i 129 Organic Chemistry. The Lubricant and Asphaltic Hydrocarbons in Petroleum. C. P. ~ B E R Y (Ind Eng. Chem. 1923 15 1233-1238).-Most crude petroleums begin to show evidence of decomposition a t a temperature of 300" even at 20 mm. pressure. In an investigation of the hydrocarbons boiling above this point applied to samples of crude petroleum of varying origin separation was therefore effected by means of fractional solution in a mixture of ether and ethyl alcohol. The fractions so obtained were examined as to density mol. weight (as determined by solution in stearic acid a t m") and composition by analysis. In all cases these heavy hydro- carbons fall into one of two classes ( D ) hydrocarbons lubricants throughout and ( H ) hydrocarbons of which the heavier are asphaltic. The latter are usually poorer in hydrogen the series identzed through the whole range of samples varying from C,H to C,H,,-m.The halogens react normally with these hydro- carbons. The nitro-derivatives of the (0) hydrocarbons separate as finely divided crystals those of ( H ) hydrocarbons as oils when poured into water. These derivatives have much lower mol. weights than the original oils and are nitro-carboxylic acids. All samples of fractions from American petroleum were found t o contain carb- oxylic acids or esters in proportions ranging from traces up to 2%. This probably accounts for irregular variations in the density of succeeding fractions. Iodine number determinations show that only the ring type of unsaturation exists in lubricant hydrocarbons.The Processes of Dehydrogenation in the Presence of Catalysts. J. K. PFAFF and R. BRUNCK (Ber. 1923 56 [ B ] 2463-2464).-The catalyst is prepared by mixing solutions of sodium aluminate and nickel nitrate and rendering the precipita- tion complete by passing carbon dioxide to saturation The paste is mixed with pure ignited aluminium oxide filtered and washed as free as possible from alkali. It is subsequently dried and reduced by hydrogen a t 320". In the presence of this material benzene is smoothly hydrogenated a t 180-200° to hexahydrobenzene but unexpectedly the latter substance is not reconverted into benzene to more than a minimal extent a t any temperature below about 500'. Purified lignite tar oil b. p. 80-150' is similarly readily saturated with hydrogen a t 180-200' but under the conditions used in the attempted dehydrogenation of hexahydrobenzene the product is converted quantitatively into methahe.Under similar conditions a purely aliphatic fraction of American petroleum yields almost entirely methane and leaves a small carbonised deposit on the catalyst; the reaction commences a t about 240" and is almost quantitative at 260'. [a. B. Feb.] c. I. VOL. CXXTV. i. fi. 130 ABSTRACTS OF CHEMICAL PAPERS. By means of the nickel catalyst the aliphatic components can readily be removed as methane from a mixture of aliphatic hydro- carbons and naphthenes. H. W. Addition of Nitrogen Trichloride to Unsaturated Hydro- carbons. I. G. H. COLEMAN and H. P. HOWELLS ( J . Amer. Chem. Soc. 1923 45 3084-3089; cf A. 1922 i 133).-Nitrogen trichloride was added slowly to a solution of Ap-butene in carbon tetrachloride a t -lo' and after washing and removal of water the p-chloro-y-dichloroaminobutane formed NCb*CHMe*CHMeCI was reduced by concentrated hydrochloric acid to p-chloro-y-amino- butane NH,=CHMe*CHMeCI ; the benzoyl derivative colourless needles m.p. 105-106' was isolated. Similar reactions with Aa-butene rzsulted in the isolation of r-a-chloro-p-benzamido- butane slender silky needles m. p. 91-92' which was reduced to r-p-benzamidobutane m. p. 84-85'. The latter subsfance was also prepared from methyl ethyl ketoxime and it had the same melting point (Pope and Gibson T. 1912 101 1702). @-p-Nitrobenzamidobutane obtained from Aa-butene and from methylethylketoxime melted a t 114.5-115.5".. Nitrogen tri- chloride reacted rapidly with p-methyl-As-butene ; no amine was produced but amylene dichloride and chloroamylene chloride were formed. F. B. Acetylene Condensations. 11. The Theory of the Form- ation of Cuprene. H. P. KAUFMANN and W. MOHNHAUFT (Ber. €923 56 [B] 2533-.2536).-The conversion of acetylene into cuprene in the presence of copper or copper compounds at 230- 300' does not take place in the complete absence of oxygen. The product is not homogeneous the composition varying between (CllHlo)z and (Cl,H,o),. In addition small amounfa of oily compounds are produced. The colour of the product ranges from pale yellow to dark brown. The authors consider that its formation is due to the production of an intermediate additive compound of acetylene with cuprous or cupric oxide which immediately undergoes pyrogenic decomposition.Possibly the variafion in temperature due to the rapid stream of gas plays a distinct part. Since the oxide which is regenerated by decomposition of the acetylide again takes part in the reaction the proportion of oxygen present (in the case of copper) need not be great. The formation and decomposition of the acetylide explains the peculiar observation that the copper catalyst which originally lies a t the bottom of the vessel ultimately becomes distributed throughout the whole reaction chamber. The superiority of copper over other metals as a catalyst is ascribed to the possibility of the simultaneous production of oxide and acetylide. The liberated acetylene must be endowed with particular reactivity as a consequence of which the reactions whidh occur are much more profound than those involved in the pyrogenic decomposition of acetylene alone and lead through the most stable forms of combination to the in- active cuprene the purely aromatic nature of which is thus readily explained (cf.Kaufmann and Schneider A. 1922 i 245). H. W.ORGANIC CHEMISTRY. i. 131 Process for Converting Halogen Substitution Products of Hydrocarbons into Hydrocarbons or other Halogen Substitution Products of Hydrocarbons containing a Higher Number of Carbon Atoms. FARBWERKE VORM. MEISTER Locms & BRUNING (Brit. Pat. 196272).-The process consists in passing halogen substitution products of hydrocarbons or mixtures of them in the presence of water over a catalyst com- prising metals (e.g. platinum) or their compounds (e.g.thorium oxide zirconium chloride bismuth oxide sfannic chloride zinc chloride) or non-metals (e.g. charcoal) carried on porous materials {particularly active charcoal) at an elevated temperature not exceeding 400”. Details are given for the production of ethyl chloride and ethylene from methyl chloride and of ethylidene chloride from a mixture of methyl chloride and methylene chloride. iCY. B. Feb.]. E. DEISS (2. Elektro- chrn. 1923 29 586-587).-!L’he ignition temperature of ethyl chloride lies below -18*5” the lower limit of explosion for mixtures of air and ethyl chloride is found with the mixtures containing 3.6% of ethyl chloride the upper limit being the mixture containing 11.2% and the maximum explosion occurs with 6.5% of ethyI chloride.J. F. S. Auto-oxidation of Chloroform. A. M. CLOVER (J. Amer. Chem. Sm. 1923 45 3133-3138).-When chloroform was exposed to diffused light it developed acidity and oxidising power. The latter reached a maximum and then decreased whilst the acidity continued to increase. On dilution with water the oxidising substance reacted to form hydrogen peroxide. The oxidising substance is probably dichlorocarbon peroxide CO,CI,. The addition of petroleum alcohol phenol and many other substances inhibits the decomposition of chloroform but the mechanism of their action remains obscure. Bromoform and methylene chloride also develop oxidising substances on standing. The Synthesis of Higher Members of the Aliphatic Series from Carbon Monoxide F.F’ISCHEE and H. TROPSCH (Fy; 1923 56 [B] 2428-2443).-An examination of the pos- sibhty of the conversion of water gaa into motor spirit. In the presence of a suitable catalyst carban monoxide is reduced by hydrogen to a mixture of alcohols ketones aldehydes etc. which is designated “synthol.” It is converted when heated under pressure into a mixture of hydrocarbons to which the name “ synthin ” is assigned. In a somewhat similar manner the direct production of hydrocarbons from mixtures of carbon monoxide and hydrogen has been patented by the Badische Aniljn- & Soda- Fabrik (D.R.-P. 293787 295203 and 295202) ; the dif3erent course of the reaction is possibly due to the fact that technical water gas containing carbon dioxide and an excess of hydrogen over carbon monoxide is used in the experiments now described whereaa in the work of the Badische Anilin- & Soda-Fabrik the carbon mon- oxide W~EI invariabIy in excess.W. T. K. B. Some Constants of Ethyl Chloride. F. B. f 2i. 132 ABS'JJRACTS OF CHEMICAL PAPERS. [With W KEtiiNxa.J-Technica1 water gas is freed as far as possible from compounds of sulphur compressed at 150 atmospheres and heated at 400-450" in the presence of iron covered with potassium carbonate; the product of the reaction separates into an aqueous and an oily layer in the volume proportion 2 1. A marked difference in the components of the two phases is not observed. Each consists of fatty acids aliphatic aldehydes ketones and alcohols; in addition the oily layer contains esters and hydrocarbons in small amounts.The presence of formic acetic propionic and isobutyric acids is established. Higher fatty acids are also present which have not been identified individually; as judged by equivalent and boiling point acids of the formula C,H,,O are produced. The presence of propaldehyde probably n-butaldehyde and isobutaldehyde is established whereas form- aldehyde could not be detected. The ketones comprise acetone methyl ethyl ketone diethyl ketone and methyl n-propyl ketone. Methyl ethyl and n-propyl alcohols are identified in addition to higher homologues. The esters have not been identified. Hydro. oarbons are present only in minor amount (about 2%). The conversion of synthol b. p. 99-225" into synthin is effected under pressure a t 400450" in an autoclave in an atmo- sphere of nitrogen.The liberated gas consists of carbon dioxide (14*5%) hydrocarbons soluble in fuming sulphuric acid (2207%)~ oxygen (o.7y0) carbon monoxide (14.6%) hydrogen (9.6%) paraffin hydrocarbons (21*8y0) and nitrogen (16-1y0). The liquid product consisfs mainly of hydrocarbons which boil over a wider range than the initial material. They are stable towards con- centrated sulphuric acid and therefore saturated. The atomic ratio C H increases from the fractions of lowest to those of highest boiling point. Whereas in the former this ratio is nearly 1 2 as is required for the simpler naphthenes in the latter its value indicates that only saturated hydrocarbons with several condensed ring systems can be present. Possibly the process consists in the initial conversion of the alcohols by loss of water into olefines which become further subdivided into small portions which unite to form naphthenes.The theory of the experiments is discussed in detail. It is pointed out that the presence of a hydrogen carrier such as iron nickel cobalt or possibly manganese is essential in addition to a base or the salt of a base with a weak acid. Apparently the production of oil is favoured by the strength of the base which however by ifself (e.g. potassium hydroxide in the presence of pumice) is not sufficient. It appears most probable that the initial product is formaldehyde which in the absence of bases passes into methane; in the presence of the latter however it becomes converted into methyl alcohol as is established by the production of large amounts of the latter from paraformaldehyde and hydrogen a t 400" under 100 atmospheres in the presence of pumice loaded with potassium carbonate.Methyl alcohol is converted by carbon monoxide either directly or through methyl formate into acetic acid the stepwise reduction of which givesOMANIC CHEMISTRY. i. 133 acetaldehyde and ethyl alcohol whilst its catalytic decomposition gives acetone. An extension of this operation yields propionic acid propaldehyde n-propyl alcohol and diethyl ketone. The non-production of members containing more than seven or eight carbon atoms is due to their instability under the experimental conditions. The production of higher alcohols is probably due to loss of water from the simpler members of the series.H. W. Alcohols and Hydrocarbons from Beeswax. GASCARD and G. DAMOY (Compt. rend. 1923 177 1442-1443; cf. this vol. i 8).-The following alcohols (2 and 4 in largest quantity) have been obtained from beeswax after alkaline hydrolysh (1) Neowyl C25H520 m. p. 75.5"; (2) ceryl C2,H5,0 m. p. 80'; (3) rno&tw& C,H,,O m. p. 84". and (4) myricyl aleoh&* Cs m. p. 87". After cryst&llising the alcohols the following gl carbons were obtained from the mother-liquors Pentacosane C25H52 m. p. 54-5445" ; heptacosane C27H56 m. p. 59.2-59.5' ; nonacosane C29H60 m. p. 63.5" and hentriacontane C,,H m. p. 68-449". All the acids alcohols and hydrocarbons obtamed from beeswax crystallise in hexagonal plates. Aa-Pentene-y-ol [Ethyl Ally1 Alcohol].J. BAU DRE NGJTIE x (Bull. Xoc. chim. Belg. 1923 32 337-339; cf. A. 1922 i 710; also Delaby A. 1923 i 741).-The following physical constants are given b. p. 114.2-114-4"/753 mm. dJ" 0.8373 n$ 1.4254. Dry hydrogen chloride is absorbed by the alcohol yielding a mixture of products one of which believed to be CH2:CH*CHEtC1 has b. p. 93-94"/759.8 mm. dy 043978 ng 1.4254. This sub- stance reacts with potassium acetate with formation of a mixture of isomerides. Hydrogen bromide gives with the alcohol a product b. p. 124-131" which is very unstable. Molecular Conductivity of Potassium Iodide in Epichloro- hydrin. N. A. YAJNIK and B. R. SOBTI ( J . Amer. Chem. SOC. 1923 45 3138-3139).-The molecular conductivity of potassium iodide in epichlorohydrin was determined by the Kohlrausch method. The results are mol.volume (litres) 60 120 240 480; specific conductivity 10 mhos 2-3 1.3 0.8 0-53 ; mol. conductivity (mhos) 13-8 15.6 19.2 25.4 respectively. Carbohydrates and Polysaccharides. V. Use of Acetylene for the Synthesis of Cyclic Acetals. H. S. HILL and H. HIBBERT ( J . Amer. Chem. Soc. 1923 45 3108-3116; cf. A 1923 i 439 753).-The following cyclic acetals were prepared by passing acetylene into a mixture of a polyhydroxy-compound and a small amount of mercuric sulphate with 93% sulphuric acid. Ethylidene trimethylene ether b. p. 108-1 ll" ethylidene a@- propylene ether b. p. 92"; ethylidene glycerol bromohydrin b. p. 170-182" ; ethylidene glycerol b. p. 189-196" ; ethylidene u8-tetramethylene ether a colourless hquid b.p. 124-127" ; ethyl- idene p h c o l b. p. 133-134" ; P-methyl~ntane- p8-diol ethylidene ether b. p. 139-140" ; monoethylidene a-methyl glucoside silky E. E. T. H. J. E. F. B.j. 134 ABSTRACTS OF CHEMICAL PAPERS. colourless crystals m. p. 77" and ethylidene glucose. The mechanism of the reaction is discussed. Carbohydrates and Polysaccharides. VI. Relative Eass of Formation of Five- and Six-membered Heterocyclic Carbon-Oxygen Configurations. H. S. HILL and H. HIBBERT ( J . Amer. Chem. Soc. 1923,45 3117-3124; cf. preceding abstract). -When one equivalent of acetylene was passed into a mixture of one equivalent of ethylene glycol and one equivalent of tri- rnethylene glycol the proportion of ethylidene ethylene ether (five-membered ring) to ethylidene trimethylene ether (six- membered ring) was 1 2. A similar result was obtained in the case of a mixture of propylene ap-glycol and trimethylene glycol whilst with a mixture of ethylene glycol and p-methylpentane- p6-diol the ratio was 1 5 .Using a mixture of trimethylene glycol and p-methylpcntane-p6-diol the ratio of the two six-membered ring derivatives was 1 2. Thus the six-membered ring compound was formed in preference to the five-membered ring compound and the presence of methyl groups attached to the glycol carbon atoms favours ring formation. Similar partition experiments with F. B. mixtilres of glyceG1 and ethylene glycol-led to the Gonclusion that ethylidenc glycerol consists of a mixture of CHMe\ /O*YH*CH2*OH O*CH - and CHMC<~:~~~>C!H*OH the latter predominating.