Organic Chemistry. Analogies between Oxygen, Nitrogen, and Carbon in similar Linkings. By EMIL ERLENMEYER, jun. (J. pr. Chem., 1900, [ii], 62, 145-1 65).-A paper which summarises the results of introducing different atomic groupings into analogous compounds, but does not lend itself to abstraction. R. H. P. Action of Bromine on 1 : 1-Dimethyltrimethylene. By GABRIEL GUSTAVSON (.I pr. Chern., 1900, [ii], 62, 270-272).-The bromine compound previously described (Gustavson and Popper, Abstr., 1899, i, 263), and obtained by the action of bromine on 1 : 1-dimethyl- trimethylene (1 : 1 -dimethylcyclopropane), is py-dibromoisobutane, CMe,Br* CHMeBr. R. H. P. Derivatives of CycZoPentadiene. By FRITZ NOELDECHEN (Ber., 1900, 33, 3348-3354).-The chlorocyclopentene obtained by the addition of hydrogen chloride to Kraemer and Spilker's cyclopenta- diene (Abstr., 1896, i, 289) interacts with aniline below 10' to form anilinocyclopentene, C,H,*NHPh, a colourless oil boiling at 152-1 53' under 25 mm., and at 260' under the ordinary pressure ; the hydro- chloride crystallises from absolute alcohol in short prisms, and melts and decomposes a t 140-142O ; the platinichloride (with l$H,O) de- composes at 140' ; the picrate melts and decomposes a t 154-155', the sparingly soluble sulphccte at 197', and the oxakate at 122'.The ucetyl derivative, C,H,*NAcPh, crystallises from water in long needles, and melts at 128' ; the benxoyl derivative separates in transparent, hexa- gonal prisms from light petroleum and melts at 76-77'. cyclo Pentenyldiphenylcarbanzide, NHPh* CO *NPh*C,H7, obtained by the action of phenylcarbimide on the base at the ordinary temperature, separates from absolute alcohol in small leaflets and melts at 112'; the analogous thiocnrbamide cry stallises from absolute alcohol in lustrous, colourless needles and melts at 130'.Anilinocyclopentene interacts with nitrous acid to form a reddish- yellow, oily nitrosoamine, which shows Liebermann's reaction, and is reduced by zinc dust and acetic acid to cyclopentenylp?ienylydraxilze, NH,-NPh-C,H7, the hydrochloride of which forms silvery scales and melts and decomposes at 2 15-217'. On heating anilinocycZopentene with hydriodic acid, or with concen- trated hydrochloric acid €or 2 hours at ZOO', aniline is formed, together with a red, amorphous, insoluble substance. On attempting to reduce the base with sodium and amyl alcohol, an isomeric anilinocyclopentene is formed, instead of the expected anilinocyclopentane ; its hydrochloride is more sparingly soluble than that of the original base, and forms long, white needles melting and decomposing a t 168'; the platini- chloride (with 2H,O) decomposes at 135'.Piperidylcyclopentene, C,H,,N* C,H7, from chlorocyclopentene and piperidine at - 5', boils at 94-96' under 23 mm., and at 206-207O VOL. LXXX: i. P62 ABSTRACTS OF CHEMICAL PAPERS. under the ordinary pressure ; it absorbs carbon dioxide from the air, yields a crystalline methiodide, and a hygroscopic hydrochloride and sulphute, the former decomposing at 190'. Abnormal Behaviour of Polyhaloid Compounds with Alco - holic Potash. By IWAN L.KONDAKOFF (J. p. Chem., 1900, [ii], 62, 166-188. Compare Abstr., 1899, i, 556).-The previous work (loc. cit.) has been repeated, and it is now shown that the action of alcoholic potash on by-dimethyl-P-butylene di bromide produces diisopropenyl, By-dimethyl-/3-butylene, and an unsaturated ether, which boils at 136--146O, and, when treated with dilute sulphuric acid, gives pinacone, pinacolin, and an aldehyde. by-Dimethyl-P-butylene di- chloride, when treated with alcoholic potash, yields diisopropenyl and the ether boiling a t 136-146'. Diisopropenyl forms two dihrontides, the one is an oil, and the other crystallises in colourless needles, which have an irritating odour and melt at 47O, both yield the same tetrabromide melting at 137'.The crystalline dibromide, when oxidised, yields two glycols, of which one has the composition C6H1202Br2, crystallises in prisms, and melts a t 94O; the other, obtained in very small quantity, melts at 1 6 0 O . The paper contains a discussion of the constitution of bromides formed by unsaturated hydrocarbons from the point of view of Thiele's theory of I' partial " valencies (Abstr., 1899, i, 554). W. A. D. R. H. P, Diethyl Peroxide. By ADOLF VON BAEYER and VICTOR VILLIGER (Bev., 1900, 33, 3387--3393).-Diethyl sulphate was shaken witb hydrogen peroxide of 12 per cent. strength (by weight), 60 per cent. aqueous potassium hydroxide being added little by little ; the tempera- ture was not allowed to rise above 20', and the operation was continued (for some 11 hours) until the presence of hydrogen peroxide could be detected no longer.The product was then made acid with sulphuric acid and fractionated; the fraction coming over at 55-75O con- sisted mainly of diethyl peroxide, that distilling a t 75-100O probably contained some ethyl hydrogen peroxide. Diethylproxide, 02Et,, boils at 6 5 O , and has a sp. gr. 0.8273 at 15'/4O; it is strikingly inert in its reactions, almost resembling an ether ; permanganate, chromic acid, and sodium amalgam do not affect it, and it oxidises alkaline pyro- gallol and potassium iodide but slowly ; it is, however, reduced quanti- tatively to ethyl alcohol by zinc in the presence of acetic and dilute sulphuric or hydrochloric acid ; the " active " oxygen in it may be determined in this way by taking a weighed quantity of zinc and measuring the deficit in the hydrogen evolved as compared with that equivalent to the amount of zinc taken.The inflammability of the vapour is most striking; it inflames in air at 250°, or 50° below the kindling temperature of carbon disulphide vapour, and when a hot copper wire is brought near it in an atmosphere of carbon dioxide, the liquid disappears rapidly, without any noise, without any flash, and without boiling. As a result of this internal eombustion, form- aldehyde, carbon monoxide, and ethane are formed, A mixture of the vapour with air or oxygen explodes more violently than a mix- ture of hydrogen with air or oxygen. On the other hand, the liquidORGANIC CHEMISTRY, 63 could not be made to explode by hammering, or by the use of mercury fulminate. The ready reduction of diethyl peroxide to ethyl alcohol is regarded as strong evidence in favour of the formula HO*OH, rather than O:OH,, for hydrogen peroxide. Optically Active Forms of a-Bromopropionic Acid.By LUDWIG RAMBERG (Ber., 1900,33, 3354-3356).-0n adding cinchonine gradu- ally to an aqueous solution of a-bromopropionic acid, thick prisms or plates of the salt, C,,H,,ON,,2(C,H,O,Br), of the 1-mid separate ; the pure acid appears to have La], - 7.55" at 24O, the d-acid, isolated from the mother liquxs of the foregoing salt, having [a], + 7.44'. These values, however, are to be more accurately determined. By FRITZ FICHTER and WERNER LANGGUTH (Annalerz, 1900, 313, 371-381. Compare Wallach, Abstr., 1900, i, 589).-The paper contains experimental details relating to the pre- paration of 8c-hexenoic acid (Abstr., 1897, i, 590), and of ys-hexenoic acid (Abstr., 1897, i, 14).Action of Water on Heptylamine Soaps. By FRIEDRICH KRAFFT and R. FUNCKE (Ber,, 1900, 33, 3210-3212).-Whan heptylamine oleate (m. p. la0), elaidate (m. p. 45O), erucate (m. p. 21-5'), or brass- ate (m. p. 44.5') is brought into contact with water a t a temperature above the melting point, globular or thread-like bodies are produced, which grow in size when surrounded with water, but collapse in contact with a strong salt solution, the surface of the globules acting as a semi- permeable membrane. By cooling below the melting point, the globules disappear and crystals are again formed ; within certain limits of tem- perature, globules and crystals may both be observed. Transformation of Maleic Acid into Fumaric Acid, By JULIUS SCHMIDT @el*., 1900, 33, 3241-3243.Compare Wislicenus, Vei*hccnd. K. Ges. Wiss. Leipxig, 1895, 489).-Maleic acid, dissolved in dry ether, is not affected by the nitrous fumes evolved from a mixture of arsenious oxide and nitric acid; an aqueous solution, cooled below loo, when similarly treated, yields a mixture of unaltered substance and fumaric acid, whilst at the temperature of the water-bath 70 per cent. of the maleic acid is transformed. Fumaric acid is not produced when an aqueous solution of its cis-isomeride is heated on the water- bath, and no alteration results from the addition of nitric acid free from nitrous acid (compare Edmed, Proc., 1899, 15, 190).C. F. B. W. A. D. 8E-Hexenoic Acid. M. 0. F. T. M. L. a. T. M. Dicrotonic Acid. By HANS VON PECHMANN (Ber., 1900, 33, 3323-334 1) .-Dimethyl dicrotonate (dimethyl P-methyl-a-ethylidene- glutarate), formed by the action of sodium methiodide on dimethyl crotonate, is a colourless oil boiling a t 120' under 15 mm. and at 130' under 20 mm. pressure; it is also formed when dicrotonic acid is treated with diazomethane. Diethyl dicrotonate is prepared from diethyl crotonate, and boils at 137.5' under 18 mm. pressure. Dicrotonic acid, CHMe:C(CO,H)*CHMe*CH,*CO,H, prepared from the ester by hydr- olysis, crystallises in white, compact needles melting at 129O, and boils f 264 ABSTRACTS OF CHEMICAL PAPERS. at 210' under 21 mm. pressure, partial decomposition into water and anhydride taking place.The acid is dibasic to soda, and has a con- ductivity K 0 00281. The difference of equivalent conductivity of the sodium salt at dilutions of 32 litres and 1024 litres is 11.9, an abnormally low value for a dibasic acid. The barium salt crystallises with 1H,O in lustrous scales; no acid salts could be obtained. Mono- ethyl dicrotonate, CHMe:C(CO,H)*CHMe*CH,* CO,Et, is obtained by the action of alcoholic sodium ethoxide on dicrotonic anhydride, and is an oil boiling a t 174" under 16 mm., at 186' under 34 mm., and at 192' CHMe FH2 under 44 mm. pressure. Dicrotonic anhydride, CHMe:C< formed when the acid is distilled under atmospheric pressure or treated with acetyl chloride, crystallises in white needles melting at 38--39O and boiling a t about 300'.The constitution of the acid is shown by the fact that on oxidation with potassium permanganate it yields acetaldehyde and methylsuccinic acid. GO-o*co ' P-Methyl-a-ethylideneglutaranilic acid, CHMe:C(CO,H)*CHMe*CH,* CO *NHPh, is obtained by the action of aniline on the anhydride, and crystallises in lustrous prisms melting a t 178-179O. Dicrotonic acid readily combines with bromine t o form an unstable dibromide, which loses hydrogen bromide when heated with water and forms 6-6romo-/I-methylhexolactone-y-carboxylic acid, CHMeBr*C(C02H)<o-CO>CH,, CHMe which crystallises in colourless prisms melting at 140'. When its solution in sodium carbonate is boiled, hydrogen bromide and carbon dioxide are eliminated with formation of P-methylhexenobctone, MeCH:C<CHMe'QH2, which is a colourless oil boiling at 247'.The corresponding acid, Ps-dimeth yllmvulic acid, CH,Me*CO* CHMe*CH,* CO,H, is a thick oil boiling a t 153-254' under 20-21 mm. pressure. The phenylhydraxone is a thick oil, wbilst the semicar6axonet C7H!,0,:N*NH* CO *NH,, is a characteristic, white, crystalline powder melting at 152'. When heated, it yields a pyridazinone, probably a homologue of the 3-methylpyridazinone, which is formed in a similar manner from the semicarbazone of lavulic acid. Pa-Dimethyllaevu- lic acid can be prepared synthetically from acetonedicar boxylic acid, and its formation in this way affords further confirmation of the con- stitution of dicrotonic acid. Ethyl dimethylacetonedicarboxylate reacts with ethyl bromoacetate to form triethy Z aa,-dimethykacetonedicarboxy- acetate, CO,Et*CHMe*CO*CMe(CO,Et)*CH,*CO,Et, which boils a t 19 1 -5O under 16 mm.pressure. CHBrMe*CH(CO,H)*CHMe*CH,* CO,H, is formed by the combination of hydrogen bromide with dicrotonic acid and crystallises in aggregates of needles; the acid readily loses bromine, and could not be obtained quite pure. When distilled, it forms crotonic acid together with a smaller amount of /3-methyl-yrS-IZex- 0-co P-Methyl-y-bronaoethylglzctaric acid,ORGANIC CHEMISTRY. 65 enoic acid, CHMe:CH*CHMe*CH,*CO,H, which is also formed when the acid is heated with water. It is a colourless liquid with a rancid smell, and boils at 209-210°. With bromine, it forms y8-dibromo- P-methylhexoic acid, CHBrMe*CHBr*CHMe*CH,*CO,H, which crystal- lises in rhombic tablets and melts at 135-1 36'.~-lllet?~~l-a-et?~ylglutar~c acid, CO,H*CHEt*CHMe*CH,*CO,H, is formed by the reduction of p-methyl-y-bromoethylglutaric acid and crystallises in colourless prisms melting at 100-101' ; K= 0-0067. By FRITZ FICHTEB and SYLVAIN HIRSCH (Ber., 1900, 33, 3270-3276).-Bromo-as- dimethylsuccinic acid, which could not be obtainea pure by von Baeyer and Villiger (Abstr., 1897, i, 597), yields on distillation the >0, which forms stout needles, melts at 45', pure anhydride, and boils at 121-123' under 13 mm. pressure. On evaporating its aqueous solution in a vacuum, the pure acid, C',H,O,Br, is obtained as a hard, crystalline crust melting a t 153'; if the anhydride is dissolved in benzene containing water, slender needles of the acid with $C,H, separate, which melt at 133", and effloresce in the air, the acid thus obtained melting at 143O.The B-lactone of as-dimethvlmalic acid distils at 145-150' under A. H. The P-Lactone of as-Dimethylmalic Acid. $%Te2-C0 CHBr*CO .I 13 mm. pressure, being converted into the isomeric ccnhydride, yMe,*CO >0, a colourless oil which is also formed on distilling OH* OH-CO as-dimethylmalic acid under the same conditions, although decom- pcsition occurs at atmospheric pressure. Since the anhydride readily absorbs water from the air to form dimethylmalic acid, it differs essentially from the isomeric lactone which crystallises from water unchanged. W. A. D. Ey MAX CONRAD (Bey., 1900, 33, 3432-3438).--Methyt oxalyldimethylacetoacetate, CO,Me*CO*CH,* CO C Me,.CO,Me, prepared by the action of sodium on an ethereal solution of methyl oxalate and methyl dimethylacetoacetate and purified by converting into the copper compound, is a pale yellow oil which has a sp. gr. 1.193 at 17'/15O, boils and partially decomposes a t 270-278", has a distinct acid reaction, mixes readily with ether, alcohol, or benzene, and gives a cherry-red coloration with alcoholic ferric chloride. The calcium derivative, Ca(CloH,,O,),, dissolves in ether, softens a t 115O, and melts at 125'; the cobcclt derivative, Co(CloHl,O,),, melts a t 98-100' ; the copper derivative, Cu(Cl,Hl,O,),, melts at 128-130' ; the compound with ammonia, Cl,HpO,N, forms minute, white needles, and melts at 1 10". Methyl anz~z~zo-o~~6~?/ldirnethylcccetoacetate, CO,Me*C(NHPh):CH* CO*CMe,* CO,Me, or CO,Me*CO*CH:C( NHPh).CMe,* CO,Me, crystallises from methyl alcohol in large, well-formed, sulphur-yellow prisms aod melts at Sl'; t h e monoxime, C10H150GN, crystsllises from hot water and melts at 9 lo.Oxidyldimethylacetoacetic acid forms colourless crystals, melts at 180' with evolution of carbon dioxide, and Oxalyldialkylacetoacetic Esters.66 ABSTRACTS OF CHEMICAL PAPERS, also loses carbon dioxide in aqueous solution a t 70--80°, giving an isobutyrylpyruvic acid. Methyl bromo-oxalyldimetliylacetoacetate is a yellow oil ; it forms a copper derivative, Cu(CloH12Br06),, crystalking from ether in green S FH* CO *CO,Me or needles. The thiaxyl derivative, NH:C<N: C,CMe,.CO,Me - 1 A S FH*CO*CMe,* C0,Me , prepared by the action of thiocarb- NH: c<N : C* c O,l\le amide on the &bromo-ester, crystallisea from hot water in white needles and melts a t 138'.By the action of potassium acetate on the bromo-ester in methyl alcoholic solution, methyl oxalate and the acetate of methyl hydroxydimethylacetoacetate are produced as decomposition products of methyl acetoxyoxalyldimethglacetoacetate. Ethyl oxalyldiethykucetoucetate, CO,Et*CO*CH,* CO*CEt,* CO,Et, is a colourless oil which forms a copper derivative and gives a red color- ation with alcoholic ferric chloride. By distillation, it gives ethyl aa-dieth yZacetonedicarboxyZute, CO,Et*CH; CO*CEt,* CO,Et, boiling at 275-285'. T. 11. L. Glycuronic Acid. I. By CARL NEUBERG (Ber., 1900, 33, 3315-3323).-Several of the compounds described by the author have been previously described by Giemsa (this vol., i, 11).Glycurono- lactane (glycurone) is best obtained by boiling euxanthic acid with dilute sulphuric acid. GZycuroneamylmercaptal was only obtained in the form of a viscid oil. Glycurorzethiosemicurbaxone, OH*CH<~~~~J>CHXIH(OH)*CH:N*NH*CS-NH,, crystallises from water in fascicular groups of needles melting at 223O, and is insoluble in the ordinary organic solvents. Glycurone- diphenylhydraxone, C6H,0, :N,Ph,, crystallises in needles melting at 150'. Glycuroneoxime is converted by acetic anhydride and sodium acetate into the tetraacetyl derivative of the seminitrile of d-saccharic acid, which has not, however, been obtained pure. Glycuronic acid forms characteristic salts with many of the alkaloids.The cinchonine salt, C6H,,0~,Cl,H,,N,0, crystallises in characteristic white needles melting at 204O, and has [.ID + 138.6'. The quinine salt softens at 175', melts a t 180°, and has [a], - 80.1'. The brucine salt crystallises in very slender needles uielting at 200', and the styychnine salt closely resembles it. Glycurone can readily be separated from the sugars by means of its thiosemicarbazone, and glycuronic acid by the aid of the cinchonine salt, whilst the acid is best detected in presence of the sugars by means of the p-bromophenylhydrazine compound. Acidimetry of Aldehydes and Ketones. By A. ASTRTJC and H. MURCO (Compt. rend., 1900, 131, 943-945).-A number of alde- hydes and ketones of simple and mixed function were examined as to their behaviour towards the indicators helianthin A, phenolphthalein, and Poirrier's-blue.The simple aliphatic and aromatic aldehydes are neutral towards all three indicators. Glyoxal, the only simple dialdehyde examined, reacts A. H.ORGANIC CHEMISTRY. 