-90° or if a n alcoholic solution of the methiodide is boiled an isomeric hylriodide is obtained ; this crystal- lises in clumps of small needles melts at 199' and has the properties of a quaternary ammonium iodide.R. H. P. Derivatives of Cinchomeronic Acid. By SIEGMUND GABRIEL and JAMES COLRIAN (Be?.. 1902 35 283 1-2852-).-The authors have previously (this vol. i 401) described derivatives of 2 6-benzodi-ORGANIC CHEMISTRY. 841 azine for which they proposed the name copyrine. paper deals with derivatives of 1 3 'i'-benzotriazine The present $! H:N*Q:CH*E N:CH-C:CH* CH' which is named copazoline. The action of potassium hypobromite on cinchomeronimide is de- scribed ; the properties of the 3-aminopyridine-4-carboxylic acid obtained differed From those detailed by Blulvenfield (Abstr. 1896 i 60) ; the Felting point varied according to rate of heating from 306-310° the hydrochloride melts and decomposes at 244-245' and the nitrate a t 196-197'.The methyl ester crystallises from light petroleum in long yellowish needles melts at 86-87" and forms an uurichloride cry stallising in yellow needles and a platinichloride form- ing octahedra-like crystals ; its aqueous solution deposits the hydrate C7H,O2N,,H2O; in long colourless silky needles which melt at 50' when auicklv heated. 1 J The acid condenses with chloroacetic acid forming 3-pyridylglycine- ; this crystallises with r= CH*E*NH*CH2*C0,H C H:CH* C* C0,H 4-carboxylic acid H,O in long needles pointed atAboth ends decomposes at about 160' blackens at 180° and behaves as a monobasic acid. The silver salt C,H70,N2 Ag,H,O crystallises in yellowish pointed needles and the bc~rium salt (C8H7O2N,),Ba,H2O is a yellow crystalline powder.obtained when 3-amino- NH-CO*C:CH*CH' pyridine-4-carboxylic acid is heated at 170' with carbamide and also when cinchomerondiamide is treated with brorhine and sodium hydr- oxide is a yellow microcrystalline powder sublimes without melting and is soluble in dilute acids and fixed alkalis. The hydrochloride crystallises in small needles and its aqueous solution gives a blue fluorescence when made alkaline with ammonia. The platinichloride crystallises in small short prisms and the uurichloride in golden flat lamin% which sinter at 225' and melt and decompose at 246-248'. 4-Oxycopazoline prepared from aminopyridinecarboxiylic acid and formamide crystallises from water in clusters of needles sinters at 300° and melts and partly sublimes at 315-317'; i t dissolves in acids and alkalis; the potassium salt forms slender needles the plcctinichloride yellow needles the tcurichloride yellow leaflets and the nitrate colourless leaflets.When shaken with a mixture of Dhos- 2 4-DioxycopaxoZine (? o*NH*(?:cH*M phorus tri- and penta-chlorides at 160° it yields 4-chZorocopux~Zine (?H:N'(?:CH*n which crystallises from light petroleum in yellowish N:CCl*C:CIC*CH' rods sinters a t 110' and melts a t 112'. When the chloro-com- pound is reduced with a mixture of hydriodic acid and phosphonium iodide a t temperatures not exceeding O' i t yields 3 4- (or possibly 1 2-) dilqdrocopuzoline which crystallises from acetone or ether melts at 144-145' and forms a strongly alkaline aqueous solution ; the Iydriodide C,H7N,,2HI crystallises in yellow pointed needles which decompose at 260-280° the platinichloride C,H7N,,H,PtCI is an insoluble orange-yellow crystalline powder the cvurichloride,842 ABSTRACT$ OF CHEMICAL PAPERS C7H7N3,2HAuCI crystallises in golden needles and the picrate and chyornccte are both insoluble. When condensed with acetamide the aminopyridinecarboxylic acid yields 4-oxy-2-methylcopuxoline which crystallises from water in long flat needles melting at 2S8" can be sublimed is soluble in acids and alkalis and forms a crystalline plcctinichloride.Cinchomerofi 3 -a&c cm'cl C0,H*C,NH3*CO*NH obtained when cinchomeronimide is shaken up for 1 hour with a normal solution of potassium hydroxide separates from water in clear rhomhic crystals decomposes at 200') forming the imide and when treated with bromine and sodium hydroxide yields 3-aminopyridine- 4-carboxylic acid ; the silver salt crystallises in white leaflets. Cinchomerondiarriide is best prepared by digesting the imide with alcoholic ammonia and crystallises in transparent cubes and melts at 175-176' forming the irnide ; its aqueous solutions deposit the hydmte C,H70,N3,H,0,.in glassy prisms which with silver nitrate form the crystalline additive compound BC7H70,N3,AgN0,. When cinchomeronimide is reduced with t i n and hydrochloric acid N-CH:C-CO cinchonzeroni~idine eH.CH.