&F. €3. Carbohydrates and Polysaccharides. VII. The Ease of Formation and Nature of certain Six- Seven- and Larger Carbon-Oxygen Cyclic Structures. H. S. HIr,L and H. HIBBERT (J. A?ner. Chena. Xoc. 1023 45 3124-3132; cf. pre- ceding abstract).-Thc partition of one equivalent of acetylene between one equivalent each of ethylene glycol and tetramethylene giycol shows that the five-membered cyclic acetal is formed three times as readily as the seven-membered compound. Attempts to prepare the cyclic ethylidene derivatives of octa- and deca-methylene glycols resulted in syrupy odourless acetals with very high and indefinite boiling points. The tendency of atomic chains to assume spiral ring formation is discussed. Preparation of Chloroethylsulphuryl Chloride.CKEMISCFE F-~BRIK VORM. WEILER-TER MEER (D.R.-P. 374141 ; from Chem. Zentr. 1923 iv 'i20).-Ethylenc chloride is treated with fuming sulphuric acid with or without a catalyst and the resulting chloro- ethy?suZphuryZ chloride a colourless heavy oil with an odour like that of formaldehyde b. p. 130-122"/80 mxn. is obtained by first separating through addition of ice-water and then distilling in a vacuum. Dichlorodiethyl szrlphate b. p. 1SO-lS2"/60 mm. is also obtained. G. W. R. Noteworthy Behaviour of Organic Sulphur Compounds towards Sodium Arsenite. A. GUTMANN (Ber. 1923 56 [ B ] 2365-2367) .-The mode of Combination of sulphur in certain organic (and inorganic) compounds can be distinguished by their 3'. B.ORGANIC CHEMISTRY. i. 136 behaviour towards sodium arsenite.Those which convert the arsenite into sodium thioarsenate Na,AsSO contain sulphur in the polysulphide form ; these also convert cyanide into thiocyanate ; those compounds which through- the intermediary action of water oxidise the arsenite to arsenate contain sulphur in the persulphide form corresponding with the peroxide form of oxygen. Di- xanthogen disulphide diacetyl disulphide and cupric sulphide all belong to the first class ; tin disulphide and ultramarine however contain sulphur only in the bivalent form and are not reactive. Diamyl disulphi de diphen yl disulphide dit hio -N- dimethylaniline and phenyl ethyl disulphide all oxidise arsenite to arsenate and are reduced to mercaptans; they contain one atom of persulphide sulphur. Methyl trisulphide with sodium arsenite gives both arsenate and thioarsenate and is reduced to methyl mercaptan; it therefore contains one atom each of polysulphide- and persulphide- sulphur.The free thiocyanogen of Soderbacks (A. 1920 i 219) and the phenylthiolthiocyanate of Lecher and Wittwer (A. 1922 i 641) both contain 1 atom of persulphide sulphur whilsf the disulphur dithiocyanate of tlhe same authors contains 2 atoms of polysulphide and 1 atom of persulphide sulphur. When cupric thiocyanate is heated with sodium arsenite a green precipitate is first formed which on boiling changes into red cuprous oxide arsenate being formed. In acid solution white cuprous thio- cyanate and arsenate are formed. In this reaction the formation of cuprous salt is not due to the redycing action of the arsenite; this is oxidised to arsenate by the thiocyanic acid formed when the cupric salt is heated.The Stereoisomerism of Brassidic and Erucic Acids D. HOLDE (Ber. 1923 56 [B] 2405).-A claim of priority in this field zgainst von Auwers (cf. A. 1923 i 294). A New Unsaturated Fatty Acid in Sperm and Dolphin Oils. M. TSUJIMOTO ( J . Chem. Ind. Japan 1923 26 608-620).-By the bromo-ester method of Griin and Janko (2. deut. Oel-Fett Ind. 1921 553 572) and the lead salt-light petroleum method a new tetrndecenoic acid C14H2602 has been isolated from sperm and dolphin oils the amount being about 3% of the material The acid was found to be chiefly responsible for the iodine absorption of the lower fractions of the methyl esters. It is a colourless liquid b. p.172"/5 mm. d:F 0.9079 1.4566 iodine value 106.8 (methgl ester b. p. 140"/5 mm. barium salt a white powder) and gives myristic acid C,4H2802 by reduction with hydrogen in the presence of platinum black and dihydroxymyristic acid C,,H,,( OH),02 m. p. 118-119" by oxidation by Hazura's method. By oxidising with potassium dichromate and sulphuric acid the acid gave nonoic acid. On treating the acid with ozone in a chloroform solution an ozonide peroxide C!,H2,O2 was obtained as a viscid colourless liquid the decomposition of which with water gave nonaldehyde nonoic acid glutaric acid semialdehyde ( ?) and glultaric acid. From these facts it is concluded that the formula is CH,*[CH,],*CH:CH*[CH2]3*C0,H. K. K. E. H. R. E. H. R.i. 136 ABSTRACTS OF CHEMICAL PAPERS.Preparation of the Highly Unsaturated Acids of Fish Oils. M. TSUJIMOTO and KANESUKE KIMURA (J. Chern. In&. Japan 1923,26,891-893).-The lithium salt-acetone method of Tsujimoto (A. 1921 i 78) for the separation of highly unsaturated acids is applicable to the quantitative analysis of the acids but unsuitable for the preparation of the acids owing to the need of large amounts of acetone and lithium hydroxide; a modification of the method is therefore proposed for the latter purpose. The fatty acids from fish oil (10 g). are dissolved in acetone (95 c.c.) neutralised with ammonia and mixed with an aqueous solution of the equivalent amount of lithium acetate or chloride the sulphate not being suitable for the purpose owing t o its smaller solubilify in water.The amount of water is kept such that the resulting acetone solution is of 95% strength. It is well shaken for thirty minutes and then cooled in ice-water for one hour. Highly unsaturated acids are dissolved chiefly as ammonium soaps and the lithium salt acts as the precipitant for less unsaturated acids. The solution is filtered through a dry filter-paper in a cold funnel. After evapor- ation of the solvent the residue is treated with a dilute mineral acid and thus highly unsaturated acids are isolated. The yield of the acids by this method is less than that by the peroxide method but the properties of the products are almost the same. K. K. The Decarboxylation of Dimethylpyruvic Acid and its Preparation. H. K. SEN (Biochem. Z. 1923 143 195-200).- Dimethylpyruvic acid (a-ketoisovaleric acid) was obtained by the following process used in preference to the method described by Rassow and Bauer (A.1909 i 632). Ethyl isopropylacetoacetate was treated with dry ethyl nitrite gas in the presence of sodium ethoxide and from the resulting sodium derivative the oxime of ethyl dimethylpyruvate was obtained and purified by distill- ation in a vacuum. From the oxime dissolved in 85% formic acid and treated with nitrosyl sulphuric aeid ethyl dimethylpyruvate together with the free acid was obtained. Hydrolysis of the ester with 5% aqueous potassium hydroxide yielded dimethylpyruvic acid boiling a t 76-78"/11 mm. The semicarbazone (prismatic needles) had m. p. 102-103". Dimethylpyruvic acid in the presence of phosphate buffer mixt,ures is fermented by preparations of dried yeast to give isobutaldehyde in 50% peld A 75% yield of the aldehyde is obtained when the fermentation IS carried out in the presence of acetate and sodium sulphite.isoButyl alcohol is not formed in detectable amount. Keto-enolic Tautomerism. 11. The Combined Applic- ation of Chemical Methods to the Estimation of -01s. H. P. KAUFMANN and G. WOLFF (Ber. 1923 56 [B] 2521-2526; cf. A. 1922 i 985 ; 1923 i go).-Fission of the dienolic form of ethyl diacetylsuccinate by ozone a t a low temperature gives rise to acetic and oxalic acids alcohol and ethyl diketobutyrate. The course of the reaction is explained by assuming that ozonisation occurs a t only one double bond and that the product then suffers fission The reaction is studied quantitatively by estimating the J.P.ORGANIC CHENISTRY. i. 137 oxalic acid produced in the form of calcium oxalate. Fission of the semi-enol by means of ozone occurs in a similar manner and gives rise to the same products. On the basis of these observations it is possible to investigate the equilibrium of ethyl diacetylsuccinate dissolved in hexane carbon tetrachloride or ether. The proportion of a$-ester is determined by the bromine titration method; the colormetric estimation with ferric chloride gives the sum of a-ester and a,p-ester whereas the fission by ozone gives the sum of all the enols (each of which gives a molecular proportion of oxalic acid). The examples which are cited show that chemical methods in t-hese instances lead to results which cannot be obtained by physical means.The relative proportions of the three enols can be estimated with sufficient exactitude but there is no process available for est,imating directly the proportion of the ketonic form. Starting from the @-ester numerous investigations of the equilibria of diacetylsuccinic ester in various solvents have been made. The main difficulty in establishing an exact relationship between the velocity of transformation and the proportion of the enol consists in obtaining absolutely pure solvents free from catalytically active substances. It is however certain that equilibrium is established most rapidly and that the keto-forms predominate in liquids of high dissociating power. Thus in the presence of water the (3-variety is remarkably favoured and all the isomerides are converted into it on contact with water.In nitromethane (e=39.4) a small proportion of the a,p-ester (4.0%) but no other enol is present. In the series of the alcohols the a,@-ester is capable of existence; in addition the a,@-compound is present to a considerable extent (42% in ethyl alcohol). In solvents of smaller dissociating power such as hexane the relationships are displaced greatly towards the other side. The p-ester is not present in appreciable amount and the small percentage of ketonic form exists as the ).-ester. The proportion of a,p-ester recedes whereas that of the a,p-compound attains 50% and the dienolic form is capable of existence. The slight dissociating power of hexane carbon tetrachloride and ether influences markedly the rate of transformation of the isomerides. Loss of the enolic hydrogen atom which takes place instantaneously from the dienol rapidly from the semi-enols in the presence of solvents of higher dielectric constant becomes so retarded thaf even the very strongly acidic dienolic variety is preserved.The primary formation of the a,@-ester in the establishment of all equilibria is very distinct. Equilibrium in the System Calcium Oxalate-Dilute Hydro- chloric Acid. E. CARRIARE and M. AUMBRAS (Compt. rend. 1923 177 1288-1290).-The equilibrium in the system calcium oxalate4ilute hydrochloric acid has been studied by observing the disappearance of the calcium oxalate precipitate a t a certain concentration of acid. Four influences are studied (1) that of concentration of oxalic acid produced ; by plotting concentrations of hydrochloric acid against those of oxalic acid an almost straight line is obtained; (2) that of temperature the concentration of H.W f*i. 138 ABSTRACTS OF CHEMICAL PAPERS. hydrochloric acid is roughly proportional to the solubility product of calcium ortalate a t different temperatures; (3) that of excess of calcium chloride the concentrations of hydrochloric acid are approximately proportional to the square root of the concentra- tions of calcium chloride; (4) that of excess of oxalic acid the concentrations of hydrochloric acid are roughly proportional to the square root of tlhe concentrations of oxalic acid. The Catalytic Bromination of Aliphatic Acid Chlorides. W. F. GOEBEL ( J .Amer. Chem. Soc. 1923 45 2770-2771).- a-Bromoanhydrocamphoronyl chloride (Bredt A. 1895 i 242) is prepared as follows. Anhydrocamphoronic acid is warmed with phosphorus pentachloride until the reaction ceases a small quantity of iron powder is then added and while the mixture is heated on the water-bath bromine is slowly added; the heating is then con- tinued for forty-five minutes and t,he mixture allowed to cool. The crude product (yield 75%) is purified by washing with dry The Supposed Autoxidation of Cysteine. 0. WARBURG and S. SAHUMA (Ppiiqer’s Archiv 1923 200 203-206; from Chem. Zentr. 1023 iii 1290; cf. A 1923 i ll).-The autoxidation of cysteine described by Abderhalden and Wertheimer consists in reality of the oxidation and reduction of a metallic cysteine corn- pound.G. W. R. The Oxidation of Hydrocarbons with Special Reference to the Production of Formaldehyde. V. The Slow Oxid- ation of the Higher Liquid Saturated Hydrocarbons. T. S. WHEELER and E. W. BLAIR ( J . Soc. Chem. I d . 1923 42 491- 497~).-Experiments on the oxidation of hexane were made using a method previously described (A. 1923 i 1175) in which the hydrocarbon mixed with oxygen is passed through a hot tube. The temperatures used were 480° 520° 540° and 590° the time of heating being 2 sec. The products obtained included higher aldehydes unsaturated hydrocarbons formaldehyde acids in small quantity carbon monoxide carbon dioxide hydrogen- a t higher temperatures and water. In presence of excess of oxygen much of the hexane consumed appears as higher aldehydes just as with other hydrocarbons except methane (cf.T. 1923 123 2079). The amount of carbon dioxide formed also increases when more oxygen is used and as the rate of oxidation of the hexane does not increase as fast as would be expected from the law of mass action it is clear that surface action is predominant. As the temperature increases less of thB higher aldehyde appears in the product but more formaldehyde unsaturated hydrocarbon carbon monoxide and carbon dioxide. The unsaturated hydrocarbon at all temperatures is mainly ethylene and the higher aldehydes tend towards acetaldehyde with increasing temperature. No saturated hydrocarbons appear in the products showing that thermal decom- position of the liexane does not occur appreciably otherwise methane would appear in quantity.The results are discussed in connexion E. E. T. ether and then recrystallking from benzene. w. s. N.ORGANIC CHEMISTRY. i. 139 with those obtained by other workers and the probable course of the slow oxidation of hydrocarbons generally is shown diagmm- matically. E. H. R. Condensation cf Aldehydes to Esters by Aluminium Ethoxide. W. C. CHILD and H. ADKINS ( J . Amer. Chern. Xoc. 1923 45 3013-3023).-During an investigation on the con- densation of acetaldehyde t o ethyl acetate using aluminium ethoxide as catalyst it was found that the latter existed in two forms. When prepared by the method of Wislicenus the a-form only was produced and this solidified at a little above the ordinary temperature; it was partly converted into the P-form in.p. 140" on distillatlion. The P- was completely converted into the or-form by heating in a sealed tube at 275" for fifteen hours. Both forms had the same catalytic activity being more active than Henle's ethoxide (A. 19.20 ii 446). The presence of water in the catalyst or in the aldehyde was detrimental. The effect of the addition of a third substance on the rate of reaction was studied and the results show that alcohols containing fewer than six carbon atoms are inhibitors methyl alcohol being the most effective whilst tlic chlorides of aluminium mercury calcium and zinc are promoters. The addition of increasing amounts of aluminium chloride was accompanied by increasing yield of ethyl acetate to a certain value ; further increase in the amount of promoter caused a decreased pro- duction of ester and an increase in the rate of paracetaldehyde formation. The reaction apparently takes place in a homogeneous system and the exclusion of light has no effect.The temperature coefficient of the reaction in xylene solution is approximately I 630 for a rise of 10" in the vicinity of the ordinary temperature. F. B. The Activation of Hydrogen in Organic Compounds. E. H. USHERWOOD (Chemistry and Industry 1923 42 1246- 1251).