67 with one equivalent of alkali, but the process is slow. Halogenated aldehydes, such as. chloral hydrate, chloral alcoholate, and bromal, are neutralised by one equivalent of alkali. Hydroxybutyraldehyde and aldehydic sugars are neutral towards all three indicators, whereas tsalicylaldehyde, p-hydroxybenzaldehyde, methylprotocatechuic alde- hyde (vanillin), and methybnoprotocatechuic aldehyde (piperonal) are neutral towards helianthin but monobasic towards phenolphthalein or Poirrier’s-blue. The simple aliphatic and aromatic ketones are without action on either of the three indicators.Acetylacetone is exactly monobasic fowards Poirrier’s-blue, but behaves less definitely with phenol- phthalein. The exact titration of methylacetylacetone is impossible with either of these indicators. Acetonylacetone is neutral. Chloro- acetone and bromoacetophenone are neutral towards helianthin and monobasic towards phenolphthalein or Poirrier’s-blue. The ketonic sugars are neutral, Pyruvic and lzevulic acids are exactly monobasic towards phenolphthalein or Poirrier’s-blue, but with helianthin the neutral point is reached before one equivalent of alkali has been added. N. L. Search for other Sugars than Xylose and Dextrose in the Products of the Hydrolysis of Wood from the Trunks of Trees.By FRANCIS H. STORER (Bull. Bussey Inst., 1908, 2,437-467). -The author has submitted samples of wood from the trunks of the sugar maple (Acer saccharinurn) and birch (Betula populqolia), and from the root of the former tree to the action of hydrochloric and sulphuric acids under various conditions, and determined the cupric- reducing and rotatory powers of the solutions thus produced, in order t~ obtain, if possible, indications of the presence in wood of substances hitherto undeteoted. Cotton cloth was also subjected to the same treatment. The results of these experiments led to the following conclusions, When strong sulphuric acid is allowed to act on cellulose, and the product boiled with dilute acid, the whole of the cellulose is not readily converted into dextrose, as has been frequently stated.The oompounds which carbohydrates form with sulphuric acid are very difficult to decompose by long continued boiling, and, as a general rule, a considerable part of the organic matter with which the strong acid a t first united is not changed into dextrose when sub- sequently boiled with the dilute acid ; some part of this undecomposed substance remains admixed with the dextrose syrup, and tends finally to contaminate the solid dexfrose. I f the calcium or barium salts of these compounds of carbohydrates with sulphuric acid are boiled for a long time, some quantity of the salts is liable to remain undecomposed and render the dextrose syrup impure; when such syrups are con- centrated, crystals of two kinds are obtained, one of which consists entirely of inorganic! matter, Bdchamp (AM.chim. phys., 1831, [ii], 48, 502) appears to have mistaken the latter substance for sugar, and it is probably due to the same cause that Berthelot (Ann. chim. phys., 1859, [ iiiJ, 55,293) was led to state that the dextrose from wood differs from all other dextroses.68 ABSTRACTS OF CEEMICAL PAPERS. The quantity of dextrose which is usually said to be obtainable from a given weight of cellulose is largely in excess of that observed by the author ; such statements, however, are generally based merely on the reducing power of the product of hydrolysis, whereas in the solutions obtained, substances other than dextrose are present which are capable of reducing considerable quantities of Fehling's solution.The portion of the product of hydrolysis which is insoluble in alcohol is usually regarded as ' dextrin,' but its high reducing power suggests the presence of a sugar analogous to isomaltose. If, however, pure dextrose is treated with sulphuric acid under conditions similar t o those observed in the hydrolysis of wood, a part of the residue ob- tained is insoluble in aloohol, and resembles the ' dextrin ' from wood ; it may be, therefore, that in each case some of the dextrose is converted by the alcohol into the insoluble dextrose anhydride. The difficulties attending the study of the hydrolysis of cellulose are greatly increased by the reversion of dextrose to dextrin which may occur in the process. By LOUIS HENRY (Be?.., 1900, 33, 3169-3171.Compare this vol., i, 16, and Strauss, ibid., 17).- A number of amino-alcohols have been prepared by the reduction of the corresponding nitro-compounds with tin and hydrochloric acid, or from cyano-alcohols by reduction with sodium and alcohol. They are somewhat viscid liquids with a fishy odour, and dissolve in water, but, with the exception of methyl-a-aminoethylcarbinol, are insoluble in ether : E. G. Formation of Amino-alcohols. Boiling point. Sp. gr. P-.Aminoethyl alcohol, y-Aminopropy 1 alcohol, 6-Aminobutyl alcohol, P-Aminoisopropyl alcohol, Methyl-a-aminoet hylcar binol, Whennitroacetone is kept for some time it turns brown, whereas OH*CH,*CH,*NH ,.................. 171' I1.022 at20° OH*[CH,],*NH, ..................... 18'7-188 1.020 a t 12 OH*[CH,],*NH ,..................... 206 0.967 at 12 OH*CHMe*CH,*NH ,............... 160-161 0.973 a t 18 OH*CHMe*CHMe*NH,. ........... 159-160 0.9423 at 18 nitroethyl alcohol remains iolourless even when kept for some years. J. J. S. Hydraaides and Azoimides of' Organic Acids. XVII. Syn- thesis of ay-Diaminopropane and aC-Diaminohexane from Glutaric and Suberic Acids respectively. By THEODOR CURTIUS and HANS CLEMM (J. p. Chem., 1900, [ii], 62, 189-211).-Glutaric di- hydraxide, CH,(C1H2*C0*NH*NH2),, obtained by boiling hydrazine hydrate with ethyl glutarate, crystallises in silky leaflets which melt at 176O, reduces Fehling's solution, forms a colourless hydrochloride, and when shaken with benzaldehyde yields dibe~xylideneglzctaric dihydv- axide, which crystallises from glacial acetic acid in small needles melt- ing at 231-232O.Glutaric diccxoimide, CH,(CH,*CO*N,),, is obtained by adding a cold solution of sodium nitrite to a cooled solution ofORGANIC CHEMISTRY. 69 glutaric dihydrazide hydrochloride under ether ; it is a clear, mobile, explosive oil with a suffocating odour, does not solidify at -15', is decomposed by sodium hydroxide, yielding sodium azoimide ; when treated with ethyl alcohol, it yields diethyl trimethyleneurethane, CH,(CH,*NH*CO,Et),, which is a viscous oil boiling and decomposing at 290-300°, and solidifying to feathery crystals after standing in a freezing mixture for some time; when heated in a sealed tube a t 100- 110' for some hours, it yields trimethylenediamine hydrochloride. Glutaric diazoimide, when slightly warmed with water, explodes with the formation of small quantities of trimethylenecccrbamide which melts at about 250'.The corresponding suberic compounds were obtained by analogous methods. Xuberic dilhydraxide, C2H4( CH,*CH,*CO*NH*NH,),, crys- tallises in large, colourless, lustrous leaflets which melt at 185--186O, and yields a dibenzylidene compound which crystallises in small, white needles and melts at 197". Xuberic diuxoimide is obtained in compact crystals which melt at 25' and explode when heated further ; when treated with alcoholic ammonia, it yields suberamide, which crystallises from alcohol and melts at 216' ; when treated with aniline, it yields hexumeth ylenedicarbunilide? C,H,,( NH*CO*NHP h),, which crys tallises in long, thin, colourless prisms and melts at 220' ; when treated with anhydrous alcohol, it yields diethyl hexamethylenediuvethane, which crystallises in long, lustrous, colourless needles melting a t 84' ; with alcohol in the presence of water, it yields the urethaieecarbarnide, CO(NH*[CH,]G*NH*C02Et),, which is a colourless, crystalline com- pound melting a t 132' ; when treated with water, it yields hexrxmetlbyl- enecurbamide, which crystallises in long, lustrous, colourless needles melting a t 84'.a[-&mainohezane dihydrochloride, C,H,,(NH2),,2HC1, best prepared by the hydrolysis of diethyl hexamethyleneurethane with concentrated hydrochloric acid, crystallises in colourless needles, melts at 248', and when treated with solid potash yields at-diumino- hexane (hexamethylenediamine), which cry stallises in silky, colourless leaflets, melts at 42', boils at 100' under a pressure of 20 mm., is very hygroscopic, and absorbs carbon dioxide with the formation of a car- bonate; it forms a diacetyl derivative which crystallises in small needles melting a t 125-126', a dibenxoyl derivative which crystallises in colourless plates melting at 157--158O, apicvate, C,H1,N,,2C6H3O7N3, which decomposes at about 200', an oxalccte, C6Hl6N2, 2H,C,0,,H20, which melts and decomposes a t 1 6S0, a pZ~ctinichZoride,C~H~~N~,H,PtCl, which decomposes between 222' and 2 2 4 O , an uurichlorzde which crys- tallises in long, compact, lustrous yellow prisms, and a mercui-ichloyide, C6H,BN,,2HC1,4HgCl,, which crystallises in long leaflets and melts at 228-230°, all of which are analogous to the salts and derivatives of pentamethylenediamine ; it dissolves uric acid, and has a very similar physiological action to piperazine and urotropine.The melting points of the diamines, like those of the dibasic acids, of the normal hydrocarbons containing an even number of carbon atoms are higher than those containing an uneven number, whilst the boiling points increase regularly with nurn ber of carbon atoms. C6H12( NH*C02E t)2, R. H. P.70 ABSTRACTS OF CHEMICAL PAPERS. Hydraeides and Aeoimides of Organic Acids. XVIII. Synthesis of a0-Diaminooctane from the Azide of Sebacic Acid. By THEODOR CURTIUS and WILHELM STELLER (J. pr. Chem , 1900, [ ii], 62, 212-231).--Xe6acic dihydraxide, C,H,(*[CH,]*,CO*NH*NH,),, obtained by the action of hydrazine hydrate on diethyl sebacate, crys- tallises in lustrous, rhombic leaflets, melts at 184-185', and when dry hydrogen chloride is passed into its anhydrous alcoholic solution, yields a dihydrochloride which forms rhombic crystals melting acd de- composing about 250' ; it condenses with benzaldehyde, forming di- benxylidenesebacic dihydruzide, which melts at 158-159', forms a tetrat6enxoyZ derivative which melts a t 250°, and when treated with an alcoholic solution of iodine ( 2 mols.iodine to 5 mols. dihydrazide) CO*NH yields s-sec-sebacic hydrazide, C,Hl,<co.&H, which crystallises from alcohol and melts at 142'. Xebacic diaxoimide, C,H,,(CO*N,),, ob- tained by the action of nitrous acid on the dihydrazide, is a stable, colourless compound, which melts at 33-344 and is not explosive.When treated with aniline, it yields octomethylene dicarbamanilide, C,Hl,(NH*CO*NH*Ph),, which crystallises in flat, right-angled needles melting at 206-2@7' ; when treated with water, octomethylenecadj- amide is formed, which is an insoluble, bluish-white powder decomposing at 216' ; when treated with moist ethyl alcohol, s-dioctomethylenedi- ethylurethanecarbmnide, CO(NH*[CH,],*NH*CO,Et),, is obtained as an amorphous compound melting at 132-133'; when treated with abso- lute ethyl alcohol, diethylootometl~ylenediurethane, C,H,,(NH*Co2Et),, is formed, and crystallises in feathery aggregates melting at 78-80' ; when treated with methyl alcohol, the corresponding dimethylurethane which melts a t 114-115' is obtained.Octomethylenediamine dihydrochloride is best prepared by boiling either the diethyl- or dirnethyl-urethane with concentrated hydrochloric acid for six hours. The derivatives and salts of octomethylenediamine are analogously constituted to those of hexaruethylenediamine (see preceding abstract) ; the dibenxoyl derivative crystallises in silky prisms and melts a t 140', the pic~ate melts at 182-183', the oxalate crystallises in lustrous, white lamins and melts at 223', the rnercuri- chloride crystallises in pinkish aggregates and melts at 189-19 lo, the ccurichloride forms microscopic crystals and melts at 188-189O ; it also forms a characteristic salt with cadmium chloride, which crystal- lises in white aggregates from hydrochloric acid, and does not melt below 300O.When treated with nitrous acid, the diamine yields a greenish oil, which has the odour of octyl alcohol, and is probably octometh y Zeneg lyco 1. Hydrazides and Azoimides of Organic Acids. XIX. Syn- thesis of apy-Triaminopropane from Tricarballylic Acid. By THEODOR CURTIUS and AuausT HE~SE (J. pr. Chem., 1900, [ ii I, 62, 2 3 2-2 46). -Tricar ball y lic trih ydrazid e, C,H,( GO NH* NH,),, obtained by the action of hydrazine hydrate on triethyl tricarballylate, is a crystalline substance melting at 195--196O, and forms a very soluble trihydrocMoride, which melts and decomposes a t 1 48O, a tripicrate which crystallises in small, yellow plates and melts at 1739 and condensation R. H. P.ORGANIC CHEMISTRY. 71 products with benzaldehyde and salicylaldehyde, which are white, microcrystalline substances melting at 2 18' and 205-206" respec- tively; when treated with nitrous acid, it yields tricarballylic triaxomide, C,H,(CO*N,),, which is a clear, explosive oil; this, when treated with anhydrous ethyl alcohol, yields triethyl glycei.yltr iurethane, C,H,(NH*CO,Et),, which melts a t 91-92' ; when treated with water, diglycerylca~bamide, CO NH*C,H5<zE>CO),, which is a white, crystalline substance, is formed.u/3y-Triaminopropane, C,H,(NH,), (compare Gabriel and Michels, Abstr., 1893, i, 31), is a colourless oil which boils at 92-93' under 9 mm. pressure, and forms a trihydi*ochloYide, which is obtained by the hydrolysis of the urethane with hydrochloric acid, crystallibes, with H,O, in colourless, compact plates, and, when anhydrous, begins to sinter at 220°, and melts and decomposes about 250'; it forms an uurichloride, C,H,(NH,),, 3HCl,AuCl,, which melts and decomposes at 210-212', a platinichlokiik, C3H,(NH,),,3HC1,PtCl,, which crystal- lises in needles and decomposes a t 220°, a tvipicrate, which crystallises in long, yellow needles and does not melt below 270', and a tribermoyl derivative, which is a microcrystalline substance melting at 206-207', and is particularly suited for the purification of the base, as when hydrolysed with strong hydrochloric acid it yields the hydrochloride in a pure state.By BRONISLAW PAWLEWSKI (Ber., 1900, 33, 3164).-Pure canarin is readily formed when ammonium persul- phate is added gradually to a solution of ammonium thiocyanate con- tained in an open dish.When a woollen fabric is dipped in ammonium persulphate solution and then in ammonium thiocyanate and the operations repeahed several times, the fabric becomes dyed intensely with canarin. J. J. S. By CARL D. HARRIES and NAURUS WEISS (Ber., 1900, 33, 3418--3149).-The hydrochloride of the ethyl ester of glycine, when treated with potassium cyanate, is converted into ethyl hydantoate, which crystallises in compact needles, melts at 1 3 5 O , and when treated with nitrous acid yields a nitroso- derivative melting at 66-67'; this ester, when heated at 135' for seven hours, or when warmed with 25 per cent. hydrochloric acid, is converted into hydantoin. The hydantoin formed by the latter method melts at 21'7-220' instead of at 215'. Quantitative yields are obtained in all the stages from glycine.By JULIUS TAFEL and ARTHUR WEINSCHENK (Ber., 1900, 33, 3378-3383).-Methyluracil, CO<CEZFG>CH, was dissolved in 50 per cent. sulphuric acid and reduced electrolytically either at 15' or at 50°, between prepared lead electrodes (Abstr., 1900, ii, 588), with a current concentration of 120-150 amperes. The resulting liquid was freed from free sul- phuric acid and evaporated under diminished pressure ; the residue was extracted with boiling chloroform, in which methyltrimethylem- ( R. H. P. Formation of Canarin. A Method of Preparing Hydantoin. R. H. P. Electrolytic Reduction of Methyluracil.72 ABSTRACTS OF CHEMICAL PAPERS. carbarnide, CO<NH-cH, NH*CHMe>CH2, dissolved, whilst the suIphate of ay-diamimo62ctafie, NH,-CHMe*C H,*CH,*NH2, remained behind. Methyltrimethylenecarbamide melts at 200-202°, and is neutral in reaction; it forms a picrate, which was analysed; it is not easily hydrolysed, but when heated with concentrated hydrochloric acid a t 200' (or less well with 30 per cent.sulphuric acid), it loses carbon dioxide and forms diaminobutane. ay-Diaminobutane boils a t 140.5-141*5° under 738 mm. pressure, and has a sp. gr. 0.86; its hydrochzoride, which melts a t 170--172O, and picrate, which is very insoluble and explodes when heated, were analysed. These reactions afford a convenient means of preparing ay-diamino- butane. Methyluracilis reduced electrolytically in the mannerdescribed; the resulting liquid is freed from so much sulphuric acid that three parts of the latter still remain for every 1 part of methyluracil, the liquid is concentrated unkil only 10 C.C.remain per 1 gram of uracil, and the residue is heated for 6 hours a t 2 0 0 O . By JULIUS TAFEL and ARTHUR WEINSCRENK (Ber., 1900, 33, 3383-3387).-Barbituric acid, or malonylcarbamide, CO<NH.Co>CH2, was reduced electro- lytically at 1 6-21°, and the product worked up as in the case of methyl- uracil (preceding abstract). The residue after the evaporation con- tained trimethylenecarbamide, CO<NH. KH-CH CHi>CH2, and hydrouracil, CO<:EZ;6>CH2 ; the latter remained behind when the residue was extracted with cold water, whilst the trimethylenecarbamide dis- solved, and could be recovered from the solution by means of its picrate, which is almost insoluble in cold water.Hydrouracil melts at 274O, and in small quantities sublimes unchanged; it does not dissolve more readily in dilute hydrochloric acid than in water, but it does so in aqueous sodium or barium hydroxide; from these solutions, i t is precipitated by carbon dioxide. By CHARLES CLOEZ (Compt. rend., 1900, 131, 899-90l).-When a disub- stitution derivative of benzene contains a basic group NH, or NR,, and the second group is neutral (Me,Cl) feebly acid (OH) or acid (CO,H), nitration takes place in the para- or ortho-position with respect to the amino-group. Nitration in the meta-position is obtained only in presence of a large excess of sulphuric acid. When the benzene derivative contains an OH group with the groups Me, C1, NO,, or COH, nitration takes place in the ortho- and para- positions, but if the hydroxyl group is converted into an alkyloxy- group, nitration will take place also in the meta-position.With the derivatives CO,H : OH = 1 : 3, three compounds are obtained with the NO, group in the position 2 or 4 or 5. When the derivative contains a Me or C1 group with a NO,, CO,H, or COH group, nitration takes place in the ortho- or para-position with respect to the C1 or Me group. C. F. B. Electrolytic Reduction of Barbituric Acid. NH*CO C. F. B. Nitration of the Disubstitution Derivatives of Benzene.ORGANIC CHEMISTRY. 