&.CH,>NH is obtained ; this crystallises with H,O in compact yellow prisms or from acetone or ethyl acetate in clusters of yellowish needles ; the plcctinichloride (C7H,0N,),,H:,PtC16 separates in amber-coloured octahedral crystals the ccuvichloride in leaflets and the picrate in needles which darken at 200" ; the hydro- cldoride C,H,OK,,HCl,H,O cry stallises in compact glassy prisms which lose their colour a t 225" and melt and decompose at 248-250° and the stunnichloride C7H,0N H8nC1,,H20 crystallises in compact pointed rods.Cinchomeronimidine when heated at lS0" with red phosphorus and hydriodic acid yields a mixture of 4-methylpyridine-3-carboxylic acid methyl- and dimethyl-pyridine and a new di-acid base merimine y--CH:Q* CH C H*OH C CH,>NH* Merimine is an oil and in aqueous solution is strongly alkaline and absorbs carbon dioxide ; the hydrochloride forms colourless flat crys- tals the plcctinichloride a yellowish-red powder consisting of needles the auriclJoride compact prisms and the picrccte a n insoluble crystal- line powder which decomposes at 211-212".isoNitiwosocinc~~o~ne~onimidine was obtained as a yellow microcrys- talline powder which sublimes when heated and is decompose2 by hydrochloric acid yielding cinchomeronic acid hydroxylamine and ammonia. The plutonichloride is a yellow crystalline powder and the aurichloride crgstallises in small slender needles. R. H. P. Isomerism of antiDiazo hydrates and Primary Nitrosoamines. By ARTHUR HANTZSCH and WILLIAM POHL (Ber. 1902 35 2964-297S).-The authors show that antidiazotates "'E when treated with carbon dioxide yield yellow primary nitrosoamines N*OMORGANIC CHEMISTRY.843 R*NH*NO. The antidiazo-hydrates which are all white when treated with hydrochloric acid yield diazonium salts but the nitrosoamines yield hydrochlorides of the type NO*NHR,HCI. A further difference is shown by the rate of coupling as the antidiazohydrates couple much quicker than do the nitrosoamines. An aqueous solution of 2 6-dibromoanisoIediazonium nitrate yields when treated with a n ice-cold concentrated solution of potassium hydr- oxide potctssiurn syndiueo-2 ; 6-clibronaoccnisoZe which was obtained as a n unstable white precipitate and when treated with a hot concentrated solution of potassium hydroxide yields the isomeric potussiunx antidiaxo-2 6-dib~omoanisoZe which crystallises in stable needles. The antidiazotate when treated with acetic acid yields the OMe*C6H2Br,*?!f 0K.N OMe-C6H2Br2*g white 2 6 -dibromouniso Zeantidiuxo-hyclrcc te N.OH 7 whit is reconverted into antidiazotate when treated with alkalis and when treated with hydrocbloric acid acetyl chloride or phosphorus penta- chloride yields the diazonium chloride. When the potassium anti- diazotate dissolved in ice-cold water is treated with carbon dioxide the 2 6-dibromounisolenitroso~~~~ine OMe*C,H,Br,*NH*NO is ob- tained; this is a n amorphous substance oi a deep yellow colour behaves as a pseudo-acid and when treated with a n ethereal solution of hydrogen chloride forms a hydyochloride which crystallises in small bright yellow needles. Benxophenone-p-antidimxo-hydrate was obtained as a white voluminous precipitate and 6enaophenone-p-nitrosoamine as a yellow unstable sub- stance.Potussiunz 2 4 ; 6-tribromobenxeneantidiazot~cte crystallises in reddish needles which are very unstable ; the corresponding anticlimo-hgdrute is obtained when an ice-cold solution of addiazotate is acidified with acetic acid as a white precipitate which is immediately transformed t o the orange-yellow amorphous 2 4 6-t~ibromo~henyZni€~osoum~~ae ; this is also obtained when the corresponding diazonium salts are treated with a solution of sodium acetate; it melts and decomposes at 85-86O and forms a light yellow hydyochloride and hgdrobromide. The antidiuxotutes antidiuxo-T~ydrcctes and nityosounaine obtained from 2 4 6-tribromo-m-toluidine are very similar to the compounds derived from 2 4 6-tribromoaniline but are much less stable.Potassium 2 6-d~bro~no-p-to~ueneant~~~u~otccte crystallises in long white needles the antidiuxo-hydrute and the nitrosoccmine are unstable. The analogous p-nitro- o-nitro- and p-bromo-compouuds were prepared and are very similar to