-The presence of activated hydrogen in an organic com- pound may be recognised by a number of properties among which may be mentioned cliad or triad tautomerism ability to form i?ietallic derivatives and capacity for alkylation. The ability of a compound to take part in an ddol reaction a Michael reaction / / [HI-C- +>C=C< + [H]-&-t]-Cy or a T h o r p reaction \ I I ./ / [HI-CK + [H]-N=C-C ivay also he taken as I cviclence of the presence of an activated hydrogen atom indicated above in square brackets. The phenomenon of tautomerism may be regarded as due to the migration of an activated hydrogen atom within the mo!ecule thus >C[H]-&O >&=CO[H]. There is a strong formal resemblance between this reaction and the aldol reaction >C[H]X + >C:O >CX-&O[H] and this resemblance is intcmsified by a recent demonstration that the aldol reaction is reversible. Keto-enol tautomerism may therefore be I p 2i. 140 ABSTRACTS OF CHEMICAL PAPERS. regarded as an intramolecular aldol reaction. There is a similar analogy between three-carbon tautomerism and the Michael reaction. The structural conditions necessary for the activation of a hydrogen atom to give rise to the above phenomena may be provisionally embraced in two formulae (1) The hydrogen atom represented by fH] in the group [HIC-X is activated no matter whether X is C or N; (2) The hydrogen atom in the group [H]C-X=Y or [HIGC-XY is activated no matter whether X is C or N provided Y is either the electronegative 0 N or S or is C which itself is iiivolved in the group =C-X=Y or =C-X-Y.The benzene nucleus considered as a Kekule individual forms a special case of the second rule and it enters into a number of reactions which show that it possesses an activated hydrogen atom. A number of such reactions are discussed including the addition of benzene to cinnamic acid the conversion of p-imino-y-cyano-or-phenylpropane into 1 3-naphthalenediamine and Skraup’s quinoline synthesis.E. H. R. Production of Acetone by the Action of Potassium Acetate on Acetic Anhydride. E. LUCE (Compt. rend. 1923 177 1306-1 309) .-When an equimolecular mixture of potassium acetate acetic acid and acetic anhydride is heated under reflux for thirty hours in a Path kept at 170-180” some acetone and carbon dioxide are formed. Equimolecular mixtures of potassium acetate and acetic acid or of acetic anhydride and acetic acid when similarly treated give practically no acetone. An equimolecular mixture of potassium acetate (100 8.) and acetic anhydride how- ever gives 12-32 g. of carbon dioxide corresponding with a con- siderable production of acetone most of which is lost by polymeris- ation or evaporation.If the acetone is allowed to distil as fast as it is formed about 24% of the theoretical quantity (see below) is obtained. This type of rearction was observed first by Perkin (T. 1886 49 317) whose explanation has now been confirmed. Thus when a mixture of potassium butyrate and acetic anhydride interacts acetone and methyl propyi ketone are formed as would be expected from the decomposition of the intermediate compound OK*CPP (OAc) whereas if the reaction were due simply to the decomposition of the acid anhydride acetone alone would result whilst interaction (with elimination of potassium carbonate) of 2 mols. of alkali salt would only lead to the formation of dipropyl ketone.Keten and Methyl- keten. C. D. HURD ( J . Amer. Chem. Xoc. 1923 45 3095-3101; cf. A. 1911 i 30’7).-Acetone vapour was decomposed by contact with a hot platinum wire filament but the yield of keten was not so good as in the method previously described (A. 1923 i 1060). Both methyl ethyl ketone and diethyl ketone gave a mixture of methylketen and keten. The presence of keten in the product from diethyl ketone must be due to the decomposition of methyl- keten. F. B. E. E. T. Ketenic Decomposition of Ketones.ORGAXIC CHEMISTRY. i. 141 Oxidation of Carbohydrates. J. STIEGLITZ (Proc. Inst. Ned. Chicccgo 1916-1917 1 41-50).-1n the oxidation of dextrose an intra-atomic phenomenon involving the loss of electrons by the carbon atoms and essentially like that of an element the productioii of an electric current has been observed.The presence of alkalis causes great acceleration and of acids retardation ; the former condition yields decomposition products more readily oxidised than dextrose itself. There is evidently some fundamental specific factor probably the oxidising enzymes having a paramount influence on the physiological processes of oxidation of carbo- hydrates. CHENICAL ABSTRACTS. Sources of the Rare Sugars XI. Preparation of Man- nose. XII. Preparation of Inulin. T SWANN HARDING (Sugur 1923 583-585 636-638) .-Mannose.-A modification of the method of Hudson and Sawyer (A. 1917 i 321) is described Ivory sawdust is mixed with its own weight of sulphuric acid (76y0) hydrolysed as directed by Hudson and Sawyer (Zoc. cit.) and barium carbonate added until the reaction is neutral to Congo- red paper.After adding sufficient phosphoric acid to impart a slight acidity using the same indicator and also some decolorising carbon the liquid is filtered. Basic lead acetate is added to the filtrate which is concentrated to a thin syrup in a vacuum and treated with twice its volume of alcohol. After further concen- tration and the addition of a little glacial acetic acid crystallisation is readily effected the mass obtained being diluted with alcohol containing 1% of nitric acid and the sugar filtered and washed with the acid-alcohol on a Buchner funnel. Lastly it is dried in a vacuum at the ordinary temperature ground finely and the drying continued for twenty-four hours while gradually raising the temperature to 46" mannose free from acetic acid thus being obtained. Indin.-A mixture of 1,OOO g.of finely ground chicory root and 5 litres of water is boiled for one hour filtered and the residue washed with hot water. The filtrate and washings are treated at 40" with basic lead acetate using a slight excess over that required for the precipitation of the impurities decolorising carbon is added the excess of lead thrown down with hydrogen sulphide and the liquid filtered After concentrating the filtrate to about 500 c.c. and adding twice its volume of SOYo alcohol the mixture is allowed t o remain over-night when 10-15 per cent. of inulin will deposit. This is dissolved in 1,000 C.C. of 40% alcohol treated with decoloris- ing carbon and filtered.Two volumes of SOYo alcohol containing 1% of nitric acid are added the liquid is left over-night at a low temperature and the inulin obtained dried in a vacuum at about 35" and reprecipitated. G . R ~ ~ ~ ~ W I T A N O and M. CATOIRE (Cmpt. rend. 1923,177,1309-1311).-A 1% aqueous solution of potato starch was obtained (heating not above 80°) the cooled product consisting of two layers then being diluted to one-tenth of its original concentration and the clear portion J. P. 0. Solubility and Insolubility of Starch.i. 142 ABS!l'RAOFS OF CHEMICAL PAPERS. evaporated. The gelatinous stapch separating did not give a clear solution with boiling water and on being dried merely swelled when so treated. After washing with water and then with alcohol the product (containing like the original material combined phosphorus calcium magnesium and silicon) resembled cotton dissolving in water only when heated at 150" with the latter and being reprecipitated on cooling.On treatment with acids etc. it gave a product resembling soluble starch. It is concluded that the solubility of starch depends on the inorganic matter present starch itself b e g amylaceous matter combined with phosphates and silicates (of calcium and magnesium) Starch Paste. I. Relation between the Viscosity of Wheat Starch Paste and the Concentration and Temperature. MORIZO YOSHINO ( J . Chem. Ind. Japan 1923 26 870-873).- The viscosity was measured by Ostwald's capillary viscosimeter at 20° 30° 40° and 50" for the range of concentration of 0.5- 2.5%. The relation between viscosity and concentration is expressed with sufficient accuracy by Arrhenius's formula log q/qo= 8C where C=lOOp/[lOO-(n+l)p] p being the number of grams of starch in 100 grams of paste and n the hydration factor.The amount of water absorbed decreases according to the elevation of temperature. The values of 8 and n were observed to be as follows 0.412 and 12.6 at 20" 0.407 and 10.0 at 30" 0.407 and 7-6 at 40° and 0.408 and 5.7 a t 50". When the values of p become 7.4 at ZOO 9.1 at 30° 11-6 at 40" and 14.9 at 50" the viscosity becomes infinite ; that is the solution changes into a solid. K. K. Cellulose. VIII. K. HESS W. WELTZIEN and E. MESSMER (Annalen 1923 435 1-144).-( A ) Cuprammonium-cellulose solutions E. MESSMER [and in part (FRL.) ELLY J A G u ] .- I t has already been shown (A. 1921 i 401) that the copper is present in cellulose-cuprammonium solutions as an optically active com- plex anion and as (kation) an ammine. The solutions have now been examined further from a mass-action point of view and the molecular complexity of the dissolved cellulose has been deter- mined. In order to make such a determination trustworthy the following points had to be proved (1) Cellulose (in cuprammonium solutions) undergoes no hydrolytic decomposition. This is clearly the case since the maximum rotation for a particular concentration is reached immediately dissolution of cellulose is effected. (2) The rotation is due to a single complex copper compound of high rotatory power. This is shown by the form of the rotation curves (concentration of components of solution against rotation etc.).Moreover a maximum rotation is observed when the solution con- tains 1 atom of copper to 1 mol. C,H,,O,. (3) The copper complex is in equilibrium with very weakly rotating cellulose (the latter functioning in dissolving as a base). This is shown by other curves connecting rotation and concentration of copper. A slight excess (1 mol.) of copper is necessary to drive back the dissociation of the complex. When excess of copper is present addition of E. E. T.ORGANIC CHEMISTRY. i. 143 cellulose within limits causes a rectilinear rotation-increase curve. (4) The (reacting) copper is used entirely to give the strongly rotating complex. This is shown by studying the effect of sodium hydroxide which does not increase the rotatory power of the solution (see equation 2 below).( 5 ) The copper dissolves unimolecularly. This is shown by a parallel investigation of dextrosemonoacetone (below). The above relations are expressed by the equation mCu+ n(C6H1005) Cellulose-copper Complex and since it has been shown ( 2 above) that an atom of copper corresponds with C6H1005 in the given solution m=nz. The formation of a cellulose+mprammonium solution is expressed by the following equations (1) In absence of alkali cellulose is dissolved by cuprammonium hydroxide (a) (C6Hlo05),(solid) + the complex of high rotatory power) [C6H905],[Cu(NH,),]+ (2) In presence of alkali (which takes the place of cuprammonium hydroxide) Na[ C6Hs05] + [Cu( NH3),]( OH) =+= [ C ,H ,05Cu]Na + 4NH3+2H,O.The equations (1) and (2) may be summarised thus [C,Hs05]'+ [Cu ( NH3),]'*+ 20H' =$= [ C6H ,O 5Cu]'+ 4NH3+ 2H,O. (3) In presence of excess of alkali [C,H905]Na+ [C,H,O,Cu]Na + c6 9 5cu Na (the last formula relating to the copper-sodium-cellulose complex precipitated in presence of excess of alkali). Since in equation (1) above the copper has two functions the investigation of this solution will throw little light on the question at issue. In presence of alkali (2) however the copper has only one function. If a=rotatory powet of the copper complex a and b are respectively the total number of copper atoms and C6f-I,005 units present in volume v and x is the number of C6HlOO5 umts m the combined cellulose then for the interaction of m atoms of copper and n molecules of cellulose K the reaction constant is given by K=(a/v-m .a . k)m(b/xv-nak)"/a. k. Various values (1 to 4) were taken for m 72 and x and k and K determined whence knowing a and b a could be calculated. Approximate agreement between a (found) and a (calc.) was only obtained f o r (1) n=m=x=l (2) n=m=l x=2 (3) n=2 m=3 x=1 and (4) n=3 m=4 z=1. Of these possibilities (2) (3) and (4) are excluded on other (experimental) grounds as is also the possibility of expressing (1) as n=m=x=2 (i.e. 2Cu Cl$€mO1o -i.e. cellobiose) or as n=m=x=3 and so on. From the above it follows that in cuprammonium solutions of cellulose (say one containing 28 mols. of cellulose 15 mols. of copper and 25 mob. of sodium hydroxide) cellulose reacts as if it possessed the molecular formula C6HlOO5.The correctness of this conclusion was established in other ways. Thus solutions containing z mob. of cupric hydroxide and y mols. of celluloee gave the same rotation as solutions containing y mols. of cupric hydroxide and z mols. of cellulose. [Cu(NH3),I(OH) * 2H,0+ [C6H905],[Cu(NH,)*] ; ( b ) (giving 2[Cu(NH3),] (OH )z * [c6H,05cu],[ cu(NH3)4] + 8NH3 + 4H@- rf?:7:5 1i. 144 ABSTRACTS OF ClHEB6ICAL PAPERS. Experiments were also carried out (cf. A. 1921 i 401) with cuprammonium solutions of other carbohydrates or their deriv- atives. Cellobiose had [a]435.8 +50*6O +50*6" and +160*Oo in aqueous in ammoniacal sodium hydroxide and in sodium hydr- oxidwuprammonium solutions respectively. The investigation of the solutions is rendered difficult because of mutarotation oxidation etc.a-Methylglucoside in the above three solvents had [a]p35.8 +324" +340" and +460". The tendency of the glucoside to form copper complexes is very strong. Although for this reason the equilibrium relationship could not be experi- mentally investigated clear evidence was obtained that the in- creased rotation of the cuprammonium solutions was due to a complex 1 glucoside 1 copper p-Methylglucoside in the above three solvents had [ Q ] ~ ~ ~ . ~ -57.4" -53-3" and +38.1" re- spectively. The quantitative study of the cuprammonium solutions of the last three compounds is complicated by the rotation possessed by these compounds. In the case of dextrose monoisopropylidene ether which had in the above three solvents -24.8" -31.6" and -212.5" respectively the equilibrium was amenable to experi- ment and the existence of the complex containing 1Cu C,H,,O definitely established. Moreover the molecular weight of the dissolved dextrose monoisopropylidene ether was determined as in the case of cellulose and also by direct cryoscopic measurement in aqueous solution when a normal result was obtained.Dextrose monopropylidene ether was found to have m. p. 1606-161" [XI -12.12" (cf. Fischer and Rund A. 1916 i 363). Laevoglucosan gives no complex in cuprammonium solutions the rotation in the latter being the same as that of an aqueous solution. (B) The acetylation of cellulose (W. WELTZIEN [and in part R. SINGER H. JENSEK and A. R~~]).