73 With o-nitro- or p-nitro-benzoic acid, the second nitration takes place in the meta- or para-position with respect to the first nitro-groups. C. H. B. Nitro-derivatives of o-Dinitrosotoluene and o-Dinitroso- xylene.By THEODOR ZINCKE and P. DROST (Annalen, 1900, 313, 299-316. Compare Abstr., 1899, i, 75 1).-Nitro-o-dinityosotoluene [Me : NO, : (NO),= 1 : 2 : 3 : 4 or 1 : 6 : 3 : 41, prepared from 3 : 4-di- nitrosotoluene and fuming nitric acid, crystallises in pale yellow needles which melt and decompose a t 164'; it is also formed when the imide of o-nitro-p-toluidine is added to fuming nitric acid and the product heated in a brine bath, 2 : 6-Dinitro-3 : 4-dinit rosotoluene, obtained by the action of fuming nitric acid on a solution of the nitro-deriva- tive in concentrated sulphuric acid, crgstallises from concentrated nitric acid in silky yellow needles melting and decomposing at 133'. produced when dinitro-p-diazotolueneimide is heated a t 11 O', crystallises from glacial acetic acid in lustrous, yellow leaflets melting a t 145'; dinitro- p-diaxotolueneimide, formed on dissolving nitrodiazotolueneimide in fuming nitric acid, crystallises from alcohol in colourless needles aud melts at 97'.5-Nityo-2 : 3-dinitrosotoluene crystallises from alcokol in yellow leaflets and melts at 70'. 5-Nitro-o-diaxotolzceneimide [ 5-nitrot oluene- 2-tcxoimide], NO2*C6H3Me*N3, melts a t 69O, and when treated with fuming nitric acid is converted into 3 : 5-dinitrotoluene-5-axoimide, which crystallises from alcohol in pale yellow needles, and melts a t 61' ; the latter substance yields 5-nitro-2 : 3-dinitrosotoluene when heated on the water-bath. Nitrodinityosotoluene [P Me : (NO), : NO, = 1 : 2 : 3 : 41, obtained by dissolving 2 : 3-dinitrosotoluene in fuming nitric acid, forms pale yellow, feathery crystals and melts at 162'; a mixture of concen- trated sulphuric and nitric acids converts it into dinitrodinitrosotoluene (? Me : (NO), : (NO,),= 1 : 2 : 3 : 4 : 61, which melts and decomposes a t or 1 : 3 : 4 : 2 : 51, produced by the action of fuming nitric acid on 3 : 4 : 5- nitro-m-xyleneazoimide, crystallises from alcohol in white leaflets melting at 82'; when heated at l l O o , it yields nitrodinitroso-xylene, which crystallises from alcohol in yellow needles, and melts at 116'.1 : 3 : 4- tolylenefurazan and nitric acid, crystallises in long, yellowish needles, and melts at 83'. Dinitroaminocresol [? Me : OH : (NO?), : NH, 7 1 : 2 : 3 : 5 : 41, formed when dinitro-p-tolueneazoimide, is dissolved in concentrated sul- phuric acid, crystallises from boiling water in small, red needles, and melts a t 172', when it decomposes ; the acetyl derivative forms yellow crystals, and melts a t 171'.Dinitroaminocresol [Me : OH : (NO,), : NH, = 1 : 4 : 3 : 5 : 2 or 1 : 6 : 3 : 5 : 21, obtained from dinitro-o-tolueneazo- imide, crystallises from boiling water in small, yellow needles. The compound C7H705N3, a bye-product of the nitration of nitro- p-tolueneazoimide, separates from alcohol in lustrous crystals, and Nitro-o-dinitrosotoluene [? Me : (NO), : NO, = 1 : 3 : 4 : 51, 122-1 23'. Dinitro-m-xyleneaxoimide [Me, : N, : (NO,), 7 1 : 3 : 4 : 5 : 6 Nitrotolylenejhrazan, N0,.C,H2Me<N>0, N prepared from74 ABSTRACTS OF CHEMICAL PAPERS, melts, decomposing, a t 146'; the acetyl derivative melts and evolves gas at 142O. Electro-chemical Reduction of Mononitro-compounds in slightly Alkaline Solutions. By EARL ELBS (Zeit.E'lectrochenz., 1900, 7, 133 and 144).-The author gives a r6sum6 of the results ob- tained in the reduction of 56 mononitro-compounds by the metbocl described by him (Abstr., 1899, i, 270). He shows that, in every case, these results are in harmony with the following representation of the electrolytic reduction of nitrobenzene, due t o Haber and Schmidt M. 0. P. (Zeit. phy.sikml. Chenz., 1900, 32, 271) : e PhXNPh- PhN-NPh' \I \G PbNH*OH. &HPh*sHPh I The vertical arrows indicate electrolytic reductions, the slanting ones indicate purely chemical reactions which take place between the different products.The nature and relative quantities of the final products will, of course, depend on the properties of the compound undergoing reduction. pNitroaniline, for example, yields p-phenylene- diamine, owing to the fact that the nitroso-compound first formed changes very readily into quinoneimide oxime, which can only lead to the diamine ; m-nitroaniline, on the other hand, yields m-diaminoazo- benzene, owing to the fact that the meta-compounds have no tendency to form quinone derivatives. The nitroso- and hydroxylamine com- pounds formed by the direct reduction, therefore, react yielding the azoxy-compound which is further reduced. The azo-compound is always formed by oxidation of the hydrazo- compound; in cases, therefore, where the latter is not readily formed the azo-compound is not produced.The dinitro-compounds behave in an entirely different manner. Isolation of Sulphonic Acids by Vacuum Distillation. T. E. By FRIEDRICH ERAFFT and w. WILKE (Bey., 1900, 33, 3207-3209. Compare Krafft and ROOS, Abstr., 1892, 1219.)--In addition to the sulphonic esters, a number of sulphonic acids can be purified by distillation, when the cathode-light' vacuum is used (Abstr., 1896, ii, 464). The boiling points and melting points of the acids are as follows : B p. at Height of M. p. 0 mm. vaponr column. ............ Benzenesulphonic acid 66' 135' 90 mm. Toluene-p-sulpbonic acid ......... 35 147 65 ,, p-Xylenesulphonic acid.. .......... 48 149 55 ,, p-Chlorobenzenesulphonic acid.. .68 148 60 ,, p-Bromobenzenesulphonic acid.. . 103 155 60 ,, T. M. L.ORGANIC CHEMISTRY. 75 up-Dichlorostyrenes and some Acetylenes. By FRANZ KUNCHELL and R. KORITZKY (Bev., 1900, 33, 3261-3264. Compare Abstr., 1 9 00, i, 6 3 8) .-aap-Dic~~loro-p-ethylstyrene, C,H,Et*CCl: CHCI, prepared by heating chloroacetyl-p-ethylbenzene with phosphorus pentachloride, is a colourless oil boiling at 265"; i t has a sp. gr. 1.2565 a t 17". p-Ethyll0henylchZoroacetyZene, C,H,Et*Ci CCI, obtained by boiling the preceding compound with alcoholic potassium hydroxide, is a yellow oil with an odour of oranges boiling a t 160-170" under 35 mm. pressure ; it has a sp. gr. 1.0871 a t 17". p-Ethylphenylacetylene, C,H,Et*CICH, readily produced by treating up-dichloro-p-ethylstyrene with sodium in ethereal solution, possesses an odour of anise, boils a t 110" under 10 mm.pressure and has a sp. gr. 0.9086 a t 18". p-Czcmyl chloromethyl ketone, which crystallises from alcohol in needles and melts a t 55-56", yields up-dichloyo-p-isopopylstyrene, colourless oil boiling at 190-ZOOc under 23 mm. pressure and having a sp. gr. 1.2736 a t 17". p-isoPropplphenylchloroacetylene, CHMe,-C6H,*C ICCl, a yellow oil boiling at 170-180" under 30 mm. pressure, has a sp. gr. 1,0852 a t 17". p-isoPropyZphenylacetyZene, a liquid having an ethereal odour, boils a t 110-120° under 10 mm. pressure and has a sp. gr. 0.9124 a t 17". ap-Dichloro-2 : 4 : 6-trimethyZstyrene7 C,H,Me,*CCl:CHCl, is a colourless oil boiling at 285-289' under atmospheric pressure ; i t has a sp.gr. 1.1998 at 17". 2 : 4 : 6-17rimethy~hertylchloroacetylene, C,K,Me,*CICCl, a pale yellow oil boiling at 180-190" under 20 mm. pressure, has a sp. gr. 1.0349 at 18". 2 : 4 : 6-~rimethylphenylacety~ne, C,H,Me,*CiCH, has an ethereal odour and boils a t 168-175' undm 20 mm. pressure; it hapa. sp. gr. OWi'31 at 17O. cymyl chkwomethyl ketone, CHMe,*C,H,Me*CO* CH,CI, crystallises fromalcoho1 in needles and melts a t 18-20". up-Dichloro-2 (or 5)-methyZ- 5 (or 2)-isopropylstyrene, CHMe,*C,~H,Me*CCl:CHCl, obtained from the preceding ketone, is a colourless 011 boiling at 268" under atmospheric pressure and having a sp. gr. 1.1296. 2 (or 5)-MethyL5 (or 2)-isopopyl- phenyZchEoroacetylene, CHMe,*C,H,Me*CICCl, a yellow oil, boils at 2 1 5 O under 40 mm. pressure and has a sp.gr. 1.0512 at 17". 2 (or 5)-Methyl- 5 (or 2)-isopropylphenyZacetykne, CHMe,*C,H,Me-CICH, boils a t 128-130" under 50 mm. pressure and has a sp. gr. 0.8882 at 174 The sodium derivatives of tbe above unchlorinated acetylene, obtained in ethereal solution, are very unstable substances, being de- composed even by rubbing on a porous tile; water converts them into the corresponding acetylene and sodium hydroxide. G. T. M, Some Chloromethoxystyrenes. By FRANZ KUNCKELL and K. ERAS (Ber., 1900, 33, 3264-3265. Compare preceding abstract).- a/3-DichZoro-pmethoxystyrene, OMe*C,H;CCl:CHCl, prepared from chloroacetylanisole and phosphorus pentachloride, is a colourless oil boiliaqg at 1 5 5 O under 12 mm. and at 268"mder atmospheric pressure ; it solidifies on cooling and has a sp.gr. 1.291 at 18". B~sdichlo~oethyleneanisole, OMe*C,H,(CCl: CHCl),, obtained from di-76 ABSTRACTS OF CHEMICAL PAPERS, chloroacetylanisole boils a t 160-170° under 17 mm. pressure and has a sp. gr. 1.460 at 21'. I n the case of these methoxystyrenes, the removal of hydrogen chloride by alcoholic potash takes place only in sealed tubes ; sodium fails to withdraw the halogen atoms even at the temperature of the water-bath. G. T. M. Condensation Products of Indene. By JOHANNES THIELE (Ber., 1900, 33, 3395-3401).-The so-called condensation product obtained by Marckwald (Abstr., 1895, i, 535) from indene and benz- aldehyde is shown to be the additive product hydroxybenzylbenzyl- ideneindene, C2,H1,0, and Marckwald's acetate, produced by the action of acetyl chloride, is its chloro derivative, C2,H17C1, which with moist silver oxide yields the hydroxy-compound, and when reduced with zinc dust and acetic acid yields a colotirless, crystalline compound, (C2,H,&, which melts a t 212-213', and is probably a polymeride of benzyl- benzylideneindene.Benxylideneindene, CH<3g>C:CHPh, ob- tained in small quantities by the condensation of benzaldehyde and indene in the presence of alcoholic potash, crystallises in yellow leaflets, melts at 88O, and with concentrated sulphuric acid gives a yellowish-green coloration. Indene and cinnamaldehyde condense readily in the presence of alcoholic potash, with the formation of cin- namylidensindene, CH<Eg:>C:OH*CH:CHPh, which crystnllises in yellowish-red needles, muel& a t 190°, and gives a brown coloration with concentrated sulphuric acid, and an additive compound, C2?H@, which is analogous to hydroxybenzylbenzylideneindene, crystallises in slender, yellow needles, melts a t 160-161°, and gives a green cdora- tion with sulphuric acid.Ethyl indeneoxnlate and p-nitrobenzoyl chloride condense in acetone solution in the presence of pyridine, -I forming ethyl p-nityobenxoylindeneoxalate, which is a yellow, crystalline compound melting 2 113--114" ; the corresponding benxoyl compound is a red oil. Indeneoxalic acid, ob- tained by the careful hydrolysis of the condensation product of ethyl oxalate and indene, crystallises in small, lustrous, red prisms and melts and decomposes at 153-154'. R. H. P. The Phenanthrene Series : Action of Nitrous Acid on Phen- anthrene.By JULIUS SCHMIDT (Bey., 1900, 33, 3251-3260)- Nitrodihydrophenanthrene oxide, O(C,,H1,,*N02)2, obtained in colourless, cubical crystals by saturating a benzene solution of phenanthrene with the fumes evolved from arsenious oxide and nitric acid, melts at 154-155'; it is extremely insoluble in the organic solvents, and, when recrystallised from benzene, separates in transparent prisms containing 1 mol. of benzene and melting a t 134-135'. The sub- stance gives the Liebermann reaction for nitroso-compounds, and on freatment with sodium methoxide yields a nitrophenanthrene meltingORGANIC CHEMISTRY. 77 at 116-11 To, which is not identical with the mononitro-derivatives obtained by the direct nitration of the hydrocarbon.Bismortonitrodih~drop~enanthrene, NO2* C14Hlo Ci4HlO *NO,, which separates from the benzene mother liquor in the preceding experiment, consist’s of small needles melting a t 199-200°, and crystallises from alcohol in pyramidal prisms; it also gives the Liebermann reaction, and develops a brownish-green coloration with cold concentrated sul- phuric acid, which becomes deep green on warming, and changes to yellowish-brown on the addition of alkali. Nononitrobbphenanthran (mononitrobisdi~ydrophenanth?.yZene~, C,4H1~: C1,Hg*N02, produced by heating the preceding compound for 10 minutes a t 200-205*, crystallises from benzene in lustrous, yellow prisms and melts at 210-212°. The author proposes to employ the term “phen- anthran ” for the bivalent radicle, C14H19, derived from dihydrophen- anthrene, and the preceding compound is named in accordance with this nomenclature.Dinitrobisphenant~~ran, N02*C14Hg:C, ,H,*N02, results from the action of sodium ethoxide on bismononitrodihydrophenanthrene ; i t slowly decomposes at 300’ and has not been obtained crystalline owing t o its insolubility in the ordinary solvents. By MOSES GOMBERG (Bw., 1900, 33, 3144-3149 ; J. Amer. Chem. Xoc., 1900,22, 752-757. Compare E. and 0. Fischer, Abstr., 1879, 384).-The triphenylmethane obtained by so many authorities by the action of benzene on carbon tetrachloride in the presence of aluminium chloride is due to a second- ary decomposition of the triphenylchloromethane, which is the first product formed. A 70-87 per cent. yield of the latter may be ob- tained by heating together carbon tetrachloride, benzene, and alumin- ium chloride, and a t the end of the reaction running the well cooled mixture on to a large quantity of powdered ice contained in a vessel surrounded by a good freezing mixture.For a good yield, it is essential that the original substances should be thoroughly dry, and that the product should never be left in con- tact with water for any length of time. Triphenylmethyl. An hstance of Tervalent Carbon. By Moms GOMBERU (Ber., 1900, 33, 3150-3163 ; J. Anzer. Chem. Xoc., 1900, 22, 757-771).-Triphenyl-bromo- or -chloro-methane is not acted on by metallic sodium, but zinc, mercury, or ‘‘ molecular ” silver remove the bromine or chlorine and, in the absence of air the unsaturated hydro- carbon triphenylmethyl, CPh,, is quantitatively formed, but when air is not completely excluded, a considerable amount of triphenylmethyl peroxide, CPh,*O*O*CPh,, is produced.The author recommends the action of pure powdered zinc on a benz- ene solution of the chloro-compound, the operation being conducted in an apparatus free from rubber or cork connections. When the benz- ene solution is concentrated at 30-35’ in an atmosphere of dry car- bon dioxide, a solid residue of the unsaturated hydrocarbon is left ; it does not melt at 60°, dissolves readily in benzene or carbon disulphide, and when a solution is kept for several weeks large, transparent crystals G. T. M. Preparation- of Triphenylchloromethane. J. J. s. VOL. LXXX. i, 978 ABSTRACTS OF CHEMICAL PAPERS.are deposited ; it has not been found possible to obtain these in a pure form, as they rapidly absorb oxygen. Triphenylmethyl peroxide is readily produced when the hydrocarbon is left exposed t o the atmosphere, when air is aspirated through a benz- ene solution of the hydrocarbon, or when the benzene solution is treated with an aqueous solutionof sodium peroxide. It is only spar- inglysoluble intheusual solvents, but may be crystallisedfromchloroform or carbon disulphidein the form of six-sided plates melting a t 185-1 8 6 O ; it is stable in the air but slowly decomposes when its solutions are boiled, When dissolved in cold concentrated sulphuric acid, it gives a yellow solution which quickly darkens, and on dilution triphenylcarbinol is precipitated. When nitrated, it yields Izexanitrotrip~e~~ylmethyl peroxide, O,[C(C,H,*NO,),],, melting a t 2 10' and sparingly soluble in most solvents.Triphenyliodomethccne, CPh,I, is readily obtained when a carbon disulphide solution of the unsaturated hydrocarbon is treated at O0 with a solution of iodine in the same solvent, and is best isolated in an atmosphere of dry carbon dioxide. It is unstable, readily darkens and loses iodine, melts at about 1 3 5 O , and by water, especially in t,he presence of alkalis, is transformed into the carbinol ; boiling with alcohol converts it into triphenylmethane. The corresponding brorno- and chloro-compounds cannot be obtained by a similar process as bromine and chlorine form substitution as well as additive products. J. J. 8. Action of Ethyl Acetonedicarboxylate on Aniline.By EMIL BESTHORN and E. GARBEN (Ber., 1900, 33, 3439--3447).-Ethyl- p-arzilinogl~taconc~te, CO,Et*CH,* C(NHPh):CH*CO,Et, prepared by the interaction of aniline and ethyl acetonedicarboxylate a t the ordinary temperature, crystallises from methyl alcohol in transparent crystals melting at S7", bnt melts at 97-98' when crystallised several times from dry ether; the variation in melting point is explained by the supposition that two isomerides are produced ; the ester is insoluble in water but soluble in organic solvents, .gives a yellowish-brown coloration with aqueous alcoholic ferric chloride, and is hydrolysed by cold dilute mineral acids. Three products are formed when ethyl acetonedicarboxylate is heated with aniline in a sealed tube a t 100'.Acetonedicccrboxydianilide, CO(CH,* CO-NHPh),, crgstallises from absolute alcohol in small, colourless needles, melts, evolving gas, at 155', gives a violet coloration with ferric chloride, and dissolves without decomposition in cold dilute sodium carbonate ; concentrated sulphuric arid gives sulphanilic acid, but the anilide condenses in presence of 80 per cent. acid on the water-bath to 2-quinolone-4-acetic acid. The monoanilide of ethyl P-anilinoghtaconate, NHPh*CO*CH,*C(NHPh): CH* CO,E t, sepzrates from methyl alcohol in well-formed crystals, and when crystallised from dry ether melts a t 129-130'; with ferric chloride, it gives a yellowish colour, rapidly passing to violet as the compound is hydrolysed by the acid of the ferric chloride. The monoanilide of ethyl acetonedicarboxylte, NHPh*CO*CH,*CO*CH,*CO,Et, which is best prepared by the action of cold dilute hydrochloric acid on the preceding compound, crystallises from dry ether, melts at 75-76", dissolvesORCfAh'IC CHEMISTRY, 79 slightly in hot water and separates on cooling in minute felted needles; it dissolves unchanged in cold dilute sodium hydroxide, and can be reprecipitated a t first by carbon dioxide, but hydrolysis of the ester gradually takes place ; it is converted into 2-quinolone-4-acetic acid by warming with concentrated sulphuric acid during 2 hours on the water-bath, NH*C H CO-CH 2-&wino~one-4-ncetic acid, I ' '>C*CH,* CO,H, is only slightly soluble in water and organic solvents, crystallises from hot water in white, felted needles, melts, evolving gas, at 205-206') and by further heating is converted completely into lepidone and carbon dioxide.The ethyl ester, CI3Hl3O3N, crgstallises from benzene in colourless, flat needles, melts at 172--173", and forms soluble crystal- line salts with mineral acids. By W. GROTHE (Arch. Phai*m., 1900, 238, 587-600).