the substances just described. R. H. P. Diazoisonitrosomethyluracil and 4-Aminopyrazole. By GEORG WOLLERS and ROBERT BEHREND (Annulen 1902 323 279-283l- Diazoisonitrosomethyluracil may be regar'ded as having either 'the constitution NH- I CO*E*N:N*OH or THO CO*E*N(N0,)>x,H20. On C O*NH*C*CH:N*OH C0.NH.C-CH reduction it yields isooxanthine r"' Co*$?NH>N and this sub- CO*NH*C* CH844 ABSTRACTS O F CEEMICAL PAPERS. stance when heated with concentrated hydrochloric acid at 150-1 go' loses the elements of ammonia and carbon dioxide and becomes con- verted in to 4-aminopyranoZe7 ' fH* NH>N which is characterised NH,+-C H' by its nityate C,H,N2,2HN0~~H,0 and its benxoyl derivative C3H3N3Bz2 ; these compounds.crystallise in needles and the latter melts at 173'. G. T. M. Syntheses with Hippurazoimide. By THEODOR CURTIUS (Ber. 1902 35 3226-3228).-The following compounds have been pre- pared by condensing hippurazoimide with glycine NI€,*CH,*CO,H or glgcylglycine NH,*CH2*C0*NH*CH,*CO2H. Benzoylglycylaminoacetic acid yields a hydraxide melting at 227-2339' and a n azoimide melting at 109-110°. Benxoy Zgl yc ylgl ycy laminioacetic acid NHBz*NH*CH,*CO*NH*CH2* CO*NH* CH,*CO,H melts at 815-216' its ethyl ester at 173" its hydraxide at 245-250° and i t s axoimide at 162'.Benxo y Zg lycylg ZycyZgl ycylaminoacet ic acid NHBz*CH2*CO*NH*CH,*C0."H.CH2*CO*NH*CH2*C02H melts at 235' and i t s amide at 213'. T. M. L. 4-Methylbenzylazoimide. By THEODOR CURTIUS and A. DARAP- SKY (Bey. 1902 35 3229-3233).-p-Methylbenzylazoimide is stable towards alkalis but is readily decomposed by acids in a similar manner to benzylazoimide. The decomposition proceeds in four dif- ferent ways (1) C,H,Me*CH,*N -+ C,H,Me*CH,*N< + N C,H,Me*CH:NH -+ C,H,Me-CHO + NH,. (2) C,H,Me*CH,*N3 + C,H,Me-UH,*N< + N -+ C,H,Me*N:CH -+ C6H4Me*NH2 + CH,O. (3) C,H4Me-CH,*N3 -+ C,H,Me-CH2*NH2 + N,O. ( 4 ) C,H,Me*CH,*N -+ C,H,Me*CH<OH + N,H. The products actually obtained were hydrazoic acid p-methylbenzyl chloride p-methylbenzaldehyde (converted into the aldazine) am- monia p-toluidine and p-methylbenzylamine.T. M. L. Azoaldoximes and Hydrazidines. By HUGO VOSWINCKEL (Bey. 1902 35 3271-3274).-Since the composition of phenylazoacetald- oxime has been settled the constitution of the following substances previously described by the author can be fixed C,H,0,N3C1 p-chloro- phenylazoacetaldoxime (Abstr. 1899 i 958) ; C,HloON,CI p-chloro- phenylhydrazoacetaldoxime (ibid. ) ; C,H,,ON p-tolylazoncetaldoxime (ibid.) ; C,H1,ON p-tolylhydrazoacetaldoxime (ibid.) ; CI5Hl40,N4 carbanilophenylazoacetaldoxime (Abstr. 1901 i 53) ; CloH,,02N acetylphenylazoacetaldoxime (ibid.) ; and Cl4HlOOFN picrylphenylazo- acetaldoxime (ibid.). The oxygen-free reduction products have been proved to be hydrazidines (amidrazones) and the constitutions of the compounds previously described are CsH11N3 phenylethenyl- hydrazidine NHPh*NH*CMe:NH (Abstr.1899 i 958) ; C,H,,N,,ORGANIC CHEMISTRY. 845 phenylmethylethenylhydrazidine (ibid.); and C,H,oN,Cll p-chloro- phenylethenylhydrazidine. Fhenylethenylhydruxidine hydrochloride NHPh*NH*CMe:NH,HCl or NHPh*N:CMe*NH,,HCl is obtained by the action of phenyl- hydrazine on acetimino-ethyl ether in ethereal solution ; hydrochloric acid is then added and the ether evaporated. The azidine hydro- chloride is separated from the unattacked phenylhydrazine by means of alcohol. It forms silky needles which contain $H,O. The hydrated salt melts a t 140' then loses water and resolidifies after which it melts at 205O. When a mixture in molecular proportion of this salt and hydroxylamine hydrochloride is left in concentrated aqueous solution with double the molecular quantity of potassium carbonate slender orange needles of phenykccxoucetccldoxime separate Phenyl hydrazoacetaldoxime when boiled with alcohol to which water has been added gives after the addition of hydrochloric acid ethengl- phenylhydraxidine hydrochloride.J. McC. Hematin. By WILLIAM KUSTER (Ber. 1902 35 2948-2954. Compare Abstr. 1901 i 298).