-whilst dried cotton cellu- lose does not react with pure dry acetyl chloride cotton cellulose containing 6 5 % of moisture when shaken for four days with eleven times its weight of acetyl chloride a t 17-20' is converted (92% yield) into crude cellulose triacetate A .I€ the cooled solution obtained is allowed slowly to lose the hydrogen chloride present evaporated in a vacuum the residue treated with chloroform and the latter evaporated a solution of the second residue in glacial acetic acid then being precipitated with ether pure cellulose triacetate A is obtained as a pale yellow or colourless powder (607h yield). If in the original acetylation the conditions are varied by-pro- ducts (formed in the above preparation in small quantities) viz. cdMextrin acetate and acetochlorocellobiose are obtained in larger quantities although they are readily separable from cellulose triacetate A .The acetylated celluloses described by Skraup (A. 1906 i 67) and by Zechmeister (A. 1923 i 306) are mixtures (In connexion with the analysis of cellulose acetates a modification of the Ost and Katayama and the Wenzel method is described steam vacuum distillation being used. A diagram of the apparatus used is given.)ORGANIC CHEMISTBY. i. 143 Cellulose triacetate A has m. p. 270-275" (decomp. with brown coloration and frothing) is soluble in chloroform and acetic acid and insoluble in alcohol or ether Dissolution is preceded by swelling. Cellulose triacetate A has [.ID -16.7" in chloroform and + 4 4 " in glacial acetic acid. Its solutions in the latter solvent throw little light on its molecular weight a consfant depression being obtained for all solutions containing between 0.03 and 0.3% of the acetate whilst irregular results are obtained with higher concentrations. The constant depression obtained with low con- centrations may be due to the presence of water (cf.Patern6 and Salimei A. 1913 ii 849). In phenol cellulose triacetate A gives a mol. weight value of 2,380-3,350 (with a specimen obtained in a slightly different manner 2,030-2,270). Ost's cellulose acetate (in phenol) had a variable mol. weight (2,037-10,133). On treat- ment with a mixture of acetic and sulphuric acids Ost's cellulose acetate became more like cellulose triacetate A . Thus whilst originally its product of alkaline hydrolysis was practically in- soluble in alkali after the acetic-sulphuric acid treatment the hydrolysis product was soluble in alkali.Cellulose triacetate A on treatment with cold N-methyl-alcoholic sodium hydroxide affords cellulose A readily soluble in 2N-sodium hydroxide the solution affording cellulose A on acidification. Cellulose A is a white powder with [.ID (in 2N-NaOH) -12.4". It is shown by X-ray analysis to be crystalline whilst its rotatory power in cuprammonium solutions establishes clearly its structural identity with the original cotton cellulose used An alkaline solution of cellulose slowly undergoes hydrolysis reducing properties developing. In the methyl-alcoholic alkaline hydrolysis (above) a little of the reducing substances is formed and is removed by treating the alkaline solution with ammonia when pure cellulose A is precipitated. In this connexion it is found that the Schwalbe copper number does not always give trustworthy comparisons of reducing power.A method based on the precipitation of the cellulose to be tested as the sodium-copper derivative (above) is described. Pure cellulose A a'nd hydrocellulose (as prepared by Knoevenagel and Busch A. 1922 i 636) show no reduction with the improved method the crude products showing feeble reduction. Ost's cellulose acetate after acid treatment (as above) was feebly reducing whilst cellodextrin acetate and the acetyl derivative obtained by treating cellulose with acetyl chloride at 24-27' were strongly reducing. By effecting the acetylation of cellulose with acetyl chloride in presence of acetic anhydride which decreases the concentration of hydrogen chloride (Ac,O+HCl t Ac-Cl+Ac*OH) a cellulose acetate was obtained which on hydrolysis gave a cellulose less soluble in alkali than cellulose A .Cellodextrin acetate is a white amorphous powder m. p. 260" (softening at 250°) [a]? -11.0 (&2.0)" [a]:" -12.0 (-+1*5)" in chloroform. It is more soluble in solvents than is cellulose triacetate A . It gives a molecular weight in acetic acid of 318- 1,366 in phenol of 1,260-1,480 in urethane of 1,500-1,540 andi. 146 ABSTRACTS OF CBEWCAL PAPERS. in naphthalene of 1,350-1,470. On hydrolysis with methyl- alcoholic sodium hydroxide it gives dextrin as a white powder which darkens without melting reduces Fehling's solution under proper conditions (above) and is converted by acetyl bromide containing hydrogen bromide into acetobromoeellobiose whilst acetic anhydride (and a trace of sulphuric acid) converts the dextrin into octa-acetylcellobiose (m.p. 228"). (c) Jfethykztion of Cdlulose A [w. Wn~~zr~,u.]-The methylation of cellulose as effected in presence of alkali (Irvine T. 1923 123 518) gives results of doubtful value owing to the definite action of alkali on cellulose a t the temperature of methylation. Cellulose A on warming with dilute alkali is so altered that it reduces Fehling's solution and is no longer precipitated on acidification. Hydrated barium hydroxide has no effect on cellulose A and methylation carried out using this hydroxide and methyl sulphate (at 90-95") may be assumed to proceed without effecting structural changes.The product obtained in this way was a yellow glass (OMe=30-40%) insoluble in and unaffected by alkali and on further methylation with sodium hydroxide and methyl sulphate (at 80-90") for three hours gave a product (OMe=4243y0) corre- sponding with trimethyl cellulose A . Further methylation (using silver oxide and methyl iodide or piperidine and methyl sulphate) was impossible. Trimethyl cellulose A is a white powder m. p. 230-245" (softening a t 217") dissolving in cold water and separ- ating on heating this solution owing to hydrate formation etc. It has [a]$ -18" in water and is inactive in chloroform solution. The freezing-point depression of an aqueous solution slowly decreased on keeping a result in accordance with the structural similarity of trimethyl cellulose A to cellulose A .It is concluded that the results obtained by Heuser and von Neuenstein (A. 1923 i 17) indicate that these authors mere dealing with a partly hydrolysed cellulose complex. ( D ) Action of Hydrogen Bromide on Cellulose triacetate A [K. HESS W. WELTZIEN and F. KuN~u.]-~e~u~ose triacetate A when treated in glacial acetic acid solution with hydrogen bromide gave acetobromocellobiose (yield 10-30 yo). No hexa-acetylbromo- cellobiose but EL little hepta-acetylbromocellobiose was also formed. Cellulose triacetate A is unaffected by acetyl bromide but ki presence of hydrogen bromide a 50 yo conversion into acetobromo- cellobiose results. There is also formed a new a.cetobromodwtrose (white amorphous powder m. p. 60-70" [indef.] [.ID +so") which does not yield penta-acetyldextrose when treated mth silver. acetate.The new compound does not depress the freezing point of bromoform has a normal molecular weight in acetic acid and in phenol and is (twice) associated in benzene solution. It affords acetobromocellobiose when treated with acetyl bromide containing hydrogen bromide. The acetobromodextrose is readily deacetylated by the method of Fischer and Bergmann (A. 1919 i 278) whereas acid hydrolysis caused the elimination of bromine with formation in very variable yield of a new substance ceUo- glucosan C,H,,O,,H,O plates m. p. 107-log" [.ID +89-31" inORQANIC? CHEMISTBY. i. 147 aqueous solution. The molecule of water is firmly attached and the suhtance (which is accompanied in its formation by a bromine- free amorphous substance) is not hygroscopic like some glucosans (below).TribenzoyZcehgZwoogEucosan. has m. p. 126-128". Cello- glucosan is unaffected by boiling alkali but affords reducing com- pounds on acid hydrolysis. It is quantitatively converted by methyl alcohol containing a trace of hydrogen chloride into a-methyl- glucoside a fact which is difficult to reconcile with Karrer's sug- gestion that cellulose is derived from p-glucose (A. 1920 i 370). Celloglucosan in many respects resembles glucosan (Pictet and Castan A. 1920 i 594) but unlike the latter substance does not reduce Fehling's solution. The rotation of an aqueous solution of celloglucosan is higher than that of a similar solution of glucosan but falls to the rotation of the latter if a little hydrochloric acid is added.The formation of the new acetobromodextrose which cannot like its previously known isomeride be obtained from cellobiose proves that cellulose may be converted into derivat>ives of dextrose without the intermediate formation of cellobiose. It is concluded (in a comprehensive survey of the whole of the work) that natural (cotton) cellulose is built up from glucose anhydride units which are associated not condensed or polymerised . The X-ray diagrams of natural cellulose and of the cellulose (shown to be a chemical individual) obtained by precipitating cupram- monium solutions suggest but do not prove the identity of these two products. Cellulose and cellulose A give identical values for k and K when examined by the above (cuprammonium) method whilst the hydrolysis product of Ost's cellulose acetate is also shown to be identical from the same point of view with cellulose.If 2 3 6-trimethylglucose is produced (Irvine Zoc. cit.) without structural change cellulose will be I- 0 . OHCH,CH.CH-CH( OH ).CH ( OH ~ C H . At variance with this formula however are the results of the action of hydrogen bromide on cellulose triacetate A . The authors prefer t o write cellulose as I in the scheme below when its dis- solution in cuprammonium solution (which effects satumtion of the partial valencies involved in the association of the sinzple cellulose units) is expressed thus +pu(NH3)4]"+30H' -f Lo o:~C6H7(O-)}~>Cu]'+3H,0 \ etc. Such a formula for cellulose explains its amphoteric character and its behaviour towards neutral salts such as zinc chloride.An interesting but probably misleading fact is the identity of the heats of combustion of cellulose and of laevoglucosan.i. 148 ABSTRACTS OF CHEMICAL PAPERS. Natural cellulose may contain as its crystal unit (cf. X-ray analysis) four C,H,,05 residues associated together. An important result also emerges cellobiose need no longer be regarded as a degradation product of cellulose the converse being nearer the truth. Comparative Investigations of Cellulose and Lignin. F. FISCHER and H. TROPSCH (Ber. 1923 56 [B] 2418-2428).- ,4 restatement and extension of the work carried out in the authors' laboratory during recent years The hydrogenation of cellulose and lignin by hydriodic acid uiider pressure does not appear to be suitable to the elucidation of the genetic relationships between the substances since the come of the change is not obvious and has led to very conflicting results in the hands of various workers.Cellulose is far more stable than lignin towards aqueous alkali hydroxide under pressure and at elevated temperatures. It is completely dissolved at 300" with production of much carbon dioxide. Lignin on the other hand is decomposed by 9.5N- potassium hydroxide solution at 300" with production of phenols or phenolcarboxylic acids and adipic acid and by 10N sodium hydroxide solution at 250" with formation of succinic and oxalic acids. Lignin easily becomes autoxidised in the presence of sodium hydroxide yielding humic acids non-volatile acids such as succinic.oxalic and ( ? ) isophthalic in addition to acetic formic and carbonic acids ; cellulose is comparatively little attacked. Similar differences are observed in the oxidation of the substances under pressure ; it is significant that whereas cellulose yields aliphatic acids aromatic acids are in addition obtained from lignin. The ready nitration of lignin by 5N nitric acid is in harmony with a phenolic structure. The comparative behaviour of cellulose and lignin when subjected t o distillation under diminished pressure is described in detail. The yields of coke and tar are widely different with the two com- pounds The most significant result however appears to be the absence of optically active compounds in the aqueous extracts of lignin tar whereas under like conditions laevoglucosan is obtained from cellulose.It appears therefore improbable that the ligniii molecule is composed of polysaccharide components Lignin-content of Spruce Wood. P. &ASON (Cellulose- chemie 1923 4 81-84).-The sulphuric acid method for the determination of lignin is recommended; easy filtration is secured by using a weaker acid than the 72% concentration prescribed by Ost and Wilkening; the washed lignin retains sulphuric acid but not in the form of a combination. About 1 g. of finely rasped wood is suspended in 50 C.C. of 64% sulphuric acid and allowed to remain over-night. The liquid is diluted and the residue collected on a tared filter then washed with cold or warm water. The resin and fat are extracted by washing with 50 C.C.of hot alcohol and the lignin is then neutralised with water containing 5 C.C. of .iV/lO-potassium hydroxide washed and dried a t 105'. E. E. T. H. W.ORGAMC CHE116ISTRY. i. 149 The correction for ash includes any sulphuric acid not removed in the washing. Calculated on dry substance the values for an eighty-year old spruce stem were l i p i n corrected for sulphate 29.4%; sulphuric acid 3.6%; resin and fat 101%. The lignin showed on analysis C 63.97%; H 5.32%; pentosans 1.7%. Another stem from the same forest but of one hundred years’ growth yielded only 26.6% of lignin. Deposits of “red wood” in the branches contained locally up to 37.1% of lignin. For the direct extraction of fat and resin from wood ether appears to be the best solvent free from drawbacks which accompany the use of benzene or alcohol. The benzene extracts always show reactions of lignin and the alcohol extract which is indefinite in quantity increasing with the time of extraction contains very substantial quantities of lignin and carbohydrates in about equal proportions. AS a rapid and approximate method for the determination of resin and fat the washing of the lignin residue after treatment with sulphuric acid may be considered to be satisfactory.Chloro-bismuthates. A. GUTBIER and MANFRED MUUER (2. anorg. Chem. 1923 128 137-152).-By treatment of one molecular proportion of bismuth trichloride with three molecular proportions of the hydrochlorides of organic bases in presence of hydrochloric acid three new series of compounds have been pre- pared viz.,.~-dichloro-octachloro-di~ismuthates [NHR3],[BiCI,]? of which the dimethylanilinium and diethylanilinium salts are descnbed p-irichloro-hexachloro-dibismuthates [NH3Rl3[B&Cl9] of which the methylammonium tetramethylammonium triethylammonium tetraethylammonium n-propylammonium tripropylammonium n-butylammonium isobutylammonium and isoamylammonium salts are described and hexachloro-bismuthates [RNH,],[BiCl,] of which the dimethyl- trimethyl- ethyl- diethyl- isopropyl- diim propyl- and allyl-ammonium salts the methyl- ethyl- and isoamyl- anilinium salts and the guanidinium pyridinium a-picolinium I?-picolinium lutidinium collidinium quinolinium and isoquino- h i u m salts are described. The first and second series may be regarded as hexa-co-ordination compounds by assuming the formulze given the two bismuth atoms being linked through two and three chlorine atoms respectively.All the compounds are extremely sensitive to changes in environ- ment and decompose at once in contact with water or moist air. The Derivatives of Hexachloro-antimonic Acid. A. GUT- BIER and W. H~USMANN (2. anorg. Chem. 1923 128 153-168).- By combination of antimony pentachloride with alkyl- and aryl- amines in hydrochloric acid solution a large number of com- pounds of the general formuh [R-NH3][SbC1,] [R$?Hz~[Sbc1,] [R,NH][SbCl,] and [R4N][SbC16] as well as pyridine and piperidhe derivatives have been prepared. They are moderately stable crystallking unchanged from hydrochloric acid in colourless well- formed crystals; they dissolve in water to colourless solutions which slowly become cloudy and deposit white precipitates but J.F. B. s. I. L.i. 1% ABSTRACTS OF CLEMICAL PAPERS. from alcohol solution they may be recovered for the most part unchanged. The moho- di- tri- and tetra-methylammonium salts the mono- di- tri- and tetra-ethylammonium salts the mono- di- and tri- propylammonium isopropyl- bhtyl- i.sobutyl- and diisobutyl- ammonium salts the allyl- isoamyl- and benzyl-ammonium salts the dibenzylethylammonium ethylenediammonium salts and the a-picolinium collidinium and piperidinium salts are described. s. I. L. Derivatives of Hexachloro-stannic Acid. A. GUTBIER G. KUNZE and E. GUHRING (2. anorg. Chem. 1923 128 169-178).