-ChIoroncetyl derivat ives of amines, NHR*CO*CH2C1, were prepared by mixing chloroacetic acid with the amine and cooling well, after which the product was mixed with excess of phosphoric oxide. I n the case of rnethylaniline, chloroacetyl chloride was adiied to the well-cooled amine; indeed, this method is preferable in all cases for work on any but quite a small scale. There were prepared (the temperatures given are melting points) : the chloroacetyl derivatives of aniline ; 0- and p-toluidine ; 1 : 3 : 4-xylidine, 109' ; 1 : 2 : Ei-xylidine, 153' ; p-phenetidine, 148' ; methylaniline, 70'.These chloroacetyl derivatives form sulphonacetyl compounds, NHR*CO*CH,*SO,*R, when boiled with sodium benzene- or p-toluene- sulphinate in alcoholic solution, When these compounds are boiled with 10 per cent. alcoholic potash, they are hydrolysed in all cases to the amine, NH,R, carbon dioxide, and a sulphone, CH,*SO,*R. Those prepared are : the phenylsulphonacetyl and p-tolylsuZphonacetyI derivatives of aniline, 142' and 168' respectively ; o-tohidine, 150' and 129O ; p-tohidine, 153O and 157' ; 1 : 3 : 4-xylidine, 141Oand 153-154' ; I : 2 : 5-xylidine, 143' and 160' ; p-phenetidine,,151° and 156' ; methyl- aniline, 125' and 11 2'.Action of Potassium Hydrosulphide, Potassium Cyanide, and Potassium Thiocyanate on Chloroacetanilides. By W, GROTHE (Arch. Phcurm., 1900,238,600-614).-When potassium hydro- sulphide is added gradually to a chloroacetanilide, NHR*CO* CH,CI, both in alcoholic solution, a dianilide of thiodiglycollic acid, (NHR*CO*CH,),S, is obtained. I n this way were prepared (the num- bers given are melting points) : thiodiglycollgl derivatives of aniline ; o-toluidine, 190' ; p-toluidine, 194' ; 1 : 3 : 4-xylidine,^ 194' ; 1 : 2 : 5-syl- idine, 210' ; .p-phenetidine, 221' ; methylaniline, 115'. By oxidation with potassium permnnganate in acetic acid solution, fhese derivatives can be converted into sulphones, (NHR*CO*CH2),S02 ; the yield is not always good, however.There were prepared : sulphono- diacetyl derivatives of aniline, 220-225' ; o-toluidine, 225-226' ; p-tohidine, 221' ; 1 : 2 : 5-xylidine, 237' ; p-phenetidine, 239' ; methyl- aniline, 152'; from 1 : 3 : 4-xylidine the corresponding derivative could not be obtained. T. M. L. Anilides of Alkylsulphonacetic Acids. C . F. B. 9 280 ABSTRACTS OF CHEMICAL PAPERS, By mixing the chloroacetanilides with potassium cyanide in aqueous alcoholic solution, cyanoacetanilides, NHR*CO*CH,*CN, can be ob- tained in some cases. There were prepared : cyanolccetyl derivatives of aniline ;. p-toluidine, 180' ; 1 : 2 : 5-xylidine, 167O; methylaniline; the corresponding derivatives of o-tolnidine, 1 : 3 : 4-xylidine) and p-phenet- idine could not be obtained.When these derivatives are heated with hydrochloric or sulphuric acid, they are hydrolysed to the amine, BH2R, carbon dioxide, acetic acid, and ammonia. When chloroacetanilides are heated with potassium thiocyanate in alcoholic solution, they form thiocyanoacetanilides, NHR*CO*CH,*SCN. There were prepared : thiocyanoacetyl deriva- tives of aniline, 86-87'; o-toluidine, 102-103°; p-toluidine, 125-126O; 1 : 3 : 4-xylidine, 102' ; 1 : 2 : 5-xyZidine, 133' ; p-phenetidine, 164-1 65'; methylaniline, 69'. C. F. B. Action of Potassium Thiocyanate on Chloroacetanilides. By GUSTAV FRERJCHS and HEINRICH BECKURTS (Arch. Pharm., 1900, 238, 615-616).-The thiocyanoacetyl compounds prepared by Grothe (preceding abstract) are derived from thiocyanoacetic acid, with the ex- ception of the methylanilide, which is derived from thiocarbiminoacetie acid.The products obtained from other secondary amines, for instance ethylaniline, are also thiocarbimino-derivatives. Compounds of prim- ary amines with thiocarbiminoacetic acid, on the other hand, are very unstable. I n one case, that of thiocnrbiminoacetyl-p-tozuidide, the compound could be prepared by allowing potassium thiocyanate to act on chloroacetyl-p-toluidide in alcoholic solution for a very short time only; if the solution is heated, this compound is transformed into thiocyanoacetyl-p-toluidide, which finally can be converted into p-tolyl- thiohydantoin. C. F. B. Some Reactions of Substituted Anilines. By WILLIAM OECHSNER DE CONINCK (Compt. rend,, 1900, 131, 945-946).-1n this paper, a minute description is given of the various colour changes and precipitates produced when solutions of methy laniline, dimethylaniline, ethylaniline, and diethylaniline in 97 per cent, alcohol are mixed with dilute or concentrated solutions of cupric chloride, sulphate, or acetate, and also, in the case of methylaniline, with solutions of cobalt or nickel chloride.N. L. Trinitrothymol and its Derivatives. By GUIDO MALDOTTI (Gazxetta, 1900, 30, ii, 365-370J.-Trinitrothymol, prepared by Lallemand (Ann. Chirn. Phys., 1857, [iii], 49, 150), has the normal molecular weight in freezing phenol. The following derivatives have been prepared. The benmyl compound, OISz*C6MePr(N02),, separates from alcohol in silky, pale yellow needles melting at 140' and boiling and decomposing at 250'; it dissolves slightly in water or light petroleum, and is very soluble in benzene, in which its cryoscopic behaviour is normal. The acetyt? derivative crystallises from benzene i u pale yellow scales or plates melting at 135'; it dissolves slightly in ether, more readily in light petroleum, and gives the normal molecular weight in benzene.The ethyl derivative is deposited from alcohol in rhomboidal, nacreous scales or rectangular prisms whichORGANIC CHEMISTRY. 81 melt at 75"; it is soluble in banzene, to which it gives the normal depression of Freezing point. The phenylhydraxine salt separates from alcohol in orange-yellow needles decomposing at 145" ; it behaves normally in freezing phenol solution. T. H. P. By JULIUS SCHMIDT (Beg-., 1900, 33, 32444246, Compare this vol., i, 89).-2 : 4- Dinitro-a-naphthol is produced when an ethereal solution of a-naphthol is saturated with the pas evolved from arsenious oxide and nitric acid ; Action of Nitrous Acid on a- and P-Naphthols. &naphthol, when sirnirarly treated, yields the dinitro-/3-naphthol melting at 195O.G. T. M. Addition of Aldehydoaminic Bases to Naphthols. By MARIO BETTI [with CESARE SPERONI] (Gaxxetta, 1900, 30, ii, 301--309).-The naphthols resemble the enolic form of ethyl acetoacetate in containing the grouping *CH:C(OH)* in their molecules; and further, they give, with aldehydoaminic bases, additive compounds similar to those ob- tained with ethyl acetoacetate. BenxyZidenec~niZ-,9-naphthoZ, NHPh*CHPh*C,,H,*OH, prepared from benzylideneaniline and /I-naph thol, crystallises from alcohol in aggre- gates of lustrous, white needles which melt at 170° and are soluble in benzene; it is readily decomposed by cold dilute acid but is stable towards alkali hydroxides, The presence of a drop of piperidine seems t o greatly accelerate its formation.m-NitrobenxyZidenean~~~-napht~oZ, N0,*C6~~oCH(NHPh)*Cl,H,*OH, separates from a mixture of benzene and light petroleum as a yeilowish- white, crystalline powder melting at 152O. Benxylidene-P-naphth yZc6mine-P~n~phthoZ,C,,H~* NH.0 HP h* C,,H6* OH, separates from alcohol as a white, crystalline powder which melts at 175" and is slightly reddened by the action of light. BenxyZideneaniEa-nap~t~oZ, C,,Hl,ON, is deposited by the addition of light petroleum t a its benzene solution in white crystals melting at 142' to an orange-yellow liquid.These compounds are insoluble in water and their alcoholic solu- tions give no coloration with aqueous ferric chloride, but in benzene solution they give a reddish-violet colour with absolute ethereal ferric chloride solution. On mixing benzene solutions of benzylideneaniline and picric acid, yellow needles of benxylideneaniline picrate, Cl9HI4O7N4, melting a t 173' are obtained. Condensation between @Naphthol, Aldehydes, and Amines. By MARIO BETTI (Gaxxetta, 1900, 30, ii, 3 10 -3 16)-Under suitable conditions, P-naphthol condenses with an aldehyde (2 mols.) and a primary amine (1 mol.) with elimination of 2H,O. The substances obtained in this way crystallise well, have a high melting point, can be boiled with 25 per cent.potassium hydroxide solution without undergoing change, whilst prolonged boiling with hydrochloric acid yields the aldehyde employed ; they are probably oxyazine derivatives. No condensation occurs if the P-naphthol is replaced by phenol or by diethyl malonate ; secondary amines cannot replace the primary nor can acetone be used instead of an aldehyde. T. H. P.82 ABSTRACTS OF CHEMICAL PAPERS. P-Naphthol, benzaldehgde, and ammonia yield i n almost theoretical quantity a compound, C,,H,,ON, crys tallising from alcohol in white needles which melt at 150' and are soluble in benzene; ethereal ferric chloride gives an intense reddish-violet coloration with the benzene solution. Fusion with potassium hydroxide yields ammonia, whilst long boiling with hydrochloric acid gives benzaldehyde and a substance separating in white needles. The ucetpl derivative of the condensation product is deposited from alcohol in lustrous, white crystals melting a t 188-189°, and in benzene solution gives no coloration with ferric chloride.P-Naphthol, benzaldehyde, and aniline yield a compound, C,oH,,ON, which is readily soluble irt benzene or chloroform, and separates from amyl alcohol in rosettes of small, white needles which begin to turn yellow at 160°, become orange-coloured a t 185' and melt a t 200'. From P-naphthol, furfuraldehyde, and ammonia, a compound, C20H,,0,N, is obtained, which separates from alcohol in mammillary tufts of long, white needles melting at 115' ; in benzene solution, it gives an intense violet coloration with ethereal ferric chloride.@-Naphthol, valeraldehyde, m d ammonia yield a compownd, C,,H,,ON, crystallising from alcohol in tufts of long, lustrous white needles melting at 92'; its benzene solution gives an intense violet coloration with ethereal ferric chloride. T. H. P. Etheriflcation of Triphenylcarbinols by Alcohols. By OTTO FISCHER (Bey,, 1900, 33, 3356-3357).-0n dissolving the malachite- green base in boiling methyl alcohol, the methyl ether, C2,H2,0K2, sepa- rates inwhite leafletswhich rapidly become green, and melt a t 150-151'; if the ether is dried rapidly over alkali, it does not subsequently become coloured. Acids, even acetic acid, remove the methoxyl group and yield salts of malachite-green, The corresponding ethyl ether, obtained a t a temperature of 80-1 TO0, forms concentrically grouped, colourless leaflets and melts at 162O ; the benxyl ether is obtained only a t tern peratures above 140-150°, and forms white, silky needles, which when dried over alkali, retain their colour.I t softens a t 195', melts at 19So, is coloured green by acids, and is decomposed by dilute sul- phuric acid at looo into benzyl alcohol and the sulphate of the mala- chite-green base. W. A. D. By H. COUSIN (Compt. rend., 1900, 131, 901-903).-When tribromoguaiacol, OH*C,HBr,*OMe, is oxidised with nitric acid in presence of acetic acid and some alcohol, it yields a compound, C,,H,O,Br,, which forms orange- red, flattened needles, melts a t 186-18S0, and is insoluble in water, but dissolves readily in organic solvents.When treated with reduc- ing agents, it yields a colourless compound, C,,H,O,Br,, which forms prismatic crystals melting at 170-1 72'. With ferric chloride, its alcoholic solution gives a green coloration which changes to violet on addition of a trace of sodium carbonate. Both compounds yield diphenyl when treated with zinc dust. The red compound is a Action of Nitric Acid on Tribrornoguaiacol. - - quinone which probably has the constitution oH*%HBr2*?, whilst OH*C,HBr,*OORGANIC CHEMISTRY. 83 the colourless compound is the corresponding quinol. The action of nitric acid on tribromoguaiacol is similar to, but not identical with, its action on trichloroguaiacol (Abstr., 1900, i, 487). C. H. B. Anildiacetic-o-carboxylic Acid. By DANIEL VORLLNDER and E.MUMME (Bey., 1900, 33, 3182-3183).-AniZdiacetic-o-car60xyZic ncid (diaceticanthrccnilic ncicl), C02H*C,H4*N(CH,*C0,H),, is obtained when anthranilic acid and excess of chloroacetic acid interact in neutral or alkaline solution, It crystallises from hot water in colourless tablets or leaflets and melts and decomposes at 212'. Its conductivity shows it to be powerfully acidic, but it cannot be titrated as a tribasic acid. It is not acted on by nitrous acid and its alcoholic solution is not coloured by ferric chloride. Unlike phenylglycinecarboxylic acid, it is readily esterified and with alcohol and sulphuric acid is converted into its trimethyl ester, CI1H8O6NMe3, melting a t 62". When the acid is heated with alkali hydroxides, it condenses to an indoxyl derivative which is oxidised by ferric chloride and strong hydrochloric acid to an indigotin-like dye, possibly C02H*CH2*~648==C_N*CH20 C0,H' The trimethyl ester, on treatment with sodium ethoxide, is converted into the methyl ester of an indoxylacetic acid, possibly 7 H *CO QO*Y6H4 OH*? ==? *CO,Me C,H,*N*CH,*CO,H' This is a well-crystallised substance and melts at 163O.Esters of Acylphenylglycine-o-carboxylic Acids. By DANIEL VOR- LBNDER~~~W.MEUSEL(B~?*., 1900,33,3183-3185).-1t hasbeen shown by Vorlander and Weissbrenner (Abstr., 1900, i, 295) that the acetyl derivatives of phenylglycinecarboxylic acid are readily converted by acidsoralkalis into indigotin. It was presumed that these esters might be A. L. - - derivatives of the type C , H 4 ~ $ ? ~ # $ ~ ~ C H * C 0 , R , the conversion of which into indigotin derivative; woufd be readily understood.Di- ethyl acetylphenylglycinecarboxylate may be prepared by the following different processes : 1, esterification of acetylphenylglycinecarboxylic acid ; 2, acetylation of the esters of phenylglycinecarboxylic acid ; and 3, action of ethyl iodide on silver acetylphenylglycinecarboxylate. Xoreover, the isomeric monoethyl esters, C,,H,,O,N, of acetylphenyl- glycinecarboxylic acid have been prepared ; that obtained by partial hydrolysis of the diethyl ester melts at 130--132O, and that by partial esterification of the acid a t 86-87O. These are not convertedinto indigo by dilute alkali and possess the normal constitutions, C02Et*C,H4*NAc*CH,*C0,H and C0,H*C,H4*NAc*CH2*C02Et. The authors have finally proved that it is possible to detect indoxyl derivatives by means of warm 60 per cent.sulphuric acid, which con- verts them into indigotinsulphonic acids. The authors draw the conclusion- that the diethyl esters referred to are true derivatives of acetylphenylglycinecarboxylic acid and that their conversion into indigotin is preceded by intramolecular change into i ndox y 1 derivatives. A. L.84 ABSTRACTS OF CHEMICAL PAPERS. Action of Air and Water on P-Benzylhydroxylamine. By EUGEN BAMBERGER and BOGDAN SZOLAYSKI (Ber., 1900,:33,3193-3201. Compare Abstr., 1900, i, 531).-When pure air is passed through /I-benzylhydroxylamine suspended in water for several months, it is converted into a dense, viscid oil, which finally becomes semi- solid.The product contains benzaldoxime, benzaldehyde, and benzoic . I - C HPh acid, benzglisobenzaldioxime, O<keCHOph, benzaldoxime anhydride, C,,H1,ON,, a neutral substance melt& at 21 2-21 3', benzylidene- benzhydrazide, CHPh:N-NH*COPh, dibenzoylhydrazine, C,,H1,O,N,. Bisnitrosobenzyl and azoxybenzyl could not be detected. As in the case of the oxidation of arylhydroxylamines, hydrogen peroxide is pro- duced in considerable quantities. The neutral substance above men- tioned crystallises in white, silky, felted needles, is very sparingly soluble in alcohol, and is indiEerent towards bases and acids; its nature has not yet been ascertained. Nitrosulphosalicylic Acids. By ROBERT HIRSCH (Ber., 1900,33, 3238-3241).-Sulphosalicylic acid (Mendius, Annalen, 1857,103, 45), prepared by the action of sulphuric acid on salicylic acid at looo, can be salted out from its solution, and can be crystallised from a concen- trated salt solution or from a little hot water.Contrary to Remsen's statement (Abstr., 1874, 1167 ; 1876, i, 594), the acid appears to be homogeneous, ncd only one potassium salt could be isolated. The nitration of salicylic acid (Hubner, Abstr., 1876, i, 593; 18'79, 380) can be carried out smoothly by dissolving in sulphuric acid and adding a mixture of nitric and sulphuric acids until no marked rise of tem- perature occurs on mixing, the temperature being kept below 10'. A nitvosuZjAosaZicyZic acid can be prepared by nitrating sulphosalicylic acid at 30-40° by the method just described. The barium salt, A.L. CO OH* C,H,( N0,)<s0,2>Ba, crystallises from hot water in yellowish- red needles, and is aimost insoluble in cold water. Hydroxyphenylcinnamic Acid. By MARUSSIA BAKUNIN (Gaaxetta, 1900, 30, ii, 370-377).-The hydroxyphenylcinnamic acid melting at 120" prepared by Vandevelde (Abstr., 1898, i, 670) by the interaction of sodium hydroxyphenylacetate, benzaldehyde, and acetic anhydride is a mixture of cinnamic acid and the hydroxyphenyl- cinnamic acid melting a t 181' obtained by Oglialoro (Abstr., 1881, 276). Thephenyh ester melts a t 1 0 7 O , and not, as stated by Vande- velde, at 74', which is the melting point of phenyl cinnamate. T. M. L. T. H. P. Addition of Hetomethane Derivatives to Unsaturated Com- pounds. By DANIEL VORLANDER (Ber., 1900, 33, 31 85-3187).