-The anhydride C,H,O previously described (Zoc. cit.) is shown to have the constitution >o. Meg*CO CO2H*CH2*CH,*C*CO When oxidised it yields succinic acid and when reduced by means of hydrogen iodide a mixture of two isomeric '' hcemotricurboxylicc " ucids having the constitution of pentane-ay8-tricarboxylic acids.These were separated by crystallisation from water ; the more soluble (1 in 7.3 parts of water a t 10') melts a t 140-141' and the other (1 in 75 parts of water at 10') at 175-176' the isomeride with the lower melting p i n t is converted into the other form by heating either alone or with water or with hydrochloric acid a t 200". The electrical con- ductivities of both acids are far less than the conductivities of tricarb- allylic acids as determined by Zelinsky (Abstr. 1896 i 349). The isomeride of higher melting point was also obtained from the imide C8H90,N previously described (Zoc. cit.). Acetylhzmin and /3-hzemin when treated with aniline yield two amorphous products hmneins which have the empirical formuh C3,H,,04N4Fe and C3,H3!04N4Fe respectively.Experiments are described which tend to show that the oxidation with chromic acid of the hzemopyrrole described by Nencki and Zaleski (Abstr. 1901 i 434) yields the anhydride of methyl-n-propyl- maleic acid. R. H. P. Lacto-serum. By ERNST FULD (Beitr. chena. Physiol. Path. 1902 2 425-429).-Lacto-serum (Bordet) is obtained by immunising animals (rabbits in the present research) with milk ; their serum $hen causes a precipitate when added to milk. The reaction is a precipitation of the caseinogen but the presence of calcium salts is essential although they may be replaced imperfectly by barium salts. The other proteids are not involved. If the original immunisation is produced with cow's milk i t is only cow's milk or its caseinogen which gives the reaction; goat's milk is easily precipitable with VOL.LXXXII i. 3 9%846 ABSTRACTS OF CHEMICAL PAPERS rennet but not by this lacto-serum; human caseinogen gives scarcely any reaction. A given quantity of lacto-serum can only precipitate a certain quantity of caseinogen. The product has not the same insolubility in salt solution that casein has. Digestion of lacto-serum with a third of its volume of horse-serum has no influence. W. D. H. Specific Precipitins. By PHILLIPPE EISENBERG (Bull. Acad. Xci. Cracow 1902 289-310).-The experiments were performed by immunising rabbits against egg-albumin and horse-serum. A sug- gestion for quantitative work on the ‘ precipitins ’ obtained is to take measured quantities of the serum diluted so that i t only just gives the reaction The amount of precipitin ‘ absorbed ’ means that which takes part in the process of precipitation.The ‘precipitin’ has many of the characters of coagulated albumin and contains both precipitin and ‘precipitable substance,’ but not all of either. An excess of both is present which can be detected by a further precipi- tate occurring when more of either substance is added. Excess of ‘ precipitable substance ’ inhibits precipitation ; this is attributed to an inhibitory substance in the ‘ precipitin.’ All immune substances are not contained in the pseudo-globulin fraction but were found also in the eu-globulin fraction of the serum W. D H. Action of Superheated Steam on Keratin. By RICHARD BAUER (Zeit. physiol. Chem. 1902 35 343-357. Compare Kruken- berg Sitxungsber.Jena Ges. Naturwiss. 1886).-When keratin obtained from horn shavings is heated with water in sealed tubes a t 150° for 24 hours considerable amounts of hydrogen sulphide and a second volatile sulphur compound presumably methyl mercaptan are formed. The solution contains two compoulrds corresponding with Neumeister’s atmidalbumin and atmidalbumose which the author terms atrnidkemtin and cctmidkeratose. They are most readily obtained by concentrating the solution and saturating i t with powdered sodium chloride when atmid keratin is precipitated. The filtrate from this precipitate on treatment with hydrochloric acid saturated with sodium chloride yields first a mixture of the two compounds and then atmidkeratose. The compounds are only slowly acted on by pepsin and trypsin.J. J. S. Glutinpeptone. By W. FAHRION (Chem. Zeit. 1902,26,675-677). -Glutinpeptone obtained by warming animal hide or gelatin with alcoholic sodium hydroxide is strongly basic. Unlike its hydro- chloride it is insoluble. in alcohol. The saponification number increases with the duration of warming with alkali; the increase is more rapid in aqueous solution than in aqueous-alcoholic solution. The saponifica- tion number is lower when air is completely excluded than when it has free access to the solution. From this behaviour it is concluded that glutinpeptone contains no alcoholic hydroxyl