- A series of alkylammonium arylammonium and pyridine and quinoline derivatives of the general formula X2[SnCI,] has been prepared.They are generally colourless and crystallise readily from hydrochloric acid solution. They dissolve readily in water hydrolysing slowly in the cold; the freshly prepared alcoholic solutions are neutral. Tripropylammonium hexachlorostannate [NHPr,],[SnCl,] crystallises in two forms one bright rose- coloured tablets the other deep reddish-brown leaflets. The following compounds are described the methyl- dimethyl- trimethy I- te tramethyl e thy1 - die t h yl- triet h yl- tetrae t h y 1 - normal and isopropyl- dipropyl- tripropyl- normal and isobutyl- diisobutyl- triisobutyl- allyl and isoamyl-ammonium salttj the ethylene- and propylene-diammonium salts and the anilinium Raneenographic Determination of the Structural Formula of Hexamethylenetetramine.H. W. GONELL and H. MARK (2. phpikal. Chem. 1923 107 181-218).-The crystal structure of hexamethylenetetramine has been investigated by means of X-ray spect>ra and Laue figures. It is shown that hexamethylene- tetramine does not belong to the hexakisoct'ahedral class Oh as has been assumed from macroscopic examination but more pro- bably it belongs to the hexakistetrahedral class Td or possibly to the tetrahedral pentagonal dodecahedra1 class T. The elementary cube has an edge 7-02 A. long and contains 2 mols. of hexamethylene- tetramine. Each nitrogen atom lies between the three nearest carbon atoms in close spherical packing. The shortest distances between neighbouring atoms in the molecule are N-C=1.48 A.and C-C=2.58 A. The lattice is a molecular lattice. The structure thus deduced confirms that found by Duden and Schadf (A. 1896 i 122) from purely chemical investigation according to which the molecule is built up of trimethylenetriamine rings. The present work furnishes an example where Rontgenographic investigation enables a decision between possible structural formulae to be reached when such has not been possible by purely chemical treatment. J. F. S. The Reactivity cjf Different Amino-acids in the Presence of Blood Charcoal and cf Hydrogen Peroxide. E. NEGELEIN (Biochem. Z. 1923 142 493-506).-Measurements pyridinium collidinium and quinolinium salts. -s. I. L.OIWKNIC CHEMISTBY. i. 151 have been made of the rate of oxidation in an atmosphere of oxygen and of the adsorption constants of various amino-acids in the presence of blood charcoal.The considerable variations found in &he former when equimolecular solutions of the vlllrious acids are brought into equilibrium with the adsorbent are ascribed to Werences in the extent of adsorption. In general primary and secondary amino-acids are much more reactive to oxygen in the presence of charcoal tha.n are the tertiary acids. Closely parallel results are obtained when the rates of oxidation of the amino-acids by activated oxygen (hydrogen peroxide) a t pH 9.2 are memured the tertiary acids being again much less reactive than the others. The similarity of the two types of oxidation lends support to the views of Warburg in which the oxidation of amino-acids in the presence of charcoal is ascribed to activated oxygen.The Configuration of Amino-acids. 11. P. KARRER (Helv. Chim. Acta 1923 6 957-959).-The conversion of d-serine into I - py-diaminopropionic acid shows that these must have the same configuration.. d-Serine was converted into its methyl ester which by the action of phosphorus pentachloride was converted into d- 7-chloro-p-aminopropionic acid as described by Fischer and Raske (A. 1907 i 900) for the corresponding I-compounds. The d-chloroaminopropionic acid was converted into I-diaminopropionic acid by heating with liquid ammonia. The product contained some racemate its rotation being [a] -18-1" instead of -24.9". It follows that I-serine must have the same configuration as d-di- aminopropionic acid which has been shown to correspond with I-asparagine and Z-aspartic acid (A.1923 i 660). It therefore follows that the following constituents of natural albumin all have the same configuration d-alanine I-serine I-cystine I-asparagine and E-aspartic acid. It would appear to be a general rule that naturally occurring amino-acids have the same configuration. Aliphatic Dialkylaminoalkyl Compounds. PARBWERKE VORM. MEISTER LUCIUS & BRUNING (U.S. Pat. 1429922; from Chem. Zentr. 1923 iv 591).-Additional data are given for com- pounds already mentioned (A 1922 i 529). Ethyl or-diethyl- aminoethylacetoacetate has b. p. 132-135"/10 mm. ethyl or-di- rnethylaminoethylacetoacetate b. p. I24"/12 mm. ethyl diethyl- aminobutylacetoacetate b. p. 138"/10 mm. J. P. E.H. R. G. W. R. The Electro-chemical Preparation of Cyanuric Acid and Allophanic Esters from Formamide. K. SCHATJM [with H. SCHNEIDER] (Bey. 1923 56 [B] 2460-2462) .-isoCyanuric acid is obtained when formamide is elect,rolysed between plattinurn elec- trodes a t a temperature not exceeding 45" with a pressure of 70 volts. A yellow substance the nature of which has not been elucidated is obtained as by-product; it is obtained in greater quantity if higher temperatures and current densities are employed. The electrolysis of mixtures of formamide and an alcohol leads to the formation of allophanic esters of which the methyl ethyl isopropyl and isobutyl compounds have been'prepared in goodi. 152 ABSTRACTS OF CHEMICBL PAPERS. yield. Apparently cyanic acid is formed intermediately either by discharge of a formamide-ion or by anodic oxidation of formamide ; the former process appears to predominate when small quantities of water are present the latter when the quantities are more con- siderable.The electrolysis of molten acetamide does not give well-defined products. H. W. Crotononitriles. A. BUELENS (Bull. Soc. chim. Bdg. 1923 32,334-337) .-Crotononitrile prepared by three different methods dehydration of a-hydroxybutyronitrile and of P-hydroxybutyro- iiitrile and catalytic transformation of ethyl crotonate by Mailhe's method (A. 1920 i 476) is obtained in each case as a mixture of tlhe two stereoisomerides that of higher b. p. predominating. In the tlhird case the author shows that isomerisation occurs during catalysis as the mixture is formed in the same proportions by submitting the isomeride of higher b.p. to the conditions under which catalysis is effected. H. J. E. The Vapour Pressure of Hydrocyanic Acid.. RYGSABUR~ HARA and HEIMA SHINOZAKI ( J . Chem. Ind. Japan 1923 26 884-890).-The vapour-pressure curve of hydrocyanic acid has been determined by Smith and Menzies's static isoteniscope method (A. 1910 ii 1036) within the range of 0 4 6 " . It is believed that the observed values are correct to &0.2%. The equation log Pmm- 1836-63/T1'U5 +7.5030 shows satisfactory agreement with the observations. For obtaining the pressure at any desired temperatures between O".and 47.5" the following two values observed were used for the above formula 519.4 mm. at 15.88" and 1128-4 mm.at 36.68". The boiling point of the acid was found to be 25.7" instead of 26.5" as generally accepted. Considering the acid as an ideal gas the heat of vaporisation of the acid was calculated from the Clausius-Clapeyron formula to be 246.4 cal. a t 0" 245.5 cal. a t 20" and 244.5 cal. a t 45". The results are tqabulated. K. K. Cacodyl Derivatives. F. A. LEE C. THING and W. M. DEHN ( J . Amer. Chem. Soc. 1923 45 2996-2998).-Cacodyl prepared by Bunsen's method is converted into the chloride b. p. log" which gives the bromide b. p. 130" the iodide b. p. 155-160" and the cyanide b. p. 138" when heated with the molecular pro- portion of potassium bromide iodide and cyanide respectively. Oxidation of the chloride with moist air gives hydrated cacodyl oxychloride m.p. 85". Cacodyl chloride reacts with mercurous and mercuric chlorides cuprous and cupric chlorides to form additive compounds which are described. Aliphatic Arseno-compounds. I. Arsenoacetic Acid and Tetra-arsenoacetic Acid. C. S. PALMER ( J . Amer. Chem. SOL 1923 45 3023-3029) .-The barium salt of arsinoacetic acid (AsO,Ba*CH,*CO,),Ba was quantitatively produced from chloro- acetic acid by reaction with excess of sodium arsenite; the reaction mixture was acidified with acetic acid the precipitated arsenic trioxide filtered off and the filtrate added to a solution of barium F. B.ORBANIO CEEMISTRY. i. 1.53 chloride. The barium salt was converted into the sodium salt and treatment of the latter with sulphuric acid and sodium hypophos- phite gave arsenatcetic acid C0,H*CH,*AsfAsCH,*C02H yellow crystals decomp.above 200". Simultaneous reduction of one molecular equivalent of arsenic trioxide and two of arsinoacetic acid in the cold gave tetra-arsenoacetic acid CO,H*CH,As:As*As:As*CH,*CO,H a vermilion red crystalline powder decomp. at 180". Preparation of Arsinic Acid Derivatives of Aliphatic Carboxylic Acids. FARBENFABRIKEN VORM. F ~ I E DR. BAPER & CO. (Austr. Pat. 93325 and Swiss Pat. 97977; from Chem. Zentr. 1923 iv 721).-Aliphatic halogen carboxylic acids or their derivatives such as amides or esters are treated with arsenious acid its derivatives or its salts in the presence of alkaline reagents. For example from chloroacetic acid and arsenious oxide arsino- acetic mid is obtained as colourless crystals m. p.152". Sodium arsenite and ethyl acetate give ethyl arsinuucetute light yellow leaflets m. p. about 95". Arsinolactic acid is a viscous yellow syrup obtained from p-chlorolactic acid and arsenious acid. Di- arsinuudipic acid from dibromoadipic acid forms colourless crystals m. p. 165" (decomp.). Phenylarsine oxide and chloroacetic acid give ursinophenyhcetic acid m. p. 145" (decomp.). Oxidation of Magnesyl [Magnesium Alkyl] Derivatives by Means of Hydrogen Peroxide. B. ODDO and R. BINAGHr (Atti R. Accad. Lincei 1923 [v] 32 ii 349-353; cf. A. 1922 i 314).-When oxidised by means of hydrogen peroxide magnesium sec. - and tert. -alkyl bromides yield the corresponding alcohols. Similarly phenols are obtained from magnesium aryl bromides with the exception of magnesium phenyl bromide and substituted hydroxylamines and per-acids from the products formed by replacing the active hydrogen of primary amines and of the carboxyl group by the grouping 1ClgBr. Treatment of magnesium phenyl bromide with hydrogen peroxide may give rise to the initial formation of phenol but the products recognised are phenyl ether p-hydroxyphenyl ether benzene diphenyl and possibly phenyl peroxide.With the other organomagnesium compounds however the oxidation proceeds normally and especially with compounds of t,he types R,:CH*MgBr and R3X*MgBr with such regularity in respect to time as to furnish fresh support to the view that only one of the oxygen atoms of hydrogen peroxide is quadrivalent and to strengthen the analogy in behaviour and constitution between the peroxide and formaldehyde (Zoc.cit.). Thus with hydrogen peroxide CHR,*MgBr + CHR,*O(:H,)-O-MgBr + CHR,*[OH,]*OH -+ CHR,*OH and CR,*MgBr --+ CR,*O(:H,)*O*MgBr + CR3*[OH,]*OH + CR,*OH and with formaldehyde CHR,*MgBr - CHR,*CH,*O*MgBr + CHR,*CH,*OH and CR,*iMgBr + CR,*CH,*O*RlgBr - CwCH,*OH. Ethyl hydroperoxide may be regarded as having the aldehydic structure O:OEt*H 60 that like the aldehydes it should yield F. B. G. W. R.i. 154 ABSTILWTS 0s CIHEXXCAL PAPERS. alcohols of the tliree series when treated with the three types of magnesium alkyl derivatives. Ethyl peroxide on the other hand having the ketonic constitution O:OEt should yield always secondary and tertiary alcohols. An outline is given of the experimental results which are to be published elsewhere.T. H. P. Behaviour of Mercuric Salts of Organic Acids towards Heat. M. S. KHARASCH and F. W. STAVELEY ( J . Amer. Chem. Soc. 1923 45 2961-2972); cf. A. 1922 i 189).-The behaviour of mercuric salts of substituted acetic acids on heating depends on the character of the substituting group. Thus mercuric ua-di- methylpropionate was not decomposed when heated in a vacuum at 240" for twenty minutes or when melted in air whilst the mercury salfs of phenylacetic diphenylacetic and triphenylacetic acid gave various products but none in which the mercury replaces a hydrogen atom attached to the u-carbon atom. The ease with which the salt loses carbon dioxide is an important factor. When mercuric ua-diethylacetoacetate m. p. 103" is heated in a vacuum at 85" carbon dioxide is evolved and mercury his-u-acetyl-a-ethyl- propyZ m.p. log" is formed. Treatment of this compound with mercuric chloride gives cc-acetyl-u-ethylpropylmercuric chloride CEt,Ac*HgCl m. p. 77". On heating mercuric dimethyl- acetoacetate in a vacuum a t go" mercury bis-u-atcetyl-a-iso~opyl m. p. 120" is produced. This gives a mercuric chloride compound m. p. 124.5". Mercuric aa-dimethylpropionate m. p. 235" did not give off carbon dioxide when heated a t 240" in a vacuum. When benzoylacetic acid and mercuric oxide are heated in alcohol solution mercury diphenacyl Hg(CH,*COPh) m. p. 159.5" is formed and this on treatment with mercuric chloride gives phenacylmercuric chloride m. p. 146" which is identical with the substance of known constitution prepared by direct mercuration of acetophenone (A 1902 i 849). When benzoylacetic acid and mercuric oxide are heated in chloroform solution the product is anhydro-u-hydroxy- co mercuribenzoylacetic acid COPh*CH< >0 decomp.290". On adding a solution of mercuric acetate to a solution of pht,halide- Hg carbogylic acid mercuric phthalidecarboxylate a ( CO<!~~CH*C02)2~g is obtained. This' reacts with sodium hydroxide to give phthalonic acid and phthalidecarboxylic acid and has m. p. 195" (decomp.) forming dihydrophthalide m. p. 250". Benzoyl- formic acid in alcohol solution reacted with mercuric oxide to form the mercurous salt which is decomposed by sodium carbonate. The mercuric salt m. p. 164" is obtained by adding a solution of mercuric acetate to a solution of benzoylformic acid.Fixation of Unsaturated ,Molecules by Metals produced from their Organometallic Derivatives. A. JOB and R. REICH (Cornpt. rend. 1923 177 1439-1441).-0n keeping a solution of F. B.ferrous ethyl iodide (cf. A. 1922 i 645) metallic iron is deposited as a mirror ethylene and ethane also being formed. These changes are explained by the following scheme 2FeEtI + FeEtz+Fe& - 2C2H4+FeH,+Fe12 + C$€4+C2Hs+Fe+Fe12 where ferrous hydride reduces ethylene to ethane. This explains why Wanklyn obtained ethylene and ethane from zinc ethyl and ferrous iodide. The iron deposit which contains traces of ferrous ethyl iodide is pyrophoric and decomposes water to give hydrogen. Nickel cobalt chromium and manganese are also produced in active forms from a halide salt and magnesium ethyl bromide part of the metal being precipitated the rest remaining in (colloidal) solution.Thus when an ether-benzene solution of magnesium phenyl bromide is treated in absence of air with nickelous chloride a solution is obtained which (1) rapidly absorbs carbon monoxide in amount corresponding with the formation of nickel carbonyl Ni(CO),; (2) slowly absorbs per atom of nickel 2 mols. of nitric oxide (giving a bluish-green solution) ; (3) absorbs ethylene (2 mols. for each atom of nickel) to give a reddish-brown solution; (4) absorbs acetylene (Ni 3C2H,) ; and (5) rapidly absorbs hydrogen (2H Ni) nickel hydride being precipitated as a black very reactive powder (cf. Schlenk and Weichselfelder Ber. 1923 56 [B] 2230). Organometallic Compounds.111. Compounds formed between Tin Alkyl Halides and Ammonia and the Amioes. C. A. KRAUS and W. N. GREER ( J . Amer. Chem. Soc. 1923 45 3078-3083).