-1t is often observed that ethyl sodiomalonate will unite with ap-un- saturated ketones when benzene or ether is used as the diluent, but not if alcohol is used.The explanation of this appears to be that the reaction is a reversible one, and that the reverse change is slower i n the non-hydroxylic solvents. Thus, whilst ethyl pulegonemalonate may be prepared by heatingORGANIC CHEMISTRY 85 pulegone with ethyl sodiomalonate dissolved in benzene or ether, it is broken up into these constituents when heated with an alcoholic solu- tion of sodium ethoxide. I n a similar manner, ethyl benzylidenebis- benzoylacetate is converted by alcoholic sodium ethoxide into ethyl benzoylacetate and ethyl benzylidenebenzoylacetate (compare also Dieckmann, Abstr., 1900, i, 623).A Saturated Dicyclic Dicarboxylic Acid. By WILHELM BRAREN and EDUARD BUCHNER (Ber., 1900, 33, 3453-3456).--Ethyl A'-tetm- hydrobenxoate prepared from the corresponding acid (Aschan Abstr., 1891, 1481 ; 1893, i, 33) is an oil boiling at 206-208O, which, when heated with ethyl diazoacetate at 110-120° for 16-24 hours or until all the diazoacetate has disappeared, yields ethyl 1 : 2-norcarandicarb- >CH*CO,Et ; this, after purification by dis- oxylate, tillation in steam, forms an oil boiling a t 159-160° under 18 mm pres- sure ; on hydrolysis with alcoholic potash, it yields cis-1 : 2-norcavandi- carboxylic acid, C7H19(C0,H),, together with a n oily mass ; the cis-acid melts at 152-15309 is readily soluble in water, alcohol or ether, and is not acted on by cold permanganate in alkaline solution.When boiled for l & hours with acetyl chloride, it yields the anhydride, C,H,,:C,P,, which crystallises from cirbon disulphide in colourless plates melting at 86-87O; when this is dissolved in sodium hydroxide solution and then acidified, it yields the original acid, and hence follows the cis- configuration of the latter. Euxanthic Acid. By CARL GRAEBE (Ber., 1900,33,3360-3362).- Although the potassium and sodium salts of euxanthic acid are of the type C~gHl~OllM, the silver salt, precipitated from the potassium salt by silver nitrate, has the composition C,,H,,O,,Ag, derived from an anhydride of the acid; the methyl estey melting at 2 1 2 O , and the ethyl ester, melting at 19S0, prepared from the silver s i l t are of a similar type, C,,Hl,Ol,*R.These esters, but not the free acid, combine directly with iodine (apparently 2 atoms at most) to form gelatinous, insoluble blue substances. With acetic anhydride, the esters yield colourless acetyl derivatives, derived not from the esters themselves, but from the anhydride, C,,H,,O,,; their composition remains to be determined. With benzoyl chloride, analogous substances are formed, A. L. QH2* CH, QH-- CH,*C H,* c( C 0,E t) J. J. S. the ultimate product beini the compound C19H11010B~5. W. A. D. Lichens and their Characteristic Constituenta. By OSWALD HESSE (J. pr. Chem., 1900, [ii], 62, 321-363. Compare Abstr., 1898, i, 531, 6 7 9 ; 1899, i, 38l).-Specimens of usnic acid obtained from Usnecc ceratina, Cladonia rangifera var. silvatica, Parrnelia caprata and Placodium saxicolum var.vulgare gave [ + 494*1°, + 494*6O, i- 492*2', and + 492.7' respectively, whilst that from Cetraria pinastri gave [uID - 494.1'. When either d- or Z-usnic acid is melted, it is instantly converted into the inactive modi6cation. The d-acid melts at 195-197', the Z-acid at 1 9 7 O , and the inactive form at 192-193'. The potassium salts of the d- and Z-acids crystallise from water with 3H,O, and from alcohol with 1H,O. The inactive modifications86 ABSTRACTS OF CHEMICAL PAPERS. obtained by fusion of the d- and Z-acid respectively and that crystallised from a mixture of the two active forms are not absolutely identical, since the potassium salt crystallises in a different form in each case; the sodium salt, however, crystallises only in one form (compare Widman, Abstr., 1900, i, 235).Ebullioscopic determination of the molecular weight of the substance obtained by the action of acetic anhydride on cl-usnic acid (Hesse, Abstr., 1895, i, 298) gave 338-339, whilst a substance of the formula (C1sH1506)2.0 requires 670 ; the author concludes that the supposed anhydride is a mixture of the lactone, C,,H,,O,, and the d-acid. A further examination of ~ccndekaricc concolor has shown that the ' dipulvic acid ' previously described consists of pulvic anhy- dride together with a smaller quantity of calycin (compare Zopf, Abstr., 1899, i, 716). CandeZaria vitellina obtained from four different sources furnished a substance composed of calycin and pulvic anhydride in varying proportions.Sticta aurata yields stictaurin,' C,,H, 20, which has the properties attributed to it by Zopf (kc. cit.). Stictch Desfontccinii a-munda contains a substance melting at 232O which, when boiled with alcohol, furnishes calycin and ethylpulvic acid. If calycin (1 mol.) and pulvic anhydride (2 mols.) are dissolved in hot glacial acetic acid, a substance, C,,H,,O,,( CX8H1004)2, separates which corresponds in every way with that obtained from Sticta auvatcc and crystallised from the same solvent ; in one case, a substance, ClsHI2O5, was produced resembling that obtained directly from Sticta ccurata by extraction with ether. From a solution of calycin and pulvic anhy- dride in molecular proportion, a substance is obtained in brick-red needles which melts at 216--217°, and agrees in its characters with that yielded by Candelaria vitellina.If, however, more than 1 mol. of calycin is mixed with 1 mol. of pulvic anhydride, the excess bf the former crystallises independently. The author concludes that the colouring mat€er of these lichens is not a definite single substance, but a mixture of calycin and pulvic anhydride in varying proportions, and that the calycin protects the anhydride from alteration. Oalycium chlorellum (C. chlorinum), yields vulpic acid and traces of leprarin. CaZyciumJEavum contains chrysocetraric acid and calycin. When Acolizcm tigilkaw is extracted with ether, and the ethereal solution shaken with aqueous potassium hydrogen carbonate, the potassium salt of acolic acid separates, whilst rhizocarpic acid remains in solution.Acolic acid crystallises in small, white needles, melts and evolves gas at 176q and is fairly soluble in alcohol, benzene, or chloro- form when hot, but only sparingly at the ordinary temperature. The ammonium, p!tassium, and 6arium salts are described. The investigation of the constituents of Cetraria islandica has been continued ; the sample examined consisted chiefly of var. vulgaris and pbtyncc. Lichenostearic acid is found to be a mixture of three acids, which the author terms a-, p-, and y-lichenostearic acid. a-lichernosteccric acid, C18H3005, is a monobasic acid which crystallises in prisms or plates, melts at 122-123', gives LaJD + 2 7 * 9 O , and is soluble in benzene, chloroform, or hot glacial acetic acid ; its potass- ium, sodium, ammonium, barium, and silver salts are described.TheORGANIC CHEMISTRY. 87 methyl ester, obtained by the action of methyl iodide on the potassium salt, crystallises in colourless needles, melts at 50.5', and dissolves readily in alcohol or ether. The ethyl ester forms long, radiating crystals, melts at 29-30', and is easily soluble in ether or alcohol. When a-lichenostearic acid is heated with aqueous barium hydroxide, i t loses carbon dioxide and is converted into lichestrone, C17H30039 the lactone of lichestronic acid ; lichestrone crystallises in white, lustrous plates, melts at 83-84', is optically inactive, and dissolves readily in alcohol, ether, acetone, chloroform, benzene, or glacial acetic acid. It dissolves slowly in solution of potassium hydrogen carbonate, with formation of lichestronic acid; this change takes place more rapidly if potassium carbonate or hydroxide is employed.Lichestronic acid, C17H,,0,, is monobasic ; it crystallises from dilute acetic acid in prisms or plates, melts at SO', is optically inactive, and dissolves very easily in alcohol, ether, benzene, or chloroform; its barium salt was prepared and analysed. P-Lichenostearic acid, C,,H,,O,, crystallises from acetic acid in leaflets, melts a t 12l0, gives [.I1, +27*9', and by the action of baryta is converted into lichestrone ; its sodium, ummonium, and barium salts are described. a- and P-Lichenostearic acids are readily distinguished by means of their ammonium salts; the ammonium salt of the former acid is sparingly soluble in cold water, whilst that of the latter acid is very easily soluble, and is precipitated in a gelatinous form on addi- tion of excess of ammonium chloride, y-lichenostearic mid, C1sH3005, or CI9Ha2O5, melts at 121-1 22O, and gives [ a ] , + 16.0' ; when its solution in benzene is heated, it is to a great extent polymerised.The ammonium salt is readily soluble in wator ; the barium salt is insoluble in water, whilst that of the P-acid is very easily soluble. Paralichenostearic acid, C,oH,,O, (Abstr., 1899, i, 386), melts at 182'. The foregoing acids are accompanied by smaller quantities of two other acids, The first of these has the composition Cl,H300,; w h y crystallised from alcohol, it melts at 140°, but if crystallised from glacial acetic acid, melts at 152'; its bn~ium salt was prepared and analysed.The second acid is dilichenostearic acid, C56HGoOlo, which melts a t 272', gives [ a ] , + 15*2', and is easily soluble in ether, amyl alcohol, or hot chloroform, and sparingly in benzene, light petroleum, or hot alcohol ; determination of the molecular weight by the boiling point method gave 659 (C,GH,oO11 requires 652) ; its sodium, ammonium, and barium salts are described. The author was unable to detect any phytosterol, or similar sub- stance, among the constituents of Cetravia iskundica. The licheno- stearic acid described by Sinnhold (Abstr., 1899, i, 13), is probably the a-acid, whilst his lichenosterylic acid appears to be lichestrone. E. G. Compounds from Lichens. VII. By WILEELM ZOPF (Annalen, 1900, 313, 317-344.Compare Abstr., 1899, i, 716).-Leparia Zate- brarum (Ach.) yields roccellic acid, atranoric acid, and leprarin, which melts at 155' ; methyl, ethyl, and propyl alcohols, under the influence of hydrochloric acid, convert leprarin into Zepravinin, melting at 135'88 ABSTRACTS OF CHEMICAL PAPERS. lepraridin, melting at 120-121°, and lepulin, melting at looo, re- spectively. Gyrophoru vellea and G. spodochroa (Ehrh.) var. depressa contain gyrophoric acid, which in the former lichen is associated with gyrophorin ; this crystallises from alcohol in minute, rhombic plates, and melts, evolving gas, a t 189'. Usnic acid has been identified in Ramalina thrausta (Ach.), Alectoria sarmentosa (Ach.), Cladonia deformis (L.), C. cyanipes (Sommerfelt), and Parmelia incurvcc (Pers.).Lecanora epnora (Ach.) contains zeorin and epccnorin, which crystallises from warm ether in lemon-yellow needles, and melts at 131-132O. Par- meZia Borreri (Turn.) yields lecanoric acid, and P. sorediata (Ach.) contains diff usin ; the greenish-yellow colour of Rhixocarpon viridi- atrum (FlGrke) is due to rhizocarpic acid. The author has isolated salazinic acid and picrolichenin from Pertusaria amara (compare Hesse, Abstr., 1899, i, 383), and corrects his former statement t o the effect that Physcia caesia (Hoffm.) contains haematomic acid. The compound in Evernia furfuracea (L), at first thought to be erythrin, is now recognised as a new substance, olivetoric acid, C,7H3608, which crystallises from 55 per cent. alcohol in long, silky needles, and melts at 141--142O; when heated with methyl alcohol in sealed tubes a t 150°, it yields oliwetorinic acid, which sinters at 65O, and melts at 88'.Disulphones. V. Acetophenone and Benzophenone Disul- phones. By THEODOR POSNER (Ber., 1900, 33, 3165-3168. Compare this vol., i, 14).-According to Baumann (Ber., 1886, 19,2S03) aromatic and aromatic-aliphatic ketones do not yield disulphones by conversion into mercaptoles and oxidation ; the author has, however, succeeded in obtaining disulphones from acetophenone and benzophenone. aa-Diethylthiol-a-phenylethane (cccetop?~enonernercaptole), CMePh(SE t)z, is readily formed when hydrogen chloride is passed into an acetic acid solution of acetophenone and ethyl mercaptan. It is an oily compound, and on oxidation yields aa-diethylsulphone-a-phenylethane(acetophen0ne- disulphone) melting a t 1 19-120° (corr.) ; this compound is identical with that described by Fromm (Annalen, 1889, 253, 135) as melting at 1OO-10lo.M. 0. F. Diethylsulphonediphenylmethane (benxophenonedisulphone), forms small, nodular crystals melting at 136-137' (corr.). Action of Nitrous Acid on Benzoquinone. By JULIUS SCHMIDT (Ber., 1900, 33,3246-3250).-Nitroanilic acid 6enxopuinons, OH*C,( N0,),:02:0,:C,€14, obtained by saturating a cooled ethereal solution of benzoquinone with the fumes evolved from nitric acid and arsenious oxide, crystallises in lustrous yellow prisms, and decomposes at 160° , it is readily soluble in acetone, ethyl acetate, or the alcohols, and dissolves only sparingly in chloroform, benzene, or toluene.An intense bluish-red coloration is developed on treating its alcoholic solution with ferric chloride. When dissolved in water, it dissociates into benzoquinone and nitroanilic acid ; alkalis decompose it, yielding the quinone and an alkali nitroanilate, sodium ethoxide in alcoholic solution giving rise to the sodium salt. A mixture of benzoquinone and liquid nitrogen trioxide after re- CPh,(SO,Et),, J. J. S.ORGANIC CHEMISTRY. 89 meining for 24 hours in a sealed tube at 12O, exploded with sufficient violence to completely shatter the wrought-iron sheath surrounding the experimental tube. 6-Acetylamino-1 : 2-naphthaquinone and the isoRosindulines obtained therefrom. By FRIEDRICH KEHRNANN and A. DENR (Bey., 1900, 33, 3295-3300).-5-Amino-2-naphthol interacts with acetic anhydride a t the ordinary temperature to form 5-acetylamino-2- naphthol, which crystallises from alcohol in greyish needles and melts a t 213-214'.On dissolving it in dilute aqueous sodium hydroxide, adding sodium nitrite, and acidifying, the nitroso-derivative, N HAc* C, oH,O: No OH, is obtained; this crystallises from water, gives a bright green sodium salt, and on reduction with stannous chloride in 20 per cent. hydro- chloric acid yields 5-acety~amino-~-arnino-2-n~6phtho~, which is readily oxidised by potassium dichromate and sulphuric acid to 5-acetgllamino- 1 : 2-naphthapuinome. This crystallises from chloroform in vermilion needles, melts a t 150-160°, is easily soluble in water, and condenses at the ordinary temperature with o-aminodiphenylamine to form principally isorosinduline No.9 (Kehrmann and Steiner, this vol., i, 101) along with a small quantity of the isomeride No. 12 (ibid., 100). W. A. D. Bromofenchone. By LUIGI BALEIANO (Gazxetta, 1900, 30, ii, 382-388).-Bromofenchone, G. T. M. CH,*CH- CHMe CH,*CBr- CHMe CH,*CBr--CO or I >CMe, I 9 CH,*CH- co 1 >CMe, I obtained in small yield by gradually adding the theoretical quantity of bromine to fenchone heated at 140-150°, is a pale yellow, oily liquid which has an aromatic, terpene-like odour and dissolves in most organic solvents; it boils undecomposed at 120' under 14 mm., and at 107' under 2 mm. pressure, has a sp. gr. 1-328 a t 15'115' and [a]= - 6.8O at 9'. On reduction in alcoholic solution with zinc and sulphuric acid, it yields fenchone, but when oxidised with various oxidising reagents no definite products other than carbon dioxide, oxalic acid, and resinous acids could be obtained. Terpenes and Ethereal Oils.By OTTO WALLACH (Annalen, 1900, 313, 345-370. Compare Abstr., 1896, i, 10l).-[With H. and E. LAUFFER.]-when purified phellandrene nitrite is treated with ammonia of sp. gr. 0.93, it is very slowly dissolved, nitrous oxide being evolved ; a white solid is produced which yields nitrophellandrene when heated with water, acids, or alkalis, a.nd this disagreement with the observations of Pesci (Abatr., 1886, 1038) is due to the fact that the material employed by that investigator was not purified sufficiently. Nitrophellandrene is also produced when phellandrene nitrite is added to acetic chloride.Oxidation with nitric acid converts phellandrene nitrite into a neutral compound containing nitrogen, along with terephthalic and isopropylsuccinic acids, and an acid isomeric with the last-named sub- stance. The compound, C7H,o0,N,, melts at 88-89', and gives Liebermann's reaction for nitroso-compounds ; the acid, C7HI2O4, melts 11'. H. P.90 ABSTRACTS OF CHEMICAL PAPERS. at 85-88'. isoPropylsuccinic acid is also produced when phellandrene nitrite is oxidised with potassium pe$manganate. The constitution of phellandrene is best represented by the formula QHPrP* CH,*CH CH:CH-CH [With H. LAUFFER.]-T~~ base, C,,H17*NH2, prepared by reducing terpinene nitrosite with sodium in alcohol, boils a t 209-210°, has a sp. gr. 0,8725, and n, 1.4717 at 20' ; the carbamide derivative melts at 1729 Oxidising the corresponding alcohol converts it into the ketone, of which the oxime melts a t 96-98'.p-Cymene is the non- basic reduction product of terpinene nitrosite. [With ALFRED ScHAFER.1-when a-phonic acid is prepared by oxidising oil of turpentine, a peculiar, camphor-li ke odour is noticeable on evaporating the liquid ; this is due to nopinone, the ketone obtained by oxidising nopic acid. [With WILHELM Ro JAH~.]-P~nocamphy~amine, C, ,H,y*NH,, pye- pared by reducing pinocamphoneoxime (Abstr., 1898, I, 486) with sodium in alcohol, is a liquid which rapidly absorbs carbon dioxide; the carbamide and acetyl derivatives melt at 204' and 120' respec- tively. Pinocamphonitrile (Zoc. cit.) boils a t 224--226O, and is hydro- Qsed to pinocumpholenic m i d , C,,H1,O,, which yields the amide melting at 1 1 6 O .Whilst nitrosopinene yields a mixture of pinylamine and pinocam- phone on reduction, the additive compound with bromine is converted into dihydrocarvone and dihydrocarvylamine. Camphene. By FRIEDRICH W. SEMMLER (Ber., 1900, 33, 342(5-3432).