groups and that it is not an aldehyde ketone or lactone. A determination of the equivalent of uric acid showed that it increases in the same way as that of glutinpeptone ; from this it is assumed that the high value ofORGANIC CHEMISTRY.847 the saponification number of glutinpeptone on prolonged heating is due to the presence of imino-groups united to carbonyl groups. When glutinpeptone is oxidised in alkaline solution with potassium permanganate a substance is obt,ained which is insoluble in alcohol but which gives a soluble hydrochloride; a t the same time butyric acid is formed and a very small quantity of benzoic acid. Glut,inpeptone scarcely absorbs iodine indicating that i t does not contain doubly-linked carbon atoms in an open chain. J. McC. Nucleic Acid from Embryos of Wheat. By THOMAS B. OSBORNE and ISAAC F. HARRIS (Zeit. physiol. Chem. 1902 36 85-133. Compare Abstr. 1900 i 573),-The embryos of wheat contain relatively large amounts of a nucleic acid which the authors term triticonucleic acid.Some 3.5 per cent. of the acid is con- tained in the commercial flour freshly obtained from wheat embryos but the amount rapidly diminishes when the flour is kept. The acid has most of the properties characteristic of the nucleic acids of animal origin but is much less readily soluble in water. I t s per- centage composition agrees best with the formula C41HG,031N1SP4. It forms acid potassium sodium and ammonium salts which are soluble in water yielding solutions with strongly alkaline properties and it is found to be practically impossible to obtain the acid free from mineral matter. When hydrolysed with mineral acids triticonucleic acid yields guanine (1 mol.) adenine (1 mol.) uracil (2 mols.) and pentoses (3 mols.).The silver salt contains six atoms of silver and the free acid pre- sumably contains six hydroxyl groups. It is suggested that the acid is formed by the condensation of four P(OH) groups the four atoms of phosphorus being united with the aid of three oxygen atoms. When boiled for a short time with dilute acids only one-fourth of the total phosphorus is obtained in the form of orthophosphoric acid and a complex phosphorus acid is produced by the elimination of one atom of phosphorus together with guanine adenine and a molecule of pen tose. Triticonucleic acid may be identical with the nucleic acid obtained from yeast and somewhat resembles guanylic acid. alloOxyproteic Acid a Normal Constituent of Urine. By STANISLAUS BONDZY~~SKI and K.PANEK (Ber. 1902 35 2959-2963). -Analyses are given of the buriurn and silver salts of a new acid allooxyproteic acid which the authors have isolated from urine. The acid contains carbon hydrogen oxygen nitrogen and sulphur ap- pears to be a normal constituent of urine and is very similar to oxypro- teic acid (Abstr. 1898 i 501) ; it does not give the typical reacfiona of proteids and has not. yet been isolated in the pure state. J. J. S. R. H. P. Isolation of Malt Enzymes and the Proteolytic Enzyme of Malt By CARL J . LINTNER (Chem. Centr. 1902 ii 288-289 ; from Zeit. ges. Brazcw. 25 365-368).-The malt enzymes are best isolated848 ABSTRACTS OF CHEMICAL PAPERS. by salting out with ammonium sulphate. The small precipitate first obtained on addition of the sulphnte has a distinct diastatic but scarcely any proteolytic action ; the active enzyme is precipitated on further addition of the sulphate.The enzymes isolated by this means are capable of liquefying gelatin and have a diastatic action or fermentative power of 143 whilst that of the enzyme obtained by precipitation with alcohol seldom rises above 80. The experiments confirm the presence of a proteolytic enzyme in malt but do not indi- cate that i t plays any important part in the mashing process. The assumption that it resembles trypsin and determines the decomposition of proteids during germination is unfounded. When liquefied gelatin is digested with the enzymes for 48 hours a t 40° the glutin is scarcely attacked and only a very slight peptonisation could be detected by means of the biuret reaction The fermentative action of the enzymes should rather be compared with that of malt extracts which have been attenuated by heating and which although capable of liquefying starch paste are unable to convert the starch into sugar.E. W. W. Yeast-gum and Invertase. By KINTARO OSHIMA (Zeit. physio2. Chenz. 