-Tin trimethyl chloride forms a compound with 1 mol. of aniline and with 1 mol. of pyridine (m. p. 37"). Tin trimethyl iodide combines with two equivalents of ammonia one of which is loosely held two equivalents of aniline and one equivalenb of pyridine. The compound with pyridine solidifies homogeneously at -17". Tin dimethyl dichloride combines with two equivalents of pyridine. Mercury ethyl chloride and mercury amyl chloride each combine with one equivalent of ammonia. Solutions of the metal alkyl halides in amines are fair conductors of electricity whilst the solutions in neutral solvents are virtually non-conductors. It is E.E. T. suggested that these compounds are &f the ammonium type C,H,.N<Sn(CH,),* P. B. I Organometallic Compounds. IV. Conductivity of Tin Trimethyl Chloride in Mixed Solvents. C. A. KRAUS and W. N. GREER ( J . Amer. Chern. Soc. 1923 45 2946-2954; cf. this vol. i 25).-The electrical conductivity of tin trimethyl chloride in nitrobenzene and acetone solutions on the addition of small amounts of pyridine has been measured. A marked increase in conductivity takes place on the addition of pyridine and this effect is greater the smaller the amount of pyridine already presenf; The conductivity of solutions of tin trimethyl chloride in mixtures of 0-100% of acetone and alcohol nitrobenzene and pyridine respectively has been measured a t 25".The initial conductivity in nitrobenzene is extremely low indicating that tin trimethyli. 156 ABSTRACTS OF CliEXICXL PAPERS. chloride is not much ionised in this solvent. The initial conductivity in acetone is markedly higher than in nitrobenzene. Whilst the conductivity in acetone is increased on the addition of alcohol this increase is much less marked than it is on the addition of pyridine. The results are in keeping with the view that tin trimethyl chloride itself is not a true electrolyte and that its electrolytic pro- perties in solution are due to the formation of compounds of the oxonium and ammonium type the tin trimethyl group transferring from chlorine to quadrivalent oxygen or quinquevalent nitrogen respectively . J. F. S. The Conditions of Equilibrium and Motion of Molecules in Space.J. BOESEKEN (Ber. 1923 56 [B] E2411-2414).- A discussion of the structures of cyclohexane and cycloheptane ring systems in which a theory previously put forward (Derx A. 1922 i 651) is restated. The proof by Schrauth and G6rig (A. 1923 i 1084) that dicyclohexane can exist in three forms'is important in this connexion. E. H. R. J. H. WALTOW and J. D. JENKINS ( J . Amer. Chem. Xoc. 1923 45 2555-2559).- The equilibrium curves for the system toluene-acetone-water have been determined experimentally a t O" 20" and 30". It is shown that temperature has very little effect on the mutual solubility of the three components. J. I?. S. Catalytic Condensation of Acetylene with Benzene and its Homologues. J. S. REICHERT and J. A. NIEUWLAND ( J .Amer. Chem. ~ o c . 1923 45 3090-3091; cf. A. 1923 i 753).-Diphenyl- ethane ditolylethane and dixylylethane were prepared by passing acetylene into benzene toluene and xylene respectively at 10- 20" in the presence of concentrated sulphuric acid and a mercuric sdt. Similarly dimesitylethane was prepared from mesitylene and ethylidinebisethylbenzene from ethylbenzene. The Disulphonation of Naphthalene. H. E. FIERZ-DAVID and A. W. HASLER (Helv. Chim. Acta l923,6,1133-1146).-Anextended account of work already published in brief (Fierz-David A. 1921 i 409 ; 1923 i 1190). 1 5-Naphthalenedisulphonic acid crystallises in well-formed monoclinic tablets containing 4H20 losing 2H20 in a vacuum at 55" and the remainder a t 125"; m. p. 240-245" (decomp.). It is soluble in 0.98 part of water a t 20° and is not deliquescent.Its salts with their solubilities in parts of water per part of anhydrous salt are as follows Li2+2H,0 monoclinic; Na,+2H20 monoclinic 9 ; K,+2H20 monoclinic 15 ; Rb Cs2 TI and (NH4)2 all anhydrous monoclinic ; Ca+2H20 triclinic 40; Sr+H,O monoclinic ( a) 96; Ba+H,O rhombic 470; 250 a t 100"; Pb+3H20 monoclinic 82; Mg (22) Zn (as) Co (46) Ni (73) Cu (21) all with 6H,O form an isomorphous monoclinic series. The sulpharnide forms small needles m. p. above 310" and the sulphaniZide has m. p. 248-249". Naphthalene- 1 6-disulphonic acid crystallises in large mono- clinic striated prisms wi6h 4H,O; it loses water gradually when Ternary System Toluene-Acetone-Water. 3'. B.ORGANIC CHEXlS!L'RY. i. 157 heated and melts a t 125" (decomp.). It is deliquescent in damp air.The sulphonamide has m. p. 297-298". The salts and their solubilities are as follows Na2+7H,0 3 ; K 5; (NH4),+2H,0 2 ; Ca+4H20 10; Sr+5H20 10; Ba+3iH20 16; Pb+4H20 12; all the foregoing are rhombic; Mg Zn (3) Co (5) Ni (5) all with 6H,O isomorphous rhombic Cu+4H20 2. Naphthalene- p-sulphonamide can be separated almost quanti- tatively from the a-compound or from disulphonamide by dissolving the mixed amides in 20% sodium hydroxide solution and cooling in ice when the sodium salt of the'p-sulphonamide crystallises out. The calcium salt of the 2 6-disulphonic acid can be precipitated quantitatively in the anhydrous form by heating its aqueous solu- tion alone or mixed with other calcium salts in a closed vessel a t 130".. E. H. R. The Diphensuccindene Series. V. Colourless and Coloured 9 12-Dialkyl-A~~~~-diphensuccindadienes. K. BRAND and F. SCHJAGER (Ber. 1923,56 [B] 2541-2545 ; cf. A.,'1912 i 960 ; 1920 i 486 487).-An extension of previous work to compounds containing alkyl instead of aryl groups in the 9 12-positions. Diphensuccindan-9 12-dione is converted by magnesium methyl iodide into 9 12-dimethyldiphensucindun-9 12-diol (annexed formula) colourless needles m. p. 170". It is converted by boiling formic and glacial &\-CHAh/4\ acetic acids into 9 12-dimethyl-AgJl-di- CMe*OH HO.CMe I \> phensuccindadiene $Mez~'C,H dark red fy\,i"CH- I l 1 I C,H,*C=CMe or yellowish-brown needles m. p. 212" which is hydrogenated in alcoholic solution in the presence of palladised charcoal to 9 12-dimethyZdiphensucindune colourless needles m.p. 94". 9 12-Diethyldiphensucindun-9 12-diol forms coarse colourless crystals m. p. 102". It is transformed by a boiling mixture of formic and glacial acetic acids into 9 12-diethylidene- diphensuccindune slender colourless needles m. p. 199.5" (which is oxidised by chromic acid to acetaldehyde and diphensuccin- dandione) and 9 12-diethyl-A9J1-diphensuccinda&iene red or red- dish-brown leaflets m. p. 154" (indefinite). 9 12-Dibenxyldiphen- succindan-9 12-dioZ small colourless needles m. p. 206" is con- verted by acetic and formic acids into a mixture of coloured 9 12-di- benzyl-A9Jf-diphensuccindadiene (which could not be isolated in the homogeneous condition) and 9 12-dibenxyZidenediphc- cindune colourless needles m.p. 255"; the latter substance is oxidised by chromic acid to benzoic acid and diphensuccindan- 9 12-dione m. p. 202". The Diphensuccindene Series. VI. 9 12-DinaphthyI Derivatives of the Diphensuccindene Series. K. BRAND and K. TREBINC (Ber. 1923,56 [B] 2545-2547 ; cf. preceding abstract). -Diphensuccindadione is transformed by magnesium a-naphthyl bromide in the presence of ether and benzene into 9 12-di-a- naphthyldiphensuccindan-9 12-did colourless needles m. p. 244" which is converted by a boiling mixture of acetic and formic acids H. W.i. 158 ABSTadCTS Or CEElKICAL PAPEBS. info naphthalene and diphensuccindan-9 1Edione. 9 12-Di-s- nqhthyldiph.mmmindi.vn-9 12-diol colourle~~ needles m. p.286- 287" is transformed under similar conditions into 9 12-di-p- nap~~yyl-Ag.ll-~iphensuccindadiene reddish-brown leaflets m. p. 266'. The hydrocarbon is oxidked by chromic acid to o-p-naphthoyl- benzoic acid m. p. 168" (cf. Pickles and Weizmann P. 1905 20 201) which is converted by concentrated sulphuric acid into 1 2-naphthanthraquinone m. p. 168"; it is hydrogenated in the presence of alcohol and palladised charcoal to 9 12-di-p-naphthyZ- diphemccindtzne slender colourless needles m. p. 225". Magnesium 2-methoxy-a-naphthyl iodide appears to react normally with diphensuccindandione but the action of water on the product gives naphthyl methyl ether and diphensuccindandione. Some Colouring Matters Derived from Bidiphenylen- ethylene. F. KEHRMANN and C. BUFFAT (Hdv.Chim. Acta 1923 6 955-956) .-The red hydrocarbon bidiphenylen- ethylene (A. 1896 i 565) is readily sulphonated by concentrated sulphuric acid forming a soluble sulphonic acid having an intense orange colour which dyes wool and silk in the same way as other acid dyes. The hydrocarbon can be nitrated in glacial acetic acid; fwo dinitro-derivatives were obtained one forming deep red granules sparingly soluble in alcohol m. p. 171" the other crystallising in orange-red prisms more soluble in alcohol m. p. 170". The nitro- compounds can be reduced to amino-derivatives which form orange- coloured hydrochlorides. E. H. R. W. A. DEMOXBREUN and R. E. KREMERS ( J . Amer. Pharm. ASSOC. 1923 12 296-300).- For the nitration of cymene 67 g. is added to an equal weight of sulphuric acid cooled with ice and the mixture is stirred until 0" is reached. A cooled mixture of 105 g.of sulphuric acid agd 50 g. of nitric acid is then added drop by drop with constant stirring? common salt being occasionally mixed with the ice. About six hours are required for the reaction. After being stirred for a further thirty minutes the mixture is poured into an equal volume of cold water. The oily layer is washed with water and fractionally dis- tilled the heavier fraction having b. p. 130-135"/14 mm. P 1.0355 nz 1.5290. Reduction by tin or iron and hydrochloric acid gave 2-aminocymene gB 0.9448 ng 16395 (hydrochloride m. p. 206-207"; acetyl derivative m. p. 70-71"). H. W. 2-Nitro- and 2-Amino-cymene. CHEMICAL ABSTRACTS. p-Naphthylamine-5 7- and -6 8-disulphonic Acids.H. E. FIERZ-DAVID and M. BRAUNSCHWEI~ (Helu. Chim. Acta 1923 6 1146-1151).-A number of salts of these two acids were prepared in the hope of discovering some method of separating the two acids superior to that previously described (Fierz &' Farbenchemie," 2nd ed. p. 43). Although a separation can be effected through the magnesium salts it offers no advantages. (3-Naphthylamine-5 7-disulphonic acid crystallises with 5H,OORGANIC C r n S T R Y . i. 159 in well-formed rhombic needles (from hydrochloric acid) or glisten- ing leaflets (from water). It loses its water completely at 150". The following salts are described with solubilities at 20" in g. per 100 g. of saturated solution Na2+6H20 felted needles which melt in the hand 72.2; NaH+4H20 rhombic needles 7.91; K,+2H20 rosettes of rhombic needlw 63.9; KH+4H2O short rhombic prisms 2-58 ; (NH4),+3H20 rhombic prisms 68.1 ; Ca+4H20 monoclinic prisms 40.2 ; Sr+4H20 29.48 Ba+3H20 22.7; the following all crystallise in well-formed rhombic needles or prisms Mg+8H20 21-09 ; Zn+8H20 39.4 ; Co+8H20 29.4 ; Pb+6H20 48-1; Ni+6H20 35.5.The solubility of the free acid is 22.97. @-Naphthylamine-6 8-disulphonic acid crystallises with 4H20 in small monoclinic needles solubility 9.24 g. per 100 g. of saturated solution a t 20". The following salts are described Na,+3H20 well-formed prisms 59.04 ; NaH+4H20 long thin needles 7-46 ; K2+2H,0 lustrous prisms 51.6 ; KH+2H20 long rhombic prisms 2.47 ; (NH4),+2H,0 monoclinic 70.35 ; the alkaline-earth metal salts are isomorphous monoclinic with 3H20,Ca 29.1 Sr 20.8 Ba 12.0; Mg+8H20 8.7 Zn+8H20 34-5; Co+8H20 27-96; Ni+6H20 monoclinic prisms 33.2 ; Pb+H20 44.5 aggregates of small needles. The preparation of the two acids from p-naphthylamine is described in detail Chloroamidines.PAUL ROBIN (Compt. rend. 1923 177 1304-1306) .-Alkali hypochlorites convert amidine hydrochlorides in aqueous solution into chloroamidines (cf. Bougault and Robin A. 1920 i 568). Thus benzamidine affords benzochloroamidine NH,*CPh:NCl or NHCl-CPh:NH colourless odourless needles not affected by heating up to 100". It may be crystallised from alcohol but when heated with this solvent a t loo" in a closed tube affords benzamidine and a volatile chloro-compound. With boiling dilute acids benzochloroamidine gives chlorine whilst with aqueous potassium iodide solution one mol.of the amidine gives 2 atoms of iodine. When heated with water at 100" in a closed tube the chloroamidine affords a mixture of cyaphenin (PhaCN) benzo- nitrile benzoic acid ammonia and benzamidine. Benzochloro- amidine does not react with antipyrine but is converted by acetic anhydride in boiling benzene solution into an acetyl derivative m. p. 122" in which the chlorine is still reactive towards potassium iodide. p-Tolylchloroamidine and benzylchloroamidine CH2Ph-CN2H2CI melt respectively a t 96" and 72". Preparation of Amidines. CHEMISCHE FABRIKEN VOW. WEILER TER MEER (D.R.-P. 372842 from Chem. Zentr. 1923 [iv} 661).-Acetanilide its derivatives homologues or analogous com- pounds with the exception of arylglycine anilides are treated with carbonyl chloride in the presence or absence of condensing reagents.The following reaction is typical 2NHPh*COMe+COCI,=HCl+ CO,+ COMe*Cl+ NHPh*CMe:NPh. The reaction proceeds amoothly E. H. R. E. E. T.i. 160 ABSTRAOTS OF CHEMICAL PAPERS. without the formation of by-products. Acetanilide and carbonyl chloride give &s above diphenylacetamidine hydrochloride. p-Acetotoluidide and carbonyl chloride yield pp'-ditoZ&cetamiidhe m. p. 122". 00'-Ditolylacetamidine forms flat needles m. p. 65". Acetyl compounds of the amines of alkoxylated or halogenatd hydrocarbons or of polynuclear or condensed hydrocarbons may also be used. a-Dinaphthylacetamidine is crystalline and has in. p. 137". Basic Derivatives of p-Aminophenyl Ethyl Ether.SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pats. 96389 96606 and 96607 ; from Chem. Zentr. 1923 iv 662-663).-p-Acetarnino- phenol halogenethyl ethers NHAc*C,H+*O.CH,*CH,X or their derivatives alkylated in the nucleus obtamed by acting on alkali acetamidophenoxides with ethylene dihalogenides are allowed to react with secondary aliphatic amines. p-Acetamidophenyl /I-brmethyl ether crystals m. p. 130" gives with diethylamine p-acetamidophenyl p-diethylaminoethyl ether; the hydrochbride forms small needles m. p. above 200". p-Acetamidophenyl p-bromoethyl ether gives with piperidine p-acetamidophenyl 2-piperidylethyl ether ,- the hydrochloride forms crystals m. p. 252". From 4-acetamido-2-allylphenyl p-chloroethyl ether crystals m. p.W" and diet hy lamine 4 -a cetnmido- 2 - a1 1 ylphen yl p -dieth ylaminoeth y 1 ether m. p. 70° is obtained; its hydrochloride is crystalline and has m. p. 149". G. W. R. Methyl Sulphites of Secondary Aromatic Aliphatic Amines. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (Austr. Pat. 93319; from Chem. Zentr. 1923 iv 802; cf. Bockmiihl and Windisch A 1923 i 29).-The compounds obtained by earlier patents may also be prepared by N-alkylation of the methyl sulphites obtained from primary aromatic amines and a hydrogen sulphite compound of formaldehyde. Examples are given of the pre- paration of sodium 1 -phenyl-2 3-dimethylpyrazole-5-one-4-ethyl- aminomethyl sulphite and sodium N-ethylphenetidine methyl sulphite. G. W. R. [Alkali Metal as a Reagent for Weakened Valencies in Organic Compounds.] K.ZIEGLER and F. THIELMANN (Ber. 1923 56 [B] 2453).-In their communication on this subject (A. 1923 i 921) the authors have overlooked the fact that a portion of the work has been described previously by Marcus (Diss. Jena 1914). H. W. G . W. R. The Preparation of pp'-Dinaphthyl Ether. V. M. RODIONOV and S. J. MANZOV ( J . SOC. Chem. Id. 1923 42 509-510~).- During the distillation of crude naphthol on the technical scale the formation of a large proportion of pp'-dinaphthyl ether was observed. The cause of this was traced to the presence of inorganic salts particularly acid salts during the distillation. When p-naphthol is heated at 200-210" for about ten hours it is converted entirely into pg'-dinaphthyl ether. E. H. R .ORGawIcl OHBXXST&Y.i 161 Substitution Products of Diphenylene Oxide. II. W. BORSCHE and B. SCHACKE (Ber. 1923 56 [B] 2498-2508; of. Borsche and Bothe A. 1908 i 528).