-Camphene is never oxidised to camphoric acid, and probably contains a nucleus different from those of pinene and of ' >CH,. M. 0. F. /CH,*CH,\ pinene hydrochloride. The formula CMe/-Cke23CH is sug- \C(:CH,)-/ , a, gested for camphene. Pinene dibromide is reduced to a dihydrocamphene identical with t h a t from pinene hydrochloride ; it therefore contains the same nucleus as the latter, and is the product of an isomeric change similar to that which takes place in the action of hydrogen chloride on pinene.Bromocamphene, for which the formula CMe-CMe, -CBr is \C(: CH,)--/ suggested, is reduced by sodium and alcohol to camphene, and there- fore contains the camphene nucleus unchanged. Camphene dibromide is probably formed by the addition of hydrogen bromide to the bromo- camphene which is the first product of the action, and is reconverted into bromocamphene by distilling with quinoline. It is not, however, readily acted on by alcoholic potash, and is reduced by sodium and alcohol to a dihydrocamphene identical with that from pinene hydro- chloride; it is therefore suggested that it has the same nucleus as the /CH,*CH,\ /CHO--CH9\ - \ latter, and the formula CMe'-~Me2-CBr is suggested ; the \CHBr* CH,/ORGANIC CHEMISTRY 91 conversion of bromocamphene lnto camphenedibromide would then in- volve the conversion of a Four-membered into a five-membered ring, as in the conversion of pinene into the hydrochloride.Camphene hydrobromide, ClOHI6,HBr, separates from alcohol in well- formed crystals and melts at 133' ; it is reconverted into camphene by alcoholic alkalis, and also when attempts are made to reduce it with sodium and alcohol, The hydrochloride loses hydrogen chloride less readily, and gives a mixture of camphene and dihydrocamphene iden- tical with that from pinene hydrochloride; it is suggested that the /CH,*CH,\ hydrochloride is perhaps a mixture of CNe'-CMe23CH and \-CMeCl-/ /CH,*CH,\ CMe-CMe,-CCl. \CH,*CH 2/ Camphene alcoholate, C,,H,7*OEt, prepared by boiling a mixture of camphene, alcohol, and sulphuric acid, is an oil which boils at about 200', has m, 1.4589, a sp.gr. 0.895, and is identical with isoborneol ethyl ether (Bertram and Walbaum, Abstr., 1894, i, 204) ; this reac- tion does not take place with other terpenes, although nopinene and sabinene give small yields of an ether. isoBorneol gives a small yield of camphor when oxidised with dichromate and sulphuric acid; it may be a camphane derivative, CMe-CMe,-C*OH, or a cam- /CH,.CH,\ \CH2*CH,/ ,AH2- CH,\ \CMe(OR) T. M. L. phene derivative, CMe-CMe,-/CH, or a mixture of these. The Resin-Balsam of Picea Vulgaris, Link (Jura Turpen- tine). By ALEXANDER TSCHIRCH and En. BRUNING (Arch. Pharm., 1900, 238, 616-630).-This turpentine was examined by the methods already described (Abstr., 1900, i, 678, &c.).From a solution of it in ether, 1 per cent. aqueous ammonium carbonate extracts piceapirnarinic acid, C13H2,02, an amorphous substance, which neutrahes 1 KOH both in the cold and on boiling, After this treatment, 1 per cent, aqueous sodium carbonate extracts a mixture of acids, from the solution of which in methyl alcohol piceapimuric acid, C20H30O2, crystallises ; this melts at 144--145O, and neutralises 1KOH both in the cold and on boiling ; mono-potassium, culciurn, lead, and silver salts were prepared. From the mother liquors of this acid, two isomeric piceapimarolic acids, C,,H,,O,, separate ; these are amorphous, and can be separated with alcoholic lead acetate, which precipitates the lead salt of the a-acid, but not that of the P-acid; the acids melt a t 90-95' and 88-94O respectively; both neutralise lKOH as well in the cold as on boiling.These resinolic acids all give the colour reactions of the cholesterols. After removal of the acids and further washing with dilute aqueous potassium hydroxide, the ether was distilled off, and the residue dis- tilled with steam ; an etheveal oil came over, smelling like turpentine. There remained behind a substance of indifferent character, jworesen, C,IH360*92 ABSTRACTS OF CHEMICAL PAPERS An alkaloid can be extracted from the turpentine with hot water. The turpentine also contains a Golouring matter, and it yields formic, acetic, and succinic acids when distilled ; no methoxyl is present. In 100 parts of the drug there are contained : piceapimarinic acid, 2-3 ; piceapimaric acid, 1.5-2 ; a- and P-piceapimarolic acids (the former in larger amount), 48-50 ; ethereal oil, 32-33 ; juroresen, 10-12 ; succinic acid, colouring matter, alkaloid, water and impuri- ties, 1-2 parts.C. F. B. Synthesis of Luteolin. By STANISLAUS VON KOSTANECKI, A. R ~ ~ Y C K I and JOSEF TAMBOR (Ber., 1900, 33, 3410-3417).-When 2 : 4 : 6-trimethoxyacetophenone and ethyl piperonylate dissolved in sylene are heated with sodium for 10-12 hours a t 120°, condensation ensues with the formation of 2 : 4 : 6 t~imethoxybenxoyZ-3' : 4'-methyEene- dioxyacetophenone, C,H,(OMe);CO*CH,*CO*C~H~:O,:CH,, which crystallises in small, yellow needles, melts a t 115' and when warmed with hydriodic acid yields 5 : 7-dimethoxy-3' : 4'-methylenedioxyJlavone, which crystallises in clusters of silky, white needles, melts at 232O, and forms fluorescent solutions. As this compound is not easily converted into tetrahydroxyflavone, 2 : 4 : 6 : 3' ; 4'-pentamethoxybenxoylacetophenone was prepared by the condensation of 2 : 4 : 6-trimethoxyacetophenone with ethyl veratrate ; this is precipitated by carbon dioxide from its solution in sodium hydroxide as a white, curdy precipitate and, when treated with strong hydriodic acid, yields luteolin.Hydrolysis of Solanin. By FERDINAND SCHULZ (Zeit. Zuc?c.-lnd. Bohm., 1900, 25, 89--94).-0n hydrolysis, solanin yields about 47.53 per cent. of its weight of solanidin and 42-41 per cent. of sugar (calcu- lated as dextrose), the latter being a mixture of dextrose with a methylpentose, probably rhamnose.Oxidation of Aloin with Potassium Persulphate and with Caro's Acid. By EUGEN SEEL (Ber., 1900, 33, 3212-3214).-By the action of an excess of potassium persulphate on aloin, a red substance is produced, perhaps identical with Schaer's <aloin red ' (Abstr., 1900, i, 5 12). Caro's reagent gives a tetvahydroxymethylanthraquinone, C15H1006, which is perhaps identical with Oesterle's ' alochrysin ' (Abstr., 1899, i, 538). Crystalline Compounds in Galanga Root. By GIumPPE TESTONI (Gaxxetta, 1900, 30, ii, 327-339).-Alpinin, C17H,,0,, which Jahns (Abstr., 1882, 866) isolated, together with campheride and galangin, from galanga root (AZpinia oficinarum), is shown by the author to be a mixture of the two last-named compounds.The methyl derivative of galangin, C,,H,,O,, is also present in galanga root and crystallises from methyl alcohol in pale yellow, square plates melting a t about 300'. It dissolves in concentrated sulphuric acid, forming a deep yellow liquid which in a short time assumes a green fluorescence ; it is also soluble in concentrated potass- ium hydroxide solution, giving an intense yellow colour, whilst with sodium hydroxide the corresponding salt is precipitated in minute yellow needles. I t s diacetyl compound, C,,,H,,O7, separates from ales R. H. P. T. H. P. T. M. L.ORGANIC CHEMISTRY. 93 hol in faintly yellow leaflets melting at 175-176O and forms a di- hornaide, C2,,HlG07Br2, crystallising from acetic acid in yellow needles melting a t 202'. The methyl derivative is transformed into galangin by hydriodic acid.Jahns (Zoc. cit.) and Gordin (Diss.) prepared diacetyl- and dibenzoyl- derivatives of campheride, but the author has obtained trisu bstituted derivatives, thus confirming the constitution given by von Kostanecki (Abstr., 1896, i, 44). T'riacetylcamphsride, C,GHgOGAc,, separates from alcohol in almost white needles melting at 193-194' and the tribenzoyl compound crystallises from acetic acid in white, marnmillary masses melting at 177-178'. On methylating campheride with methyl iodide and alcoholic potash, it yields mainly a trimethyl derivative, C,,H,,O,, separating from methyl alcohol in square or rectangular yellow plates melting a t 178', whilst ethylation yields a diethyl derivative, C2,H2,00, crystallising from methyl alcohol in slender, yellow needles melting at 137-139' and a triethyl compound, U22H2406, separating from light petroleum in long, yellow needles melting at 125-126'.I n these trisubstituted deriva- tives, one of the alkyl groups enters the nucleus of the molecule and is not present in the form of a methoxy- or ethoxy-residue. T. H. P. Tiliadin, a Constituent of the Bark of Lime Trees. By WALTER BRAEUTIGAM (Arch. Pharm., 1900, 238, 555-567).-When the bark of the lime tree is extracted with ether, the extract evapor- ated, and the residue washed thoroughly with 90 per cent. alcohol, the alcohol extracts a little vanillin. If the residue is boiled with 5 per cent. aqueous potash and then dissolved in ether, the solution deposits crystalline plates as i t evaporates ; this substance, tiliadin, C21H3202, melts at 228-229', volatilises when heated cautiously, and is dextrorotatory in chloroform solution.I n many of its reactions it resembles the cholesterols, but in others it differs from them; it has not the properties of a glucoside. It does not lose water of crystallisation when heated at 125', nor will it form acetyl or benzoyl derivatives. Strong hydrochloric acid is without effect on it, even a t 160'. Boiling with aqueous alkali hydroxides is without effect ; on the other hand, alcoholic potash at 150' converts it into a substance, C,,H,,O, which crystallises in needles, begins to melt at 179--180', and volatilises when heated cautioualy. Fusion with potassium hydroxide converts tiliadin into resinous pro- ducts, but oxalic acid is not formed.Boiling with nitric acid has no effect, but a t 160' a resinoils product is obtained. Potassium per- manganate does not oxidise i t in cold acetic acid solution, but it does on boiling, and so does chromic acid ; the product is a resinoils sub- stance, with the composition C,,H,,O,. When treated with chlorine or bromine in chloroform solution, tiliadin yields products containing chlorine and bromine; with iodine, no similar product could be obtained. On the west side of the tree, the bark frequently has a green coating of an alga, Pleurococcus uulgavis; from this a substance cryatallis- ing in needles was obtained; these crystsllise out along with the VOL. LXXX. i. h94 ABSTRACTS OF CHEMICAL PAPERS, plates of filiadin in the preparation of the latter, if the bark has not been freed from the green coating.Blue Chlorophyllin. By M. TSVETT (Compt. rend., 1900, 131, 842-844).-The blue chlorophyllin was isolated from the plants by a method which is described in detail. It was obtained in a micro- crystalline state, the crystals having a black colour and a bluish lustre. The absorption spectrum of its solution consists of six bands, the fourth band being situated near the Fraunhofer line E, and the fifth commences at the line F. Composition of the Orange Pigment of Uraster Rubens. By ARTHUR BOWER GRIFFITHS and F. U'. WARREN (Bull. h'oc. Chinz., 1900, [iii 1, 23, 874--875).-The orange pigment extracted from the skin of Uyastey rubens has the composition C,,Hi,02N4 ; its solutions do not show characteristic absorption bands.Syntheses of Coumaranone (Ketocoumaran) and its Homo- logues from Phenoxyacetic Acid. By RICHARD STOERMER and F. BARTSCH (Ber., 1900, 33, 3175-3181. Compare Abstr., 1899, i, 675).-Coumaranone is most easily obtained by the dehydration of phenoxyacetic acid suspended in benzene with phosphoric oxide, and is separated from the unaltered acid by distillation with steam ; when pure, it is quite stable and has a pleasant odour of hyacinths, It sublimes at the ordinary temperature in long, slender needles and melts at 101-102'. The semicarbaxone, C,H,O,N,, separates from alcohol in yellowish crystals and melts at 231'. The oxime, C,H70,N, crys- tallises from hot dilute alcohol and melts a t 159'. l-o-Eydroxybenxylidenecoumaranone, C,,Hi003,.separates from hot dilute alcohol in slender, yellowish crystals melting and decomposing at 208' ; it dissolves in alkalis with an intense red colour. l-p-Hydvoxy- benxylidenecoumarccnone is a greenish-yellow, crystalline substance which melts and decomposes at ,242'. The two foregoing compounds are substantive dyes. During the preparation of coumaranone, a considerable quantity of a reddish- brown substance, Cl6HI0O3, is obtained as a bye-product. This has the constitution C,H4<:6x:C<g320, and is probably formed by condensation of 2 mols. of coumaranone. C. F. B. H. R. LE 8. N. L. 6-Meth ylcoumaranone, C,H3Me<CO>CH,, -0- from o-tolyloxyacetic acid, forms yellowish-white crystals melting at l02', is volatile with steam, and dissolves readily in the common organic solvents or in hot water.With Fehling's solution, it yields a red dye similar to that obtained from coumaranone. The semicurbaxone, CioH, 102N3, separates from hot dilute alcohol in yellowish crystals melting at 229'. The oxime, C,H,02N, is yellow, dissolves in ether, benzene, or alcohol, and melts at 148'. l-o-Hydroxybenzylidene-6-methyZcoumaranone, Ci,HJ203,. cry stallises from hot alcohol in yellow needles, dissolves in alkalis, yieldiug an intense red solution and sublimes and decomposes at 196'. The corresponding pava-compound forms yellow leaflets which decompose at 2 10-2 15'.ORGANIC CHEMISTRY. 95 5-MethyZcouma?anone, CgH,02, unlike the analogous substances already described, is an oil, and boiis at 106-112' under 15 mm.pressure ; its properties closely resemble those of coumaranone. The sernicarbaxone, C10H1102N3, is yellowish and melts a t 208', the oxime CgH,02N, is yellow and melts a t 151*. The 0- and p-hydroxybenzytidene derivatives, Cl6HI2O3, are yello wish-brown, the former decomposes a t 192', the latter at 212'. 4-~ethylcouma~ccnone, C9H802, is a yellowish liquid which boils with- out decomposition in a vacuum. The semicadaxone, C,,H,,O,N,, melts a t lSl', and the oxime, C,Hg02N, at 144'. The 0- and p-hydroxy- benxylidene derivatives, CI6Hl2O3, decompose at 210' and 163' re- spectively. 4 : 6-~~methy~coumc~~ccnone, C,H2Me2<Co>CH2, from ccs-m-xylyloxy- -0 acetic acid, melts at 143O. Its oxime, C1,Hl,O2N, melts at 148'. A. L. The Cinchona Alkaloids. By WILHELM VON MILLER and GEORG ROHDE [in part with JOSEF BRUXNER and ERNST FUSSENEGGER] (Ber., 1900, 33, 3214--3237).-The identity of Pasteur's cinchonicine and quinicine (Jahresber.der Chem., 1853, 473) with cinchotoxine and quinotoxine has been established. By the action of amyl nitrite and sodium ethoxide cinchotoxine is converted into an isonitroso-derivative, C,,H2102N3, which separates in crystal' aggregates from chloroform when ether is added, melts at 169-170°, and, like other secondary piperidine bases, gives a purple coloration with nitrobenzene containing nitrothiophen ; the salts do not give this reaction. The hydrochloride, ClgH2102N3,HCI, melts at 268', crystallises from alcohol or hot water in prismatic plates, dis- solves in acids and alkalis, and gives Liebermann's reaction ; the cccetccte melts at 200°, and the suZphate, nitrate, formate, and phosphccte are also crystalline.The methiodide, C19H2,02N3, MeT, crystallises from methyl alcohol in prisms and plates, melts at 2354 and, unlike most secondary bases, is not acted on by aqueous alkalis ; when treated with sodium ethoxide, it gives a base identical with the isonitroso-derivative of methylcinchonine, and i t would therefore appear that in the removal of hydrogen iodide from the methiodide the cinchotoxine is reconverted into a cinchonine derivative. By the action of an excess of amyl nitrite on cinchotoxine, MilIer and Rohde's nitrosoisonitrosocinchotoxine (Abstr,, 1895, i, 433) is produced, and not a diisonitroso-derivative ; it would therefore appear that cinchotoxine contains only one methylene group adjacent t o a carboxyl group in accordance with the formula cH2>NH, and not CH C9NH6*cH2* CMe<CH:CH:CH2) .CH2 C9NH6*CH2* Co*CH2*CH<~$cH:CH,) .CH2 OH2>NH.The action of p-bromophenylhydrazine on quinotoxine gave a mixture of substances, one of which crystallised in yellow aggregates melting a t 141' and proved t o be a p-bromophenylhydraxone, C2eH2,0N,Br ; a second product crystallising -in minute yellow h 296 ABSTRACTS OF CHEMICAL PAPERS. needles and melting 15-20' higher is perhaps the geometrical isomeride. Nityosoquinotoxine, C,,H,,O,N,, prepared by the action of nitrous acid on quinotoxine, crystalliees from a mixture of acetone or benzene with light petroleum in colourless needles, melts a t 94', dissolves in acids and gives Liebermann's reaction; the phenyhydrcczone, C2,H2,0,NS, crystallises from alcohol and melts at 140'.Xtyosoisonitrosoquzno- toxine, C2,H,,0,N,, which is also produced in the action of nitrous acid on quinotoxine, crystallises from alcohol in large, colourless prisms, melts a t 186q and dissolves in alkalis to a yellow solution. The action of methyl iodide on quinotoxine is similar to its action on cinchotoxine, the products being methylquinine (Claus and Mall- mann, Abstr., 1881, 619) and its methiodide; the anhydrous meth- iodide melts a t 180°, not at 215-218'. isoivitrosoquinotoxine, C20H2303N3, crystallises from a mixture of alcohol and benzene in yellowish aggregates, melts at 168--170°, and gives the nitrothiopen reaction.The hydrochloride, C,,H,,O,N,,HCI, crystallises from alcohol in large tablets and melts a t 244'; the acetate, suZphate, and nitvale are crystalline and do not give the nitro- thiophen reaction. The methiodide, C,,H,,O,N,I, crystallises from methyl alcohol, melts at 175', and is not acted on by aqueous alkalis. By the action of sodium ethoxide the quinine complex is reproduced, the produdt being an isonit~osomethy~Quinine, which separates as a yellow, amorphous base, melts a t 90-100', and is identical with the base prepared from amyl nitrite and methylquinine ; the identity of the bases was also proved by conversion into the methiodide, C2,H2,0,N,I, melting a t 169-170°, and the nitrate melting at 175O. Constitution of Pyridones, Quinolones, and Analogous Bases.By HERMANN DECKER (J. p r . Chem., 1900, [ii], 62,266-270). -A discussion of the formulae of pyridones and analogous bases. The author favours formulae of the ketonic type, CHeCH* CH:CH 'O>NR, T. M. L. which he considers represent the reactions of these bases better than formulae of the type CH:CH* I 8->0, which contain quinquevalent CH:CH*NR nitrogen. R. H. P. Thio-1-methylpyridone and Thio-1-methylquinolone. BY ALEXANDER GUTBIER (Ber., 1900, 33, 3358-3359).