1902 36 42-48. Compare Salkowski Abstr. 3894 i 221 316 ; 1895 i 166 ; 1901 i 180).-When yeast gum is distilled with hydrochloric acid of sp. gr. 1.060 the distillate gives the reaction for methylfurfuraldehyde (Abstr. 1901 ii 484) and the original gum presumably contains a methylpentosan. When the gum is hydrolysed with sulphuric acid the chief product is d-mannose. Attempts were made to purify crude invertase (Osborne Abstr.1899 i 967). If the extraction with chloroform a t 34' is continued for several days the yield of invertase is somewhat better but the product contains larger amounts of gum. A considerable amount of the gum is thrown down in the first fraction when the clear chloroform extract is fractionally precipitated with 93 per cent. alcohol. A simpler method for the removal of gum is t o precipitate the invertase from a neutral solution of Osborne's crude product with a 5 per cent solution of copper acetate t o wash thoroughly precipitate the copper as sulphide and t o pour the filtrate freed from hydrogen sulphide into alcohol. Invertase of Yeast. Quantitative Experiments on the Action of Alcohol and Acids on this Enzyme. By THOUAS BOKORNY (Crhem. Zeit.1902 26 701-703. Compare Abstr. 1901 ii 568)- The author's experiments demonstrate that the inverting action of yeast is not effected by the living protoplasm but by a material which can be separated from the yeast cell this view was originally expressed by Berthelot in 1860. Four grams of fresh yeast extract at 45-40' in 15 minutes can convert from 68 to 82 per cent. of a sucrose solution varying in strength from 5 to 20 per cent. When kept for several days under absolute alcohol at the ordinary temperature the inverting action of yeast is unimpaired but a t 45' it is completely destroyed. Similarly 5 per cent. formaldehyde has little effect at the J. J. 5. Dried yeast has in no way lost this power.ORGANIC CHEMISTRY. 849 ordinary temperature but destroys the inverting power at 45'.Dried yeast extract is changed but little as regards inverting power by keeping in 0.5 per cent. oxalic acid 0.5 per cent. hydrofluoric acid 2 per cent. acetic acid or 2 per cent. lactic acid. K. J. P. 0. [Formation of Aromatic Mercury Compounds.] By LEONE PESCI (Zeit. anorg. Chem. 1902 32 227-234. Compare Abstr. 1898 i 648 ; 1901 i 576).-A claim f o r priority against Dimroth (this vol. i 656). The author also defends the views he has expressed previously on the constitution of the compounds obtained from aniline and mercuric acetate and other mercury aromatic compounds against Dimroth's criticisms. J. McC. [Formation of Aromatic Mercury Compounds.] By OTTO DIMROTH [and in part RICHARD METZGER] (Bey. 1902,35 263-3873. Compare Abstr.1899 i 154 428 and this vol. i 656).-The hydroxyphenylmercury salts (previously described) dissolve in dilute sodium hydroxide ; carbon dioxide precipitates from the solution of the ortho-compound the internal anhydride of o-hydroxyphenylmercury hydroxide C,H4<Hg ; from the para-compound a n oxide is obtained as a n insoluble white powder which cannot. be converted into o-phenylenemercury oxide. The pharmaceutical preparation Hydvarg yrum carbolicum which is prepared by heating sodium phenoxide and mercuric chloride in alcoholic solution and is generally considered to be a mercury phenoxide is now shown to consist mainly of a mixture of 0- and p-hydroxy- phenylmercury oxides and hydroxyphenylenedimercury oxide. o-Hercuryphenol (OH* C',H4),Hg is prepared by treating o-hydroxy- phenylmercuric chloride with sodium thiosulphate ; it crystallises in lustrous white plates which become coloured on heating and dissolve in alkali hydroxides but not in carbonates.The hydroxyphenyl- mercury salts give with nitrous acid at first coloured solutions and then coloured precipitates which resemble those obtained by the action of Millon's reagent on phenols proteids &c. p-Cresol and mercuric acetate i n mol. proportion give equal quantities of a mono- and a di-mercury compound; at loo' only the di- mercury compound is formed ; p-cresolmercury acetate OH* C$H3 Me Hg 0 Ac H20 is obtained by crystallising the product of the reaction from acetic acid ; i t decomposes at 200' ; addition of sodium chloride to the mother liquor precipitates p-cresolmercury chloride OH*C,H,Me*HgCl which crystallises in needles melting at 166' and decomposing a t 176' when it becomes solid.The