-An extension of previous work. In oonsequence of the communication of Mayer andKrieger (A. 1922 i 746) the compound described previously (loc. cit.) as 3-nitro- diphenylene oxide is now considered to be the 2-nitro-derivative. The nitration of diphenylene oxide in glacial acetic acid solution gives a mixture of 2-nitrodiphenylene oxide and 3( ?)-nitrodiphenylene oxide small yellow-needles m. p. about 110". The former compound is reduced by sodium and methyl alcohol to 2 Z'-azoxydiphenyZene oxide pale yellow matted needles m. p. 259-260° and by sodium and boiling amyl alcohol to 2 2'-azodiphenyZene oxide m.p. 282". It is converted by concentrated sulphuric acid into 2-nitrodiphenyl- eneoxidesulphonic acid N0,~C12H,0*S0,€€ which is isolated in the form of its sodium salt pale yellow needles. The salt is converted by phosphorus pentachloride into Z - n i t r o d i p h e n y l e n e o x ~ d ~ ~ ~ ~ y Z chloride m. p. about 200" (decomp.) which is transformed by ammonia into the correspohding umide an amorphous white powder m. p. (indefinite) 265" (decomp.). The action of tin and concentrated hydrochloric acid on sodium 2-nitrodiphenyleneoxide- sulphonate yields 2-aminodiphenylelzwxidesulphonic acid the barium salt of which colourless leaflets is described. 2-Aminodiphenylene oxide is converted by ethyl bromomalonate into et h y 1 dip hen y leneoxid e- 2 - arninorndltmute C,,H ,O*RTH *CH (C0,E t)2 pale yellow needles m.p. 100"; it is transformed when heated at 240" into ethyl diphenyleneoxideindoxylate C l 2 H 6 0 < ~ ~ ~ * c O 2 E t m. p. 191" which when fused with alkali 0 co-c= hydroxide yields '' bisdiphenylenm"d-in- digo," a bluish-black powder which remains [I I I I ' unchanged below 350" ; the annexed formula J 2 is assigned to it but the possibility of the formation of the new ring in the 2 3-position is not excluded. 2-Diphenyleneoxide-2'-aminobenzoic acid C B O*NH*C,H,*CO,H pale yellow needles m. p. 227" is obtaineb2 b$ heating 0-chloro- benzoic acid 2-aminodiphenylene oxide hydrochloride potassium carbonate and copper bronze in the presence of amyl alcohol at 14-0-150". It passes when heated with zinc chloride at 240" into 2-anilinodiphenylene oxide C1,H,O*NHPh oolourless laslfl& m.p. 132" ; the acid is transformed by the successive action of phm- phorus pentachloride and aluminium chloride into phenylene oxideacridone C1,H,,O,N green- f) ish-yellow leaflets m. p. above 350" (annexed ()NH 2-Diacetamidodiphenylene oxide is converted by nitric acid in glacial acetic acid solution fu".f I into 3( 1 ) - n i t r o - 2 - d i a c ~ m i d o d i p ~ ~ ~ l € n e oxide \/-\/ 3;~.llow leaflets m. p. 19&197" which is hydrolysed by dcohol and fuming hydrochloric acid into 3(?)% /\/\/\-NH \/-/ o:/\/ formula). VOL. CXXVI. i. 9i. 162 ABSTRACT8 OF 0'HWOAI.i PAPERS. nitro-2-amid+phn&ne oxide orangemd needles m. p. 222"- 2 3( ?)-Diamidiphylene oxide forms colourless crystals m.p. 166" (hydr&l.i&e colourless leaflets); it is charaeterised M an OFthodiamine by its ability to condense with benzil to give the - quinoxaline derivative c12H6o<gyg greenish-yellow needles . i m. p. 179" and with phenanthraqinone to give the compound C 1 2 H 6 0 < ~ ~ 8 6 2 yellow needles m. p. 297". The action of aluminium chloride on diphenylene oxide and metyl chloride in the presence of carbon disulphide leads to the formation of 3-acetyldiphenylene oxide and 3 6( '2)-diacetyldi- phenylene oxide colourless needles m. p. 140". Nitro-3-acetyldi- phenylene oxide a brown crystalline powder m. p. 105" 3-ethyl- diphenyzene oxide a colourless liquid b. p. 3lO"/atmospheric pres- sure and nitro-3-ethyZdiphenylene oxide yellow needles m.p. 96" b p. 2L8-226"/15 m. are described. Diacetyldiphenylene oxide yields a dioxime Cr,HF403N2 a colourless sandy powder m. p. 250" (decomp.) whch is isomerised by phosphorus pentachloride in the presence of ether into dia;cetyZuminod$phenyZene oxide colour- less leaflets m. p. 258" from which diaminodiphenylene oride slender colourless needles m. p. 213" is obtained. Diethyldiphenylene oxide a colourlw odourless liquid b. p. 197-199"/20 mm. 334"/750 mm. is prepred by the action of amalgamated zinc and hydrochloric acid on diacetyldiphenylene oxide. Diphenylene oxide is converted by phthalic anhydride in the presence of nitrobenzene and aluminium chloride into diphenylene- oxidephthalonic acid m. p. 203-204" which passes under the influence of anhydrous zinc chloride at 260" into phthuloyldiphenylene de,'C,H,O greenish-yellow needles m.p. 258". The latter substance is reduced by zinc dust and aqueous ammonia to a mixture of phenylenwxidedih ydroanthranol C,,H 1402 a pale yellow powder m. p. 169" and a compound C,,,Hl,O yellow leaflets with a green fluorescence m. p. 311" the constitution of which has not been elucidated. Diphthaloyldphenylene oxide C2,H1,0 crystallises in slender greenish-yellow needles m. p. 295". J. BOESEEEN (Ber. 1923 56 [BJ 2409-2411).-Methods previously described (cf. Derx A. 1922 i 651) have been applied to the determination of the configuration of isomerides of 1-methyl- 1 -phenyl- and 1 -cycle- hexyl-cyclohexane-1 2-diols. The 1 -methylcyclohexane-1 2-diol m. p. 67" obtained by oxidation of 1-methyl-A1-cyclohexene is the ck-compound (not tram see Nametikin and Janev A.1923 i 1081). With potassium hydroxide &Dd boric acid it forms a crysfahe salt C6H&e:0,:BOK,4H@. The isomeric oompound m. p. 84" has therefore the trans-configuration. cis-1-Phanykyclo- hexme-1 2-diol is the product m. p. 95" obtained by oxidation of 1 -phenyl-Al-cycbhexene with permanganatz. It is also the principal product of hydrolysis of 1-phenylcycZohexene 1 2-oxide but trans- I-pknylcyclohexane-1 2-diol is also formed in the reaction product ; 6 4 H. W. The Configuration of Cyclic 1 2-Diols.it forms short prisms m. p. 98-5". It is probably the primary product but under the experimental conditions homerises into the cis-form (cf. Nametkin and Ivanov A. 1923 i 1097).cis-l-cyclo- Hczylcyclohexune-1 2-diol m. p. 122-123" is obtained by oxid- ation of the corresponding cyclohexene and the trans-ismeride m. p. 142O by hydration of 1-cyclohexylcyclohexene 1 2-oxide. E. H. R. Action of Nitric Acid and Nitrogen Peroxide on Tetra- chloro- and Tetrabromo-pyrocatechol and the Corresponding Quinones. T. ZINCEE (Annalen 1923 435 145-173).- Tetrachloro-o-benzoquinone when treated with nitric acid (d 14- 1-51) gives according to the concentration of the acid one of two cornpunds A C,H40,C14 or B C,H,0,N2C14 which are also produced under similar conditions from tetrachloropyrocatechol. The former (A) colourless needles m. p. 95-96" is a t r i h y b t e of a tri-keto-compound ; when heated it is converted into trichloro- hydroxy-p-benzoquinone and on reduction gives trichloro- hydroxyquinol (cf.[Frl. J Weishaupt Dissert. Marburg 1923). Compound B forms white needles decomposing at the m. p. (114-115") to give water carbon dioxide oxides of nitrogen and the compound C,,O,Cl described previously (A 1909 i 591; 1912 i 964). The last compound is formed intermedialzly on boiling an aqueous solution of B then decomposing to give per- chlmoindone. Similarly on heating a solution of B in alcohol acetone or acetic or concentrated sulphuric acids the compound C,,O,Cl is formed. Compound B when treated with alkali affords a number of decomposition products depending on the concentration of alkali etc. Producfs identified include ammonia nitrogen mrbon dioxide and oxalic and nitrous acids. Mainly from this decom- position and from the fact that compound B is also produced (here not accompanied by A) by treating tetrachloropyrocatechol at 0" with liquid nitrogen peroxide the constitution I1 is assigned to B the formation of this substance from tetrachloropyrocatecho€ proceeding through the corresponding quinone and its nitrogen peroxide additive compound I co (One N02-group is probably nitro- the other nitrite *ONO).A low value is obtained for the molecular weight of B when determined cryoscopicafly in acetic acid owing to the dissociation of the hydrate (11). Whilst tetrachloro-o-benzoquinone does not d o r d compound (I) (but only tarry products) when treated with nitrogen peroxide 9 2i. I64 ABSmCTS OF CHEMICbL PAPERS. the constitution (11) assigned to B fa& into line with the abore decomposition in presence of alkali.In this process chloro-groups and a nitrite group are replaced by hydroxyl oxalic acid and the compound OH*CH:C( OH)*C( OH),-CH( OH) resulting. Further decomposition affords s-dihydroxyethylene or the isomeric glycoll- aldehyde and glyoxylic acid whence carbon dioxide and more oxalic acid are produced. When substance B is treated with aniline or phenylhydrazine red or dark-coloured substances result respectively. Tetrabromo-o-benzoquinone behaves unlike the chloroquinone towards nitric acid white insoluble poducb being formed Tetra- bromoppcatechol is however converted by nitric acid into a compound C6H405Br4 (type A4) which decomposes partly to give a substance C502Br4 m. p. 142-143". Bromo-compounds corresponding with B result when tetrabromopyrocatechol is treated with nitrogen peroxide no compound of type A being produced in this case.- The homo-compound C6H20,N2Br,,H,0 (type B) which forms colourless needles m. p. 113-114" (decornp.) on drying undergoes partial decomposition (the m. p. rising to 126-127"). On keeping or on warming in solution in glacial acetic sulphuric or formic acids the bromo-compound affords the substance CIoO,Br8 ; on boiling in aqueous solution it gives perbromoindone ; whilst with alkalis the bmmo-compound decomposes in a manner similar to that observed with the corresponding chloro-compound (B). When halogenated pyrocatechols are treated with mixed acid (HNO 88.9% H,S04 9-9:/ H20 1-2%) type A is produced to a greater extent than when nitric acid alone is used owing to increased oxidation. The corresponding quinones when treated with mixed acid give in the case of the chloro-compound tarry products and in that of the bromo-compound decomposition products of the intermediately-formed substance C,H,O,Br,.3 4 6-Trichloro-5-methyl- and 3 4 5-trichloro-6-methyl-pyro- oatechol are converted into compounds of type B (but not of type A ) C6H40,N2Cl,Me when treated with nitric acid (d 1.45-1.48) or with nitrogen peroxide indifferent results being obtained using mixed acid. The compound C,H4Me0,N2CI obtained from the 3 4 6- derivative forms white needles m. p. 116-117" (decornp.) (one specimen m. p. 110-111") crystallised from dilute hydrochloric acid. After careful drying the m.p. rises to 126-127" this m. p. being obtained when the substance is crystallised from nitric acid. The compound on melting or better on being heated in glacial acetic or sulphuric acid solution is converted into the substance C,,O CI6Me2 (m. p. 182") described previously (A. 1897 i 507). J%om the decomposition in presence of alkali of the compound C,H,lhfeO,N,CI the latter is given the constitution NO,.CHCI -CCI (NO,)CMe:CCl*C( OH),*CO,H. NO,*CRClCCl( NO,)*CClXMe*C( OH),-CO,H obtained from 3 4 5-trichloro-6-methy1pyrocatecho1 forms The isomeric compound,needles melting at 115-116" (or after drying 125-126") to give the substance C,oO,CI,Me which is more readily obtained by heating the h t compound in aqueous acetic or sulphuric acid solution and is identical with a compound (m.p. 175") previously described (A. 1897 i 509). The substance Cl,0,C18 mentioned above which is also obtained from the nitric acid decomposition product (C&O,"C14&) of tetrachloro-o-cresol by warming with concentrated sulphunc acid has been re-investigated. It was previously stated that it wa8 converted by boiling methyl alcohol into the compound C,C16(OH)*OMe (m. p. j38") which is now written as C,02C~*OMe (m. P. 136-137"). ' TGe constitution of the compound Clo0,Br8 (cf. A. 1907 i 322; 1912 i 964) is still unsettled but the possibility of it being a derivative of tetrahydmmphthalene is excluded. The compound on melting a t 207-208";m heating with glacial acetic acid and sodium acetate or on hakikg in nitrobenzene solution affords perbromoindone (m.p. 195-1969) the latter being converted by warm aniline into the anilide C,OBr,*NHPh scarlet leaflets m. p. 224" (decomp.). E. E. T. The Constitution of Weselsky and Benedict 's Dinitro- @no1 Methyl Ether. F. KEHRMANN and G. JEQUIER (Hdu. Chim. Ada 1923 6 949-951).-The comtitution of this ether given by Reverdin and de Luc (A. 1911 i 965) who concluded that it is 3 5-&nitro-4-hydroxyanisole has been confirmed by the preparation of the isomeric ether. The silver salt of 3 Ei-dinitro- quinol 1-acetate reacts with methyl iodide to give 2 6-dinitro- 4-acetoxyanisuZe small yellow crystals m p. 63" which when hydrolysed gives 2 6-dinitro-4-hydroxganzsole yellow crystals m. p. 149". The dinitroquinol monoacetate used for the prepar- ation was obtained by nitration of quinol diacetate (see following abstract).E. H. R. The Action of Nitric Acid on Quinol Diacetate. F. KEXR- BIANN and W. KLOPFENSTEIN (Helq. Chim. Actu 1923 6 952- 954).-Nitration of quinol diacetate with fuming nitric acid below 10" gives not 3 5-dinitroquinol diacetate as stated by Nietzki and Preusser (A. 1887 574) but 3 5-dinitroquid 1-monatcetate yellow tablets m. p. 94". Acetylation of this with acetic anhydride gives 3 5-dinitroquinol diacetate colourless needles m. p. 134". More careful nitration of quinol diacetate at 0" gives 3-nitro- quinol 1-acetate lemon-yellow needles m. p. 84". This can be acetylated to 3-nitroquinol diacetate colourless needles m. p. 80". It is evident that nitration of quinol diacetate cannot proceed without elimination of one acetyl group.Some Condensation Products of Hydroxyquinol Trimethyl Ether. T. SZ~EICI (Ber. 1923 56 [ B ] 2464-%68).-Hydroxy- quinol trimethyl ether condenses wi$h acetone in glacial acetic acid solution in the presence of concentrated sulphuric acid to give E. H. R.i. 166 ABSTRACTS OF OKEMIOAL PAPERS 2 4 5 2' ; 4' 5'-kamethoxydiphenylisophorone [l 5 5-tri- methyl-3 3-bis-2' 4' 5'-trimethoxyphn~l- A1-cyclohxene] (annexed formula) colour- HCH\CH less needles m. p. 207" which is converted by bromine in glacial acetic acid solution into the bromo-derivative C,,H,,O,Br colourless lustrous crystah m. p. 1190; as by-product of the condensation 2 4 5-trimethoxybenzeneiulphonic acid colourless needles m. p. 115" is obtained the sodium salt of which is described. The action of hydrogen chloride on it solution of 2 4 5-tri- methoxybenzene and alloxan in alcohol leads to the production of 2 4 5-trimethoxyp~nyldi~uric acid co <zg::E>c( oH)*c6H2( OMe) small colourless needles m.p. 248-249" (decomp.). It is con- verted by acetic anhydride and sulphuric acid monohydrate into the corresponding acetate decomp. 270-292" and is decomposed by boiling N / 5 sodium hydroxide solution into ammonia carbon dioxide and 2 4 5-trimethoxyphenyltartronimide colourless microscopic leaflets m. p. 220-221". 2 4 52%- methoxyphenacyldialuric acid slender colourless crystals m. p . 245" (decomp.) after darkening a t 220" is prepared from 2 4 5- trimethoxyacetophenone and alloxan. Benzhydrol is converted by 2 4 5-trimethoxybenzene in alcoholic solution in the presence of hydrogen chloride into 2 4 5-trimethoxytriphenylmethane C,H,( OMe),*CHPh colourless needles m.p. 117". In a similar manner 2 4 5 4'-tetra- methoxydiphenylcarbinol and 2 4 5-trimethoxybenzene yield 2 4 5 2' 4' 5' 4"-heptamethox~7.i~he~~~lmethane slender colourless needles m. p. 162" whereas 2 4 5-trimethoxyphenyl- a-naphthylcarbinol and 2 4 5-trimethoxybenzene give 2 4 5 2' 4' 5'-hexamethoxydiphenyl-~-nnphthylmet7~ane slender colourless needles m. p. 198". c6H2( ()&)3.C\/CMe I CH2 NH<C-j co\ /C(OH)=C,H*(OMe) H. W. Action of Sulphur on p-Toluidine in the Presence of Litharge. Thio-p-toluidine its Constitution and some of its Derivatives. M. T. BOGERT and &I.R. MNDELBAUM ( J . Amer. Chem. Soc. 1923 45 3045-3055).