- W&-lmethyl- pyridone, CH<~H:CH>NM~, CH* CS or s<c TMe:CH* =CH-CHH' GH obtained by heating 1-methylpyridone with phosphorus pentasulphide for 4-5 hours a t 1 30°, crystallises from hot water in yellowish-white leaflets, melts at 89 -go', and distils unchanged ; it is feebly basic, dissolving in concentrated sulphuric or hydrochloric acid.Thio- 1 -methylpinolone, obtained similarly, forms long, pointed, yellowish green prisms, melts at 11$', boils unchanged above 370°, and resembles the foregoing thiopyridone. Both substances, like 1 -methylpyridone and 1 -methyl- quinolone from which they are derived, fail t o interact with hydroxyl- amine in either neutral or alkaline solution. W. A. D.ORGANIC CHEMISTRY. 97 Action of Ethyl Acetonedicarboxylate on rn-Phenylene- diamine. By EMIL BESTHORN and E. GARBEN (Bey., 1900, 33, 3448-3453. Compare Abstr., 1898, i, 450).--EthyZ 7-amino-2-puinolone- 4-acetate is obtained when molecular quantities of ethyl acetonedicarb- oxylate and m-phenylenediamine are heated together for several hours in sealed tubes at 100'; on hydrolysis with hydrochloric acid, it yields 7-amino-2-quinoZone-4-acetic acid in the form of its hydrochloride which when washed with water yields the acid, NH .C H <C(CH20C02H):~H. 2 6 4 N H -C@ ' this crystallises from water in hair-like, colourless needles inel ting at about 271°, is only sparingly soluble in the usual organic solvents, and its solution exhibits a blue fluorescence.The calcium salt contains 5H20, the ethgZ ester crystallises in needles melting a t 197-1998', is sparingly soluble and its solutions also fluoresce. When the acid is rapidly heated a t 300°, it loses carbon dioxide and yields 7-amino- lepidone (7-amino-2-hydroxylepidine); when treated with nitrous acid, it yields 7-hydroxy-2-puinolone-4-acetic acid, which crystallises from hot water in felted needles melting at about 320' ; it forms a hydrochloride which is decomposed by water, and an ethyl ester crystallising in minute needles and melting at 204-205', but after solidification at above 2204 When the acid is carefully heated, it yields 7-hydroxy- lepidone (2 : 7-dihydroxylepidine).J. J. 8. Stereoisomeric SchifI's Bases, By ALEXANDER EIBNER and FRZ. PELTZER (Ber., 1900, 33, 3460-3469. Compare Abstr., 1894, i, 410).-When aqueous solutions of o-toluidine and acetaldehyde are mixed and kept at the ordinary temperature for 24 hours, an ethyZ- idene-o-toluidine, C,,H,,N,, crystallising in small needles and melting, after repeated recrystallisation from alcohol, at 90-92' is obtained ; it dissolves readily in both dilute and strong hydrochloric acid, but yields a sparingly soluble nitrate ; when benzoylsted by the Schotten Baumann method, i t yields a 6enxoyZ derivative, C25H280N2, melting at 179', together with a small amount of the isomeric benzoyl compound melting at 230'.Its dinitroso-derivative, C,,H,,02N4, crystallises in yellow needles melting at 130' and is sparingly soluble in alcohol ; when reduced, it yields p-phonylenediamine and 2 : 8-dimethyltetra- hydroquinoline. When the base is distilled, it yields 2 : S-dimethylquino- line together with a small amount of the isomeric base melting a t 116'. If the solution of acetaldehyde and o-toluidine is warmed, shaken, or kept at the ordinary temperature for several weeks, an ethylidene-o- toluidine melting a t 116' is obtained ; this crystallises in small prisms or plates, is readily soluble in most solvents with the exception of light petroleum, forms a hydyochloride, 3 sparingly soluble nitrate melting at 155', a diacetyl derivative melting at 155', a Jinitroso-compound melting at 155', and a 6enxoyZ derivative melting a t 230'; the latter Forms a nitroso-compound melting at 190' The base itself can be distilled without undergoing any great decomposition and is not reduced when treated with sodium and amyl alcohol.The same base is obtained when the isomeride of low melting point is heated for 4 hours at 120-125', or when its ethereal solution is treated with iodine. When98 ABSTRACTS OF CHENICAL PAPERS. the condensation takes place in acetic or hydrochloric acid solution, the compound melting at 116O is alone formed.Action of Nitrosobenzene on Aromatic Hydraxines. By OSKAR SPITZER (Chem. Centr., 1900, ii, 1108; from Oesterr. Chem. Zeit., 3, 489-490).-Whilst by the action of nitrosobenzene on hydrazobenzene, azobenzene and water only are formed, with phenyl- hydrazine, nitrosobenzene yields, not only these products, but also nitrogen and benzene. The latter reaction may be used to estimate the quantity of nitrogen present as nitroso-groups in organic corn- Founds. E. W. W. Phenylmethylpyrazolecarboxylic Acids. By CARL BU LOW (Ber., 1900, 33, 3266-3270).-The acid formerly described by Bulow and Schlesinger as 1-phenyl-3-methylisopyrazole-4 : 5-dicarboxylic acid (Abstr., 1900, i, 36) is in reality 1-phenyl-5-methylpyracxole-3 : 4-dicarb- oxglic acid (compare Stolz, Abstr., 1900, i, 252) ; i t is produced, together with Knorr and Laubmann's dicarboxylic acid (Abstr., 1889, 409), by oxidising 1 -phenyl-3 : 5-dimethylpyrazole-bcarboxylic acid with potassium permanganate ; it is identical with the substance pro- duced from diethyl benzeneazodiacetylsuccinate, and yields, by the successive elimination of its carboxyl groups, 1-phenyl-5-methylpyr- azole-4-carboxylic acid (m.p. 166') and I-phenyl-5-methylpyrazole. The isomeric acid described by Knorr and Laubmann as melting a t 198' has a melting point 203-204°, and is 1-phenyl-3-methylpyrazole- 4 : 5-dicarboxylic acid ; it yields l-phenyl-3-methylpyrazole-4-carboxylic acid (m. p. 192*5-193c) and 1-phenyl-3-methylpyrazole by the succes- sive removal of carboxyl.Preparation of Pyrazole Derivatives from Azo-compounds of Diacetosuccinic Esters. By CARL BULOW and ALFRED SCHLES- INGER (Ber., 1900, 33, 3362--3369).-The following facts form an extension of a previous paper (preceding abstract). Diethyl p-toluene- uzodiucetosuccinate, C6H4Me*N,* C Ac( C0,Et) C( CO,Et):CMe*OH, ob- tained by combining p-toluenediazonium chloride with ethyl diaceto- succinate, separates from alcohol in yellow crystals, melts at 119-1 ZOO, and on boiling with water for 8 hours loses acetic acid (1 mol.), and yields tliethyl 1-p-tolyl-5-methylpyraxole-3 : 4-dicarboxylate, G 6 H 4 N e * N < T CMe. C I CO,E t ' This crystallises from dilute alcohol, melts at 50°, and on hydrolysis with dilute mineral acids or alkalis yields 1-p-tolyl-5-rnethylpyrazole-3 : 4-dicarboxylic mid, which forms slender needles, melts a t 246O, and yields an acid silver salt, C,,H,,O,N,Ag, as a white powder, insensitive to light, On heating the acid above its melting point, it loses carbon dioxide and yields a mixture of I-p-tolyZ-5-methylpyruxole and its 4-cadoxylic acid. The former is a yellowish oil, which boils at 270-280°, is volatile in steam, and yields a crystalline platinichloride melting and decomposing a t 214O; its 4-carboxylic acid is crystalline, and melts at 199-20Oo.Diethyl P-nuphthaleneaxodiacetoszcccinate, prepared from diazotised P-naphthylamine and diethyl acetosuccinate at Oo, separates from dilute alcohol in reddish-yellow crystals and melts at 108'. RiethyZ J. J. S. G. T. M. --c* CO,EtORGANIC CHEMISTRY. 99 1 -P-naphtliyl-5-methy~pyraxoZe-3 : 4-dicarboxylate crystallises from dilute alcohol in nearly colourless, lustrous leaflets and melts at 82' ; tho corresponding dicarboxylic acid melts at 250°, and on dissolving in ammonia and adding silver nitrate, yields the silver salt, CI6H1,O,N,Ag, as a heavy, white precipitate.l-P-Nccphthyl-5-methyl- pyrazole melts a t 65", boils at 320-330°, and yields a crystalline platinichloride me1 ting a t 2 17". W. A. D. Theories of Dyeing. By PAUL SISLEY (Bull. Xoc. Chirn., 1900, [iii], 23, 865--874).-In this paper, the researches of Witt, Knecht, von Georgevics, and Gillet are briefly reviewed, and a description is then given of some fresh experiments favouring Witt's dissolution theory, according to which the dyeing of a fibre is analogous to the extraction of a colouring matter from its aqueous solution by means OF an immiscible solvent.When pure, colourless rosaniline is boiled with water, a coloured solution is obtained which quickly dyes silk; in the presence of excess of alkali (1.5 grams of sodium hydroxide per litre) no coloration is produced. According to Knecht, when silk is dyed with magenta in neutral solution, the exhausted liquid contains the whole of the hydrogen chloride of the dye as ammonium chloride. The author confirms the presence of hydrogen chloride, to some extent, at least, but no ammonia could be detected in the bath. When 100 C.C. of water are boiled with 2 C.C. of normal sodium hydroxide and a little rosaniline, a colourless solution is obtained which dyes silk and yields a red colour to amyl alcohol when boiled therewith.Malachite-green, crystal- violet, and Victoria-blue behave in a similar way; aniline may be used instead of amyl alcohol, These results are shown to be due neither to impurities in the substances employed nor to the action of carbon dioxide. Their explanation is rather to be sought in von Georgevics' hypothesis, according to which the silk, amyl alcohol, or aniline bring about the molecular transformation of the colourless base OH*C(C,H,* NH,), into a coloured isomeride, OH*NH,: c,H,: C( C,H,*NH,),. The latter does not form a coloured salt with the substance of the fibre, as required by the purely chemical theory of dyeing, but forms either a solid solution with the fibre or a liquid solution with the amyl alcohol or aniline.This view is confirmed by the observations of Hantzsch on colourless and coloured modifications of triphenyl- methane derivatives. Moreover, when silk dyed with rosaniline is boiled with alcohol, the colouring matter is readily dissolved, whilst the fibre does not lose in weight. According to the chemical theory, the alcoholic extract should either be colourless or, if coloured, should contain a portion of the acid substances of the fibre in solution. The fact that in acid solutions animal fibres are dyed with the colour of the alkali salt has been adduced as an argument in favour of the chemical theory of dyeing, the fibre being here held to play the part of a base. It is now shown, however, that amyl alcohol behaves in precisely the same manner as silk in this respect, so that the facts are really in accord with the dissolution theory. Certain facts, however, appear t o contradict Witt's view that a colouring matter, in order to be fast,100 ABSTRACTS OF CHEMICAL PAPERS, must necessarily be more soluble in the substance of the fibre than in water.Thus, when silk is dyed with a very dilute solution of a colouring matter, the whole of the latter is extracted from the liquid by the fibre, whereas when a large amount of the dye is used only a comparatively small proportion of it is taken up by the silk. The relative solubilities of the dye in the fibre and in water seem, in fact, to vary greatly with the concentration. Nevertheless, it is believed t h a t experiments now i n progress will show that in many cases the behaviour of immiscible solvents is in this respect also identical with that of animal fibres.N. L. Coloured Rosaniline Bases. By HUGO WEIL (Be?., 1900, 33, 3141-3144).-In reply to von Georgievics (Abstr., 1900, i, 569), the author adheres to his previous statments (Abstr., 1896, i, 565) : 1. That the red precipitate obtained by von Georgevics is really a mixture of rosaniline with a small amount of its hydrochloride. 2. That when a solution of rosaniline carbonate is “salted out” with pure sodium chloride the solution becomes colourless and the clear iiquid after concentration gives a blue colour with litmus. J. J. 5. Relation between the Chemical Constitution of Triphenyl- methane Colouring Matters and the Absorption Spectra of their Aqueous Solutions.By PAUL LEMOULT (Compt. rend., 1900, 131, 839--842).-Aqueous solutions of dyes of the triphenylmethaue series in all cases give an absorption spectrum which contains a characteristic band of unabsorbed light in the red. The position of the centre of this red space is constant for those dyes which contain two tertiary nitrogen atoms and also for those containing three tertiary nitrogen atoms, but its position in the latter case is quite distinct from that in the former. The solutions employed had,a thickness of 6 mm., and contained a gram-mol. of the substance in 1000 litres. H. R. LE S. Relation between the Chemical Constitution of the Tri- phenylmethane Colouring Matters and their Absorption Spec- tra in Aqueous Solution.By CHARLES CAMICHEL (Compt. rend., 1900, 131, 1001--1002).-The observation made by Lemoult (preced- ing abstract) relating to the presence of fixed red bands of unabsorbed light in the spectra of triphenylmethane colouring matters containing two or three tertiary nitrogen atoms in the para-position with reference to the methane carbon atom, is only a special case of the law enunciated by Bayrac and the author (Abstr., 1896, ii, 346), who found it to hold f o r a series of indophenols dissolved in water and other solvents. The ethereal solution of an indophenol may be advantageously employed as a monochromatic screen instead of red glass. G. T. M. The Twelfth Isom eride of Roeinduline. By FRIEDRICH KEHRMANN and G. STEINER (Ber., 1900, 33, 3276-3279. Compare Abstr., 1900, i, 463).-Phenglisonaphtha~heaazonium nitrate (Abstr., 1898,i, 154),when left with fuming nitric acid for 24 hours a t Oo, Sields aORGANIC CHEMISTRY.101 mixture of 2-nitro- and 4-nit~o- 12-phenylisonuphthaphena~onium aitrates. The former, although sparingly soluble in absolute alcohol, crystallises from dilute alcohol in lustrous, yellow needles, and on reduction yields isorosinduline KO. 10 (Abstr., 1900, i, 463), a fact which determines its structure ; the latter is easily soluble in alcohol and could not be obtained pure, although the corresponding isorosinduline (No 12) [4-camino-l2-p~enylisonuphthap~enaxo~iu~], formed on reduction, was readily isolated, by taking advantage of the slight solubility of its bromide in saturated aqueous sodium bromide. The salt crystallises in well-formed, nearly black prisms, with a bluish surface-colour ; the dichromate is a dark green, microcrystalline powder.4-Acetylamino-12 -phen ylisonapht~~aphenaxolziuln 1 2-bromide is very soluble in:water, and cannot be separated by saturating the solution with sodium bromide ; the chloride, however, crystallises on adding sodium chloride in thick, reddieh-brown, prisms or plates, whilst the platini- chloride forms dark red, granular crystals. The structure of the isorosinduline No. 12 follows from its syn- thesis from 5-acetylamino-1 : 2-naphthaquinone (Kehrmann and Denk, this vol., i, S9). Constitution of isoRosinduline No 9. By FRIEDRICH KEHR- MANN and G. STEINER (Ber., 1900, 33, 3280--3284).-Details are given for preparing 2 : 5-diamino-1 : 4-naphthaquinoneimide hydrochloride (compare Kehrmann and Haberkant, Abstr., 1899, i, 62) from Ekstrand's naphthapicric acid (2 : 4 : 5-trinitro-a-naphthol), the structure of which has recently been determined (Graebe, Abstr., 1900, i, 24; Friedlander, ibid., 150); the salt is much more stable than hitherto thought, not being changed by boiling water.The diamino-a-naphthaquinone and aminohydroxy-a-naphthaquinone derived from it by the action of alkalis have the structures [02:(NH2)2 = 1 : 4 : 2 : 51 and [0, : NH, : OH = 1 : 4 : 5 : 21 instead of those originally given (Abstr., 1809, i, 62). The 5-amino-2-hydroxy-1 : $-naphtha- quinone is best prepared by heating the hydrochloride in aqueous solu- tion with dilute sulphuric acid; it does not condense with phenyl-o- phenylenediamine in alcoholic or glacial acetic acid solution, but in 80 per cent.acetic acid solution at 100° it yields 4-c~minorosindone, W. A. D. N=C H(NH,) .I b,H,.NPh 1110 >o, which was isolated iu. the form of its ucetyd dirivative. This crystallises from alcohol in golden needles, melts a t 280°, and shows a red fluorescence in alcoholic solution ; on warming with dilute sulphuric acid, it yields pure 4-aminorosindone, which crys- tallises from alcohol in bronze coloured leaflets, melts a t 253O, and can also be obtained by the action of cold alcoholic sodium hydroxide on isorosinduline No. 9 (Kehrmann and Filatoff, Abstr., 1900, i, 60). This latter fact, together with the work of Kehrmann and Denk (this vol., i, 89), show that isorosinduline No.9 is a 4-amino-7-phenyl- naphthaphenuzonium. W. A. D. Constitution of the Naphthapicric Acid melting at 145'. By FRIEDRICH KEHRMANN and G. STEINER (Ber., 1900,33,3285-3291). -The trinitro-a-naphthol (naphthapicric acid) melting a t 145O3.02 ABSTRACTS OF CHEMICAL PAPERS. (Kehrmann and Haberkant, Abstr., 1899, i, 62) can be readily separated from its isomeride melting at 190°, on account of the sparing solubility in water of its sodium salt, which crystallises in slender, sulphur-yellow needles; the following facts show that it has the con- stitution [OH : (NO,), = 1 : 2 : 4 : 71, and the substance formerly described (Zoc. cit.) as 2 : 6-diamino-1 : 4-naphthaquinoneimide is there- fore a 2 : 7-diamino-compound. The latter, when warmed with water, yields a mixture of 2 : 7-diamino-1 ; 4-naphthapinone with 4 : 7-di- amino-1 : 2-naphthaquinone, which can readily be removed by extraction with cold 10 per cent, aqueous sodium hydroxide, in the form of the sodium derivative of the tautomeric 7-aveino-2-hyd~oxy-1 : 4-naphtha- quinoneimide.The pure a-quinone forms small prisms which are chocolate-brown with a violet tinge in colour, sublimes and partly decomposes at 230°, yields an orange-yellow hydrochloride, and does not combine with ortho-diamines ; the P-quinone forms blackish-violet crystals, and yields a violet solution with dilute hydrochloric acid. Both of the quinones when boiled with dilute caustic alkalis yield 7-amino-2-hydroxy-1 : 4-naphthaquinone along with decomposition pro- ducts which render purification difficult ; the substance isolated forms brownish-red crystals, and combines with o-aminodiphenylamine N=~+,H,(NH,~ " (1 mol.) to form a 2-aminorosindone, b,:H,.NPh------->O' which yields an acetyl derivative crystallising igluitrous, red leaflets melting at 325-335', identical with the substance formed by the oxicla- tion in the air OF an alkaline alcoholic solution of Z-acetylamino- 7-phenylnaphthaphenazonium chloride (Abstr., 1900, i, 463), the latter fact determining its structure. Confirmatory evidence as to the structure of the new naph thapicric acid is afforded by the fact that the foregoing 4 : 7-diamino-1 : 2- naphthaquinone yields with o-aminodiphenylamine a 2-aminorosinduEine, identical with the substance obtained by acting on %ace tamino-7- phenylnaphthaphenazonium chloride (Abstr., 1900, i, 463) with alcoholic ammonia, and subsequently eliminating the acetyl group ; the chloride forms slender, violet-brown needles, the acetyl derivative, U2+Kl9ON4Cl, crystallises from alcohol in dark-red needles with a brownish sheen, whilst the dichromcbte, (C,,H190N4)2Cr,0 7, is a red powder. W.A. D. The Thirteenth Isomeride of Rosinduline. By FRIEDRECH KEHRMANN and M. SILBERSTEIN (Ber., 1900, 33, 3300-3307. Com- pare preceding abstracts) .