corresponding iodide is prepared from the chloride and potassium iodide and crystallises in slender needles which begin t o decompose at 145'; the acetate prepared by dissolving the oxide in acetic acid crystallises -~ in leaflets melting and decomposing at 163'. The 0 ( OH*C,H *Hg),O oxide C6H,Me<yg is prepared as a white powder by dissolving 0850 ABSTRACTS OF CHEMICAL PAPERS. the chloride in dilute sodium hydroxide and then precipitating with carbon dioxide ; the sodium salt ONa*C,H,Me*Hg*OH crystallises in very soluble needles. The benxoyl derivative OBz*C6H,Me*HgCl prepared by the Schotten-Baumann method crystallises in slender needles melting a t 241-242'.o-lodo-p-cresol OH*C,H,MeI is prepared by the action of iodine on the iodide previously mentioned ; it crystallises in hair-like needles melting a t 35' and boiling a t 117' under 12 mm. pressure. Benzenediazonium chloride reacts with o-phenylmercury chloride forming the azo-compound N,Ph*C,H,(OH)*HgCl which is a reddish- brown powder melting a t 147'; it forms a stable additive product with 1 mol. of acetic acid which crystallises in yellowish-brown needles melting a t 126-128'; a hydrate with 1 or 1+H,O is obtained when water is added to the alcoholic solution and crystallises _in slender yellow needles which lose water when dried over sulphuric acid form- ing a very hygroscopic red powder; when dried a t loo' a red powder is obtained which is no longer hygroscopic.The azo-compound just mentioned combines with acids ; the compound with hydrogen chloride is a red powder melting a t 160'. When the azo-compound is boiled with hydrochloric acid i t is converted into p-hydroxyazobenzene. p-Hydroxyphenylmercury chloride and benzenediazonium chloride yield mainly p-hydroxyazobenzene together with a small quantity of a substancs probably benzeneazo-p-hydroxyphenylmercury chloride ; the latter melts a t 130-131" and forms a crystalline additive product with one mol. of acetic acid. Hydroxyphenyldimercury acetate and the diazonium chloride give chiefly benxeneaxo-o-hgdroxyphelzylmercury acetate ; i t crystallises in yellow prisms melting a t 197-198O; benxeneaxohyt.E1*oxyp~~enyldi~neri.cury chloride as an additive product with 1 mol. of acetic acid was also isolated by precipitating with sodium chloride and crystallising the product from acetic acid ; it melts and decomposes a t 165-1 70'. Berzxeneaxo-p-cresolmercury acetate N,Ph*C,H,Me(OH) *Hg*OAc forms red needles melting and decom- posing a t 269' ; the chloride prepared from the acetate crystallises in yellowish-brown silky needles melting and decomposing a t 249' ; both these compounds are soluble with difficulty in alkalis Thyrnolmercury chloride OH*C H,.MePr HgCl is prepared by adding sodium chloride to the acetic acid solution of the product of the reaction of mercuric acetake and thymol; it crystallises in needles melting at 139.5" ; the sodium salt forms needles ; thymoldimercury acetate OH*C6HMePr(Hg.0Ac) separates directly from the product of the reaction of thymol and mercuric acetate and forms needles melting and decomposing a t 215-216' ; the sodium salt crystallises in leaflets. A mixture of resorcinolmercury chloride and resorcinoldimercury chloride is obtained by adding sodium chloride to the product of the interaction of mercuric acetate and resorcinol ; chloroform extracts the monomercury compound C,H,( OH),*HgCI which crystallises in prisms containing chloroform and melts a t 105'; when free from chloroform it melts at 123' ; it is decomposed by water and yields a solution in sodium hydroxide rapidly becoming coloured. Resorcinol- climercury chloride forms an insoluble white powder which begins toORGANIC CHEMISTRY. 85 1 decompose at 200'. Quinol does not form a mercury compound but is oxidised t o quinhydrone by mercuric acetate. Phenol ethers such as anisole and phenetole react with mercuric acetate less readily than the phenols and yield substances which have previously been described. o-Benxophenonemercury chloride COPh*C,H,*HgCI is prepared by heating together dry mercuric acetate and excess of benzophenone converting the acetate thus formed into chloride by means of sodium chloride and separating the insoluble dimercury compound by ether ; the monomercury compound crystallises in leaflets melting a t 167-168' ; the dimei-cury compound is a yellowish powder. o-Belzxo- phenonenzercury . bromide melts at 1 7 6 O and .is converted by bromine into o-bromobenzophenone (m. p. 35'). Acetophenone and mercuric acetate yield phenacylmercury chloride COPh*CH,*HgCl the nucleus not being attacked; this substance forms needles melting at 145-1 4 6 O and is easily decomposed by bromine giving phenacyl bromide. Anhydrous mercuric benxoccte is obtained from the hydrated salt by crystallisation from chloroform ; i t forms crystals melting a t 165'; when co heated at 170° it is converted into a compound C,H4<Ha>0 which forms a powder soluble in alkali hydroxides and carbvonates and is changed by sodium chloride into chlorornerczcri6enxoic acid ; when treated with bromine o-bromobenzoic acid is formed. When dry mercuric salicylate is heated at loo' it is converted into salicylic acid and a compound OH*C,H,< >0 which is the anhy- dride of o-hydroxymercurisalicylic acid ; it is a white powder soluble in a1 kalis and identical with the pharmaceutical preparation Egdrargyrum salicylicum. By iodine it is converted into o-iodosalicylic acid con- sequently the mercury is attached to the benzene nucleus in the ortho- position relatively to the hydroxyl group. Mercuric Compounds from Terpineol and Dimethylheptenol. By JULIUS SAND and FRITZ SINGER (Ber. 1902 35 3170-3187).- Characteristic products cannot be obtained by shaking ethereal terpineol with aqueous mercuric nitrate or sulphate ; crystalline pro- ducts can however be obtained by dissolving yellow mercuric oxide in 20 per cent. nitric acid adding potassium hydroxide until basic nitrate begins t o separate and shaking with ethereal terpineol solu- tion the alkali and terpineol being added alternately until mercurous oxide begins t o be precipitated ; the solution is made strongly alkaline and on addition of potassium iodide gives an immediate precipitate of mercuricineol iodide a gradual separation of a-mercuric trans-terpin iodide from the filtrate and a further separation of p-mercuri-trans- terpin iodide on passing carbon dioxide into the solution. /CH,-CH Mercuricineol iodide CMe-0- CM&H crystallises from \CH( HgI)*CH,/ alcohol in small glistening prisms dissolves very readily in cold benzene or chloroform becomes yellow at 1 1 5 O and melts and decom- co Hg K. J. P. 0.852 ABSTRACTS OF CHEMICAL PAPERS. poses at 152-154'. The chloride crystallises from alcohol iu white felted needles melts constantly and sharply at 162' and unlike the iodide is readily soluble in alkali. The iodide does not yield a benzoate and when reduced with sodium amalgam does not yield a terpineol but a mobile oil which gives precipitates with hydrogen chloride bromide and ferrocyanide and is therefore in all proba- bility cineol. a-Mercuri-trans-terwin iodide separates from benzene in glistening colourless prisms is sensitive t o light becomes red at 120° and melts and decomposes a t 144'. It combines with alcohol to form the alcoholate CloHIQO,IHg,C,H,O which crystallises from alcohol in glistening needles and becomes red and melts a t 123-125'. The iodide is reduced by sodium amalgam or by electrolysis at a platinum cathode t o trans-terpin (m. p. 156'). P-~ercuri-trans-teipi~ iodide melts at 3S0 separates from. organic solvents as a n oil and like the preceding compound is reduced by sodium amalgam to trans-terpin ; when boiled with organic solvents it is readily converted into the stable a-compound. The a- and p-com- pounds are probably stereoisomerides differing only in the position of the -Hgl group ; as the a-compound is readily reconverted into terpineol by mineral acids it probably has the -HgI group in the cis-position relatively to the adjacent hydroxyl whilst the P-compound which is only slowly decomposed would have the -HgI in the ti-ans-position. Dimethylheptenol CMe,:CH*CH,*CH,*CMe,*OH prepared by Grig- nard's method from methylheptenone and magnesium methiodide is a highly refractive oil and boils a t 85-86' under 14 mm. pressure (uncorr.). Towards mercury salts it behaves in just the same way as terpineol giving an iodide C,H,,OIHg which is insoluble in alkalis and probably has the structure CMe,<o CMe >CH together with an iodide C,H,,O,IHg probably OH*CMe,*CH( HgI)*CH,*CH,*CMe,-OH soluble in alkalis which separates from benzene in glistening crystals becomes yellow and melts at 124-125' and probably also an isomeric oily iodide C,H,,O,THg. CH(HgI)*CH T. M. L.