-4-Anilino-6 -acet y lam ino-1 : 2-nap h t haquin- one (Rehrmann and Matis, Abstr., 1899, i, Sl) condenses with o-amino- diphenylamine hydrochloride in boiling dilute acetic acid solution to form principally 3-acetylaminophenylrosinduline chloyide (3-ncetylamino- 5 -amilkno- 7-phenyZ~p~~thaphenc~oni~m chloride), a long with a small quantity of the isomeric 12-phenyliaon~p~~t~ah~na~onium chloride ; the latter separates first in brownish-red needles, and will be described in a later communication, whilst the former is obtained only on salting out. It crystallisea from alcohol in thick, dark-red prisms with a golden sheen, and with dilute alcoholic sodium hydroxide yields the 6ase, C,,H,,0N4* OH, in brownish-red leaflets with a bronze-like lustre.ORGANIC CHEMISTRY.103 separates on boiling the acetyl derivative with alcoholic hydrochloric acid, in thick crystals with a greenish lustre ; from solutions 'contain- ing an excess of hydrochloric acid, the hydrochloride, C,,H,,N,Cl,, is obtained. sJ--C H(NH,) 3-Aminorosindone, ,IF,.NPh >0, is formed on heating 3-acetylamino-7-phenyl~os~nduline chloride with 10 per cent. sulphuric acid for 2-3 hours at 175-180°; the acetyl derivative crystallises from acetic anhydride in vermilion-red needles with a greenish, metallic lustre, does not melt or decompose a t 310°, and unites with methyl sulphate in nitrobenzene solution at 150' to form 3-acetylamino-5- methoxy-7phenylnaphthaphenazonium methyl sulphate, This is precipitated on addini ether as an orange, crystalline powder, which regenerates rosindone on boiling with water containing a trace of alkali, and yields a ylatirtichloride, (C?I,H,o?,N,~,PtC~6,. as an orange-yellow, flocculent precipitate ; on warming with alcoholic am- monia, evaporating, extracting with water, and adding sodium bromide, 3-acetylaminorosindule bromide separates.It crystallises from b d - ing alcohol in vermilion needles with a greenish lustre, and yields an insoluble microcryst alline dichromate, ( C,,H190N,),Cr,07 ; on elimina- tion of the amino-group by the diazo-reaction, it forms 3-acetylarnino-7- phenylnaphthaphenazoniurn, isolated as the chloride in the form of an orange powder, sparingly soluble in water, which in dilute aqueous solution yields, on adding nitric acid, microscopic red needles of the nitrate. isoRosinduZine No. 1 3 (3-amino-7-phenylnc6phthaphenazort~um) was obtained by heating the foregoing chloride with 50 per cent. sulphuric acid ; the bromide forms olive-green needles and dissolves in water with a brownish-red, but in alcohol with a dark-green, colora- *ion.It is somewhat unstable in solution, yielding aminorosindone on boiling ; alcoholic ammonia converts it into aminorosinduline. The above indirect method of obtaining isorosinduline No. 13 became necessary because 6-acetylamino-1 : 2-naphthaquinone with o-amino- diphenylamine yields only the isomeric isorosinduline No. 7 (Abstr. 1899, i, 525). By HANS RUPE and KARL TON MAJEWSKI {Bey., 1900, 33, 3401-3408).-The principal '' osmophoric '' groups are -OH, -0, -CHO, -COMe, -OMe, -NO,, -CN, -N3 (triazo-). Analogous compounds containing -CHO, -NO,, -CN, -N3 have similar odours. Pipronylamide, NH,*CO*C,H,:O,:CH,, obtained by treating piperonylonitrile with hydrogen peroxide, crystallises in lustrous prisms or needles, melts at 1 6 9 O , in common with piperonylonitrile has a similar odour t o piperonal, and, when treated with bromine and * A name chosen by the authors t o designate those groups the presence of which predicates an odorous substance.W. A. D. Osmophoric Groups.*104 ABSTRACTS OF CHEMICAL PAPERS. sodium hydroxide, yields p- aininocatechol methylene ether, which is a white, crystalline substance, melts a t 44-46'? boils at 144' under 16 mm. pressure, and forms a hydrochloride, and an acetyl derivative melt- ing a t 135'. Triuxopyrocatechol methylene ether, N,*C,H,:O,:CH,, ob- tained from the hydrochloride just mentioned, crystallises in yellow leaflets, melts at 128-130' and has a faint odour like piperonal as well as the anise-like odour of all triazo- (azoimide) compounds. Methyl p-triuxobenxoate, N,*C,H;CO,Me, obtained by the method described in the next abstract, crystallises in large, yellow lamins, is volatile with steam, melts a t 39-40', and has a characteristic sweet anise-like odour, very similar to that of methyl p-cyanobenxoate ; the latter ester forms colourless leaflets melting at 62'.Nethyl m-tvi- axobenxoate and metiiyl o-tyiazobenxoate are light yellow oils having odours similar t o (but weaker than) that of the p-compound. p-ITri- ccxoanisole crystallises in yellowish-white laminae melting at 36', and o-triuxounisole is a heavy, yellow oil, both having odours similar to those of the triaxobenzoates. p-Tyiuxobenzaldehyde is a colourless liquid with n strong, pleasant, anise-like odour ; p-triaxobenxonitde, however, has hardly any odour and crystallises in colourless needles, which melt a t 70'.p-Triuxoacetanilide forms colourless crystals and melts at 124'. m-Hydroxyacetophenone, obtained by the diazotisation of m-amino- acetophenone and decomposition of the resulting diazo-compound, crystallises in colourless laminae, melts a t 95O, forms a methyl ether, which is a colourless oil boiling at 128-129' under 12 mm. pres- sure, and unlike the analogous 0- and p-compounds has hardly any odour. m Cyanoacetophenone crystallises in small, white needles, melts at 98-99', and has no odour ; the corresponding m-acetylbenxoic ucid crystallises in slender, white needles, melts at 172O, is odourless, and forms a methyl ester, which is a colourless, odourless oil ; m-tri- axoacetophenone is a yellow, odourlem oil.Preparation of Azoimides (Triazo-compounds). By HANS RUPE and KARL VON MAJEWSKI (Be?.., 1900, 33, 3408--3410).-The azoimides corresponding with weak bases are most conveniently prepared by treating a solution of a diazo-salt with potassium hydr- oxylaminedisulphonate. The method gave good results with p-nitro- aniline, m-nitroaniline, methyl p-aminobenzoate, and p-bromoaniline. p-Triaxobromobenxene forms crystals melting at 20' and has a pleasant aromatic odour. Hydroxylamine hydrochloride may be used instead of potassium hydroxylaminedisulphonate, but the results are not quite so good. R. H. P. Ketochlorides and Quinones of Phenylaeiminobenzene [Phenylbenzotriazole]. By THEODOR ZINCKE and E. PETERMANN (Annalen, 1900, 313, 251-298. Compare Abstr., 1899, i, 135).- R.H. P. ~O-CCI,-~-N CCI,*CHCI*C*NPh~~' Pheny Zaziminopentachloroketotetrahydrobenxene, Y prepared by the action of chlorine on phenylaziminoaminobenzene (Nietzki, Abstr., 1896, i, 164), crystallises in lustrous, colour- less needles, and melts at 128-129' ; it liberates iodine from potassium iodide, and develops a n intense red coloration with aniline.ORGANIC CHEMISTRY, 105 QO--cCl:y-N, Phenylaximinotetrachloroketodihydro6enxene, ccl,. cc, : c.Nph>N, ob- tained when the foregoing substance is heated afone or with potassium acetate, dissolves readily in organic media, and decomposes when attempts are made to recrystallise it; the compound melts at 173-174", liberates iodine from potassium iodide, and develops an intense red coloration with aniline.Pl~en~/laxirninotrichlorosohenol, formed on reducing the last-named substance with stannous chloride, crystallises from glacial acetic acid in pale yellow needles, which melt and decompose at 2%"; the acetql derivative forms colourloss needles and obtained by reducing the pentachloroketone with stannous chloride, crystallises in colourless, prismatic needles, and melts at 177-1 78". y0-co-l;l-N Phenyluxiininodichloro-o-quinone, :ccL, C.Nph>N, is formed from trichlorophenol and tetrachloroketone on oxidation with nitric acid, and crystallises in reddish-yellow leaflets having a golden lustre ; it melts and decomposes at 210°, and gives a bluish-green solution in sodium hydroxide. The cmilino-derivative, C1,H,,O,N4C1,C,H7N, puri- fied by precipitation with water from solutions in alcohol or acetic acid, melts and decomposes at 130-140'; the axine, Cl,H,N,C1,, pre- pared from the quinone and o-phenylenedinmine, crystallises in silky needles.and melts above 250'. OH* y: c'( OH) ;c;'-N Phenylaziminodichlorocatechol, ccl : .c,Nph>N, formed when the quinone is reduced with stannous chloride, crystallises from glacial acetic acid in slender, pale red needles which melt and decompose at 217O; the diacetyl derivative forms colourless needles and melts a t 187". OH*Y:C(OH)*fi--N Phen ylaaiminochlwocutechol, C-J: c K-c. Nph >N, the other product of reducing the quinone, melts and decomposes a t 214-215". OH*fi-CO-fi--N Pheny luximinochlorohydroxy - p-pinone, CCl*CO*C*NPh>Ny pre- pared by the action of sodium carbonate on the dichloro-o-quinone, crystallises in lustrous, yellow needles which melt and decompose at 223O ; the acetyl derivative forms lustrous, yellow needles melting at 1 35-1 36", whilst the anilino-derivative, C18H,0,N,CI, and the eurhodol, C18HloON,CI, decompose at 180' and 200" respectively.Phenyl~ximinotetrcLketotet~~hyd~oben~~ne, co. c.Nph>N, obtained on oxidising the p-quinone with nitric acid, crystallises from the con- centrated acid in colourless needles which become yellow in light, and melt and decompose at 175' ; the diasine, C,,H,,N?, is sparingly solu- ble in common media, and melts above 260'. GO*CO* fl-N106 ABSTRACTS OF CHEMICAL PAPERS. OH*C*CO*C-N Phenylaaiminodihydroxy-p-quinone, oH.i.co. E.Nph>N, formed when the tetraketone is dissolved in sodium carbonate, is a red powder which gradually darkens above 200°, and melts, decomposing, at about 254'.Phe~~laximinodichlo~~otri~etotetr~hvdrobe~xene. yo-co f-h CCl 0* c10 C N P hyNt produced when chlorine ii passed into a solution of the chlorohydroxy- p-quinone in acetic acid, crystallises in small, white needles and melts, decomposing, at 150-151' ; the axine, C,,H,,0N,C12, crystallises from glacial acetic acid in grey, lustrous needles, which sinter above 210°, and decompose at 238'. prepared from the pentachloroketoni by the action of dilute sodium hydroxide, and of bleaching powder in either acid or alkaline solution, crystallises from alcohol in colourless needles melting at 148'; the sodizcm salt forms transparent prisms, and the methyl ester melts at 124'.1-Phenyl-1 : 2 : 3-triaxole-4 : 5-dicarboxylic (n-pheaylpywo-1 : 2-diaxole- N-$*C02H dicarboxylic, phenylcximinoethylenedicarboxylic) acid, N<Nph.C.CO,H' resulting from the oxidation of the foregoing acid with potassium per- manganate, has been already described by Michael (Abstr., 1893, i, 570). 1-Phenyl-4-dichloromethyl-5dichloroethylene-1 : 2 ; 3-triaxole (n-phenylimino-1 ; 2-dicczole-3-dichZoromethyl-4-dichloroethykne), N--R*CHCl, NqNPh*C*CC1:CHC1 ' produced when the monocarboxylic acid is heated alone or with acetic anhydride, crystallises from glacial acetic acid and melts a t 95-96'. The a8-diketocarboxylic acid, N<Nph.&CO.CHCI, , prepared by the action of sodium carbonate on the dichlorotriketone, crystallises in lustrous, colourless needles which darken above 105', and melt and decompose at 130'; phenylhydrazine converts i t into the diphenyt- hydrazone, C2,H,,02N7C1, which forms reddish-brown, crystalline granules sintering above 110'.4Methyldeoxyxanthine and Deoxyheteroxanthine. By JULIUS TAFEL and ARTHUR WEINSCHENK (Ber., 1900, 33, 3369-3377, Compare Abstr., 1900, i, 121 ; ii, 588).-When 4-methylxanthine is dissolved in 50 per cent. sulphuric acid and reduced electrolytically a t 1-14' between prepared lead electrodes with a current concentration of 120 amperes, the sulphate of 5-oxy-4-methyl-6 : 7-dihydropurine (4-methyl- deoxyxanthine) separates ; this salt and the p'crute were analysed, The base itself crystallises with 1H,O, and decomposes at 210-220° without melting ; although neutral in reaction to litmus, it dissolves in dilute alkalis. It is oxidised by bromine in acetic acid solution N-C*CO*CO,H M. 0. F.ORGANIC CHEMISTRY. 107 (lead peroxide is not suitable) to 5-oxy-4-methyZpurzne ; this base and its sui'phate and picrate were prepared, and the last two were analysed. Heteroxanthine was also reduced in the manner just described ; in this case no sulphate separates. The product, 5-oxy-1-methyl-6 : 7- dihydropukae (deoxybeteroxanthine), decomposes at 260-264' without. melting ; i t is feebly alkaline to litmus, and does not dissolve in dilute alkalis ; the hydyochloride, sulphate, and picrate were prepared and analysed. The base is oxidised either by lead peroxide or by bromine, in acetic acid solution, to 5-oxy-I-methylpurine (E. Fischer, Abstr., 1899, i, 175). C. F. B. Isomeric Change of Azoxybeneene. By EUGEN BAMBERGER (Ber., 1900, 33, 31 92-31 93).-TYhen azoxgbenzene is converted into p- hydroxyazobenzene by warm sulphuric acid (Wallach and Belli, Abstr., 1880, 556), a very small quantity of o-hydroxyazobenzene is formed and may be isolated by the process already described (see following abstract). A. L. Action of Diazobeneene on Phenol and Synthesis of o-Hydr- oxyasobenzene. By EUGEN BAMBERGER (Ber., 1900,33,3188-3192j.. - 0-Hydroxyazobenzene is obtained in small quantity by the action of diazobenzene on phenol and may be separated from the para-derivative by distillation with steam and purified by means of its copper salt, which is very sparingly soluble in alcohol. It is identical with the substance obtained from nitrosobenzene (Abstr., 1900, i, 531). 0-Jlethoxyaxobenxene, OMe*C,H,*N,*Ph, is obtained on adding o-anis- idine to nitrosobenzene dissolved in acetic acid. It crystallises in groups of orange-red, compact needles melting a t 40-41°, dissolves readily in most organic media even in the cold, and is converted into 0-hydroxyazobenzene by aluminium chloride. 0-Hydroxybenaeneuzo-p-toluene, OH*C,H,*N,*C,H,Me, produced in small quantity when p-diazotoluene reacts with phenol, crystallises from boiling water in thin, shining, irregular yellow tablets or leaflets with a bronzelustre melting at 100-105°. It dissolves readily in or- ganic solvents and sparingly in water. Its solution in alkali is orange- red. The copper salt, which is sparingly soluble in boiling alcohol, forms brown, silky needles which have a green, metallic lustre. On reduction with zinc dust and aqueous ammonium chloride, the dye is converted into o-aminophenol and p-toluidine. A. L. Composition of Proteids. By ALBRECHT KOSSEL and W. KUTSCHER (Zeit. physiol. Chem., 1900, 31, 165-214).-An important contribu- tion to proteid chemistry, but which hardly admits of abstraction. Impor- tant quantitative results concerning the way in which different frac- tions of the nitrogen are combined, and the yield of such decomposition products as amino-acids, ammonia, hexon ba.res, &c., are given, to- gether with quantitative methods. Protaniines, proteids proper, and albumjnoids are all brought under review. W. D. H. Decomposition Products of Proteids. By FR. KUTSCHER (Zeit. physiol. Chm., 1900, 31, 214-226).-Hausmann's method (Abstr.,108 ABSTRACTS OF CHEMICAL PAPERS. 1899, i, 653; 1900, i, 317) of determining the way in which the nitrogen is combined in proteids is untrustworthy. NOTE BY ABSTRACToR.-This has been pointed out previously by Y. Henderson (Abstr , 1900, i, 265). The Carbohydrate Group of Crystallised Egg-Albumin, , By LEO LANCSTEIN (Zeit. physiol. Chem., 1900, 31, 49-57).--It is shown that the reducing substance which can be obtained from crystallised egg-albumin is glucosamine. The direct action of concentrated mineral acid on egg-albumin does not split off the reducing substance, because of the simultaneous production of ammonia. After treat- ment with alkali, as Pavy first showed, the reducing substance is obtainable. W. D. H. The Phosphorus of Nucleins. By ALBERTO ASCOLI (Zeit. physiol. Chem., 1900, 31, 156--160).--Neither in leuco-nuclein nor in casein is any of the -phosphorus contained in the form of meta- phosphoric acid. W. D. H. A New Decomposition Product of Yeast Nuclein. By ALBERTO ASCOLI (Zeit. physiol. Chem., 1900, 31, 161--164).-Thymin has been obtained from the nucleic acid from thymus, spleen, salmon sperm, and herring roe. The amount of materal hitherto obtained from yeast nuclein did not admit of analysis. In the present research, thymin was obtained by W. Jones’ method (Abstr., 1900, i, 572) from thymus, and a similar material from yeast nuclein ; the latter substance was not thymin, but uracil. Constitution of Thymin. By H. STEUDEL (Zeit. physiol. Chem., 1900, 30, 539-541. Compare Abstr., 1900, i, 467). When thymin is methylated by Hoffmann’s method (Abstr., 1890, 31) a product, C,H,Me,O,N,, is obtained which is isomeric with Behrend’s trimethyl- uracil (Abstr., 1886, 339). It crptallises from alcohol in needles melting at 153’. When thymin is nitrated and then reduced, a substance is obtained which gives Weidel’s reaction with chlorine water and ammonia ; the author concludes that the presence of a pyrimidine ring in thymin is thus established. ‘W. D. H. W. D. H. J. J. S. Antipeptone. By FR. KUTSCHER (Ber., 1900, 33, 345’7-3460).- A polemical paper in reply to Siegfried (this vol., ‘i, 57). J. J. S. Expressed Yeast-cell-plasma (Buchner’s Zymase). By EDUARD BUCHNER (Ber., 1900, 33, 331 1-3315).-The author criticises several of the numerical results obtained by Macfadyen, Morris, and Rowland (thisvol., i, 59), and points out that the considsrable amount of autofermentation obserred by them was probably due to the presence of glycogen in the juice. The juice obtained by the author underwent very little autofermentation, the amount of carbon dioxide thus evolved being always less than one-tenth of that evolved in the presence of sugar. A. H.