-The formation of thio- p-toluidine by heating p-toluidine with sulphur a t 140" in the presence of litha,rge takes place through the mercaptan (annexed formula) which reacts with a nuclear hydrogen atom of unchanged p-toluidine. A small proportion of SH the mercaptan was oxidised to dithio-p-toluidine m. p. 88*5" acetyl derivative m. p. 213". The sul- phide produced by de-amination of thio-p-toluidine was identical with di-m-tolyl sulphide synthesised from m-iodofoluene and sodium m-tolyl sulphide. The respective sulphones and a mixture of them melted at 94'. In the absence of litharge and 8 \/ NHzomma -mY. i. 167 at 180-220" the intermediate mercaptan reacted with the methyl group of unchanged p-toluidine to give dehydrothio-p-toluidine.The authors failed to convert thio-p-toluidine into dehydrothiu- p-toluidine. The former gave a diucetyl derivative m. p. 165" (con.) which was oxidised to bis-2-acetamido-5-carboxt~phenylszrlphone m. p. above 360". The latter was de-acetylated and the resulting bis-2-amino-5-carboxyphenyZsulphone melted above 360" (decomp. j ; the methyl ester forms thin square colourless tablets m. p. 234" (COIT.) the ethyl ester forms yellow transparent prisms m. p. 206" (corn.). F. B. Formation of Liquid Crystals of Mixtures of Cholesterol and Cetyl Alcohol. A. M~ODZIEJOWSKI (2. Physik 1923 20 317-342) .-The conditions necessary for the production of liquid crystals of mixtures of cholesterol and cetyl alcohol and the approximate character of the equilibrium diagram relating to the phases of mixtures of these substances have been determined.Cholesterol exists in two solid enantiomorphic modifications the transformation temperature associated with which is about 43". Liquid cetyl alcohol on cooling deposits needle-shaped crystals at about 50". Crystalhation is accompanied by the separation of an amorphous solid phase characterised by the presence of lenticular masses. The transformation from liquid to solid is reversible. Liquid crystals of mixtures of cholesterol and cetyl a.lcoho1 may be either homogeneous or may exhibit a spherolitic or myelin structure characterised by the presence of rod-like biscuit- or worm-shaped masses in a state of agitation. Of these two varieties of liquid crystals the homogeneous variety is the more stable.Cetyl alcohol is practically insoluble in this modific- ation. The liquid crystals are probably composed of equal mole- cular proportions of the two components and on heating are reversibly converted into solid crystals provided the concentrations of the components are within certain limits. They form an eutectic mixture with cetyl alcohol. Preparation of Nucleus-substituted Hydroxyl Derivatives of p -Amino-a-hy droxy- a-arylet hanes and p -Amino- a-bisaryl- ethanes. 0. HINSBERQ (D.R.-P. 373286; from Chern. Zentr. 1923 iv 662; cf. A. 1923 i 923).-Phenols naphthols or their substitution products are allowed to react with aminoacetal or its N-mono- or di-alkylated derivatives in the presence of hydro- chloric acid under pressure.For example with equimolecular proportions of phenol and aminoacetal in the presence of hydro- chloric acid under pressure a t loo" the following reaction takes place PhOH+NH,*CH,*CH( OEt) + HCl+H,O = OHC,H,*CH( OH)-CH,*NH,,HCl+ 2EtOH. a-p-Hydroxyphenyl- p-aminoethanol thereby obtained has m. p. above 250"; the hydrochloride has m. p. 172" (decomp.). Phenol (2 mols.) and aminoacetal (1 mol.) give p-amiizo-a-bis(p-hydroxy- phenyZ)ethane which has m. p. 105". Pyrocatechol and methyl- aminoacetal yield o-dihydroxyphenylethanolmethylamine (adren- a'line). p-Cresol and aminoacetal give p-amino-a-hydroxy-a- 1 - J. S. G. T.hyd?wxy-4-ntethzJphenyZethne an unstable compound which gives =a h y W & with m. p. 120' (decomp.). Naphthenic Acid. III. Naphthenic Acids from Kubiki g e r O ~ e ~ e Distillate.Y. TANAEA and 8. NAGAI (J:Chem. Znd. Japan 1923 26 1115-1123; cf. ibid. 1923 26 309; A. 1933 i &).-A crude mixture of acid substances was obtained by acidify- h g a waste lye obtained in the refking of kerosene distillate from crude oil produced at Kubiki. Crude naphthenic acids (d? 0.9647 rig 1.4790 and acid value 202.8) were then obtained by three methods. About 86% of the crude acids distilled at 140- 210"/8-9-9 mm. The lower distillates contained some phenolic compounds and the fractions above 200" showed lower specific gravities than the preceding ones. The acid was converted into methyl esters d:" 0.9368 n; 1-4663 about 83% of which distilled at 120-180"/8.9-9 mm. and the fractions above 170" gave decreasing specific gravities.A mixture of pure naphthenic acids (di6 0.9587 n 1.4707 and acid value 244.5) was obtained by saponifying the mixed esters about 90% of which distilled a t 150-210"~8~9-9 mm. The higher fractions above 200" showed again lower specific gravities than the preceding ones. The mixed naphthenic acids and their distillates of Kubiki origin have much smaller spec& gravities than those of Kurokawa origin which indicates the presence of isomeridea having low specific gravities in the former. K. K. Normal Ammonium Salts of some Organic Acids and their Substitution Derivatives. VIII. L. MCMASTER and P. K. PRATTE ( J . Amer. Chem. Soc. 1923 45 2999-3001).-A descrip- tion of normal ammonium salts of organic acids prepared by the method previously described (A. 1918 i 263).The solubilities of the normal ammonium salts of the following acids are expressed in g. of salt per hundred g. of water methyl alcohol and ethyl alcahol in the order named. Phenoxyacetic acid 13-03 3.97 0.44 p-nitroghenylacetic acid 7-41 15.14 1-82 o-iodobenzoic acid 67.1 1 184-10 63-37 o-methoxybenzoic acid 38.25 17.85 4.82 2 4-di- nitrobenzoic acid 62.70 21-39 3.85 5-nitrosalicylic acid 4-43 4.41 7-96 naphthalene-l-sulphonic acid 45.91 34.45 9-22 na hthal- acid 11.30 20.15 2-59 6-chloro-3-nitrobenzenesulphonic acid 4.72 2.76 0.96. F. B. R. C. BROWN and R. E. KREMERS ( J . Amer. Pharm. ASSOC. 1922 11 607-608).-3 5-Di- nitrobenzoic esters of phenol (m. p. 145-146") o-cresol (133- 134") m-cresol (160-162") p-cresol (180-.-182") guaiacol (138- 139") carvacrol (76-7?") and thymol (102-103") mere prepared as a means of identification of the phenols.G. W. R. ene-2-sulphonic acid lP71,8-33,2.53,2 5-dichlorobenzenesu f phonic 3 5aDinitrobenzoates of Phenols. CHEMICAL ABSTRACTS Prdeinogenous Aminc-alcohols aqd Cholines. IfI. P. KARRER E. HORLACHER F. LOCHER and M. GI~LEB (Helv. Chim. Ada 1m3 6 905-919; ef. A. 1922 i 813).-N-~ethyl-leucinolORQBNIO 4lEEXIsTBY. i. 169 [~-d;lleth~a~ninoi~ohexyldcohol] (cf. A. 1921 i 228) condenses with p-nitrobenzoyl chloride in chloroform solution to give p-nitro- benzoyl-N-dimethyl-leucinol. This can be reduced to p-amino- benzoyl-N-dimethyl-leucinol which in the form of its hydrochloride is a very powerful local anssthetic. The corresponding N-diethyl LV-dipropyl and N-pentamethylene Cpiperidino] compounds are likewise powerful local anaesthetics.Of the four .the N-&ethyl compound is the most powerful being eight times as ackive as novocaine and a t the same time less poisonous than cocaine. p-2\.'itrobenzo~l-N-dirnethyl-leucinol hydrochloride CHMe,*CH,.CH(NMe,,HCl)*CH,O*CO*C,H .NO forms yellow needles m. p. 149.5". It is reduce4 by hydrogen in the presence of platinum black to p-aminobenzoyl-N-dimethyl- Zewinol hydrochloride bright yellow needles m. p. 196". N-Di- ethyl-Zeucine ethyl ester is prepared by condensing racemic a-bromo- isohexoic acid with diethylamine and esterifying; it forms a pale yellow oil b. p. 204-208"/720 mm. It is reduccd by sodium and alcohol to N-diethyl-leucinol a colourless oil b. p.208-211". p-Nitrobenzoyl-N-diethyl-leucinol hydrochloride forms pale yellow needles m. p. about 163" (depending on the rate of heating). p-Aminobenzoyl-N-diethyl-leucinol hydrochloride forms white leaflets m. p. 191". N-Pentarnethyleneleucine ethyl ester [ethyl a-p-'peridino- isohezoate] from a-bromoisohexoic acid and piperidine forms an oil b. p. 248-255"/726 mm.; by reduction it gives N-penta- naeth@!eneleucind [ibpiperidinoisohexyZ dcohol] b. p. 250-252". The p-nitrobenzoate hydrochloride crystallisss in nodular aggregates of thin prisms m. p. 156" and the p-anaindenzoa,te hpirochide crystalhes similarly. The synthesis of 3 4-methylenedihydroxyphenylaIaninecholine iodide m m accomplished as follows. Piperonyl bromide was obtained by the action of hydrogen bromide on piperonyl alcohol; it crystal- lises in needles and does not form a compound with magnesium in ether solution.It condenses with ethyl malonate by means of sodium in alcoholic solution forming ethyl piperonylmdonate CH,:0,:C,H3*CH,*CH(C02Et) a yellow vkcous oil b. p. 200- 220"/15 mm. which when hydrolysed gives piperonylmalonic acid m. p . 156". This was brominated to bromopiperonylmahnic acid CH,:0,.C6~CH,*CB(CO,Et) m. p. 147-148" (decornp.) which when heated at 120-130" loses carbon dioxide forming a-bromo- piperonylacetic acid. The latter waa not isolated but was heated directly with dimethylamine a t 100" ; the N-dimethyl-3 4-meth.ytene- dioxyphenylakcnine formed waa not isolated but treated with alcohol and hydrochloric acid forming the ethyl ester a Viscous yellow oil b.p. 200"/14 mm. This waa reduced with sodium and alcohol forming N-dimethyl-3 4-methylenediox~phenylalanin~ CH, 0,:C ,H,-CH,=CH (me,) -CH2*OH b. p. 180"/14 mm.; the hydruchlon'de crystallises in white leaflets m. p . 165". When the alaninol is treated with excess of methyl iodide in alcohol solution 3 4-methylenedioxyphengl&nine- chdine iodide [P-dimethylamino-y-piperonylpropyl alwhd meth- idide] m. p. 184" is formed. The following palmitic and skaric 9"i. 170 ABSTBAOT8 OB ( l m C A L PAPERS. acid esters of proteinogenous cholines are described p-methoxy- phnylalanine rnethiodide stearate bunches of needles sintern from 98" m p. 195"; the corresponding pdmitate similar crystals m. p. 138-141"; alanine methiodide stewate s a y leaflets m.p. 210-212" ; palmitate white needles m. p. 203-210" ; &nine inethochlm.de stearate hygroscopic needles m p. 202-205" and pahiitate m. p. 202-205". Effect of Silver Nitrate and Alkali Nitrates on Aromatic Anhydrides. C. V. GHEORGHIU (Ann. Xci. Univ. Jassy 1923 ii 308-309; from Clzem. Zentr. 1923 iii 1155).-Benzoic an- hydride when heated with silver nitrate explodes with evolution of gas development of the odour of nitrobenzene and formation of silver Phthalic anhydride and coumarin behave in a similar way. The alkali nitrates can also act like silver nitrate. The author supposes that benzoyl peroxide or perbenzoic acid the salts of which are explosive may be formed e.g. 4Bz,0+2NaN03= 2BzONa+3Bz20,+N2. Por the per-acids the formulze CO,H*C,H,*CO*O*OH and O~~C,H,*CH:CH*CO~O~OH respectively are given.Nitrobenzene is probably formed by nitration of benzoyl peroxide. o-Nitrophenylpropionic Acid. A. JAENISCH (Ber. 1923 56 [B] 2448-245O).-An improved method is described for the conversion of o-nitrobenzylmalonic ester into p-o-nitrophenyl- propionic acid m. p. 115"; the silver lead copper mercury barium calcium (+2H20) and zinc (+2H20) salts are described. The methyl ester is a liquid b. p. 171-172"/12 mm. p-o-Nitrophenyl- propionyl chloride needles m. p. 43" (prepared from the acid and phosphorus pentachloride) is transformed by ammonia into the corresponding amide colourless plates and needles m. p. 121- 122" which is converted by Hofmann's method into the bromo- amide C,H,O,N,Br yellow needles m. p. 136-137" and thence into p-o-nitrophenylethylamine NO,*C,H,=CH,*CH,*NH a liquid b.p. 147"/13 mm. (hydrochloride plates m. p. 174.5"; picrate m. p. 148.5"). Benzo- p-o-nitrophenylethylamide NO,*C,H,*CH,*CH,=NHBz crystallises in stellar aggregates m. p. 98"; it is reduced by phosphorus and hydriodic acid to benm- /3-o-aminophenylethylamide leaflets m. p. 135" (the hydriodide is described). p-o-Nitrophenyl- ethylphtharlimide NO,~C,H,*CH,*CH,*N:C,H,O needles m. p. 120-121 " p-o-aminophenylethylphthcclimide needles m. p. 163" p-o-nitrophenylethylsuccinimide needles m. p. 116" and p-o-amino- phnylethylsuccinimide needles m. p. 141 " are described. Reduc- tion of p-o-nitrophenylethylamine by phosphorus and hydriodic acid yields p-o-aminophenylethylamine [di-hydroiodide yellow needles and leaflets m.p. (indehite) 260" ; dihydrochloride softening a t 184"; picrate m. p. 142-143"; benxoyl derivative m. p. 139-140"]. o-o-Nitrobenzylmetophelzone stellar aggregates m. p. 68-69" prepared from o-nitrobenzylacetyl chloride benzene and aluminium chloride is reduced by phosphorus and hydriodic acid to 2-phenyl- E. H. R. G. W. R.quinoline 112. p. 81 ". u-Keto-y-o-nitrophenyl-u-an~~ylpropne pale yellow rodlets m. p. 59" and 2-anisylquinoline leaflets m. p. 123.5" are described. Similarly the reduction of ethyl 0-nitro- benzylmethylacetmcetate a liquid yields 2 3-dimethylquinoline m. p. 64*5" and not a dihydro-derivative. P-o-NitrophenylpropzsonitriEe prepared from the amidc and thionyl chloride m. p. 4 1 4 2 " is reduced by stannous chloride and hydrochloric acid to 2-aminoquinoline hydrochloride.a-Bromo-p-o-nitrophenylpropionic acid rhombohedra m. p. 115- 116" is prepared by the action of bromine and phosphorus on the parent acid or by heating bromo-o-nitrobenxylmdonic acid prisms m. p. 143" (decomp.). .a-Hydroxy-P-o-nitrophenylpropionic m i d rectangular plates m. p. 103" is prepared from the bromo-acid and silver nitrate solution; it is decomposed by sodium hydroxide solution with production of o-nitrotoluene. H. W. asp-Triphenylpropionic Acid and some of its Derivatives. [MME] P. RAMART (Compt. rend. 1924 178 93-96).-Benzyl diphenylacetate (needles m. p. 35" b. p. 205-207"/2 mm.) from diphenylacetyl chloride and benzyl alcohol when treated successively with sodamide and benzyl chloride affords benxyl uup-triphenyl- propionate (prisms m.p. S5" b. p. 270-276"/2 mm.). The latter on hydrolysis affords ucwp-triphenylpropionic acid (prisms m. p. 132"; amide needles m. p. 111"). The nitrile (m. p. 126") 1s formed from benzyl chloride and sodio-diphenylacetonitrile or from phosphoric oxide and the amide (above). Neure (A. 1889 597) obtained the nitrile but was mistaken with regard to the constitution of his acid of m. I>. 162" (cf. Bistrzycki and Mauron A. 1910 i 845). E. E. T. Higher Terpene Compounds. XVI. The Carbon Frame- work of Abietic Acid and Dehydrogenating Disruption in the Abietic Acid Series. L. RUZICKA E. SCHINZ and *J. MEYER (Helv. Chim. Acta 1923 6 1077-1096).-The annexed constitu- tional formula for abietic acid (pinabietic acid) put forward by Virtanen (A.1921 i 669) does not conform with the principle which has been foundgeneral for the sesquiterpenes that the carbon framework must be divisible into H,F/'\$.co,H isoprene residues. This formula was based partly on the observation that the hydrocarbon abietin C,,H, when oxidised with manganese dioxide "7 YH2 and sulphuric acid gives trimellitic acid. Hence CH2 it is argued that abietin must contain a benzene /\ / ring and that the corresponding ring in abietic H2$! YH acid must contain the double bond and the bridge- H,C ring (or as is now known to be the case the two double bonds) as well as the carboxyl group. A study of the oxidation of abietin abietene methyl- abietin and abietic acid leads to the conclusion that Virtanen's reasoning is incorrect.Rlethylabietin which according to Virtanen should also contain a benzene ring is com- CPrS HC</C\ MeC CHMe \/ CH2 9" 2i. 172 ABSTRACTS OF CHEMXCAL PAPERS. pletely oxidised by cold aqueous permanganate to acids and by oxidation with manganese dioxide and sulphuric acid it gives tri- mellitic acid as also does abietic acid. It is.concluded therefore that the carboxyl group cannot be in the same ring as the isopropyl group and as the 9 and 10 &\A positions are excluded (see annexed diagram and 1;; A. 1922 i 829) the only remaining positioiis qv\,/i are 2 3 and 4. The remaining methyl group ’ may be in position 11 or possibly in 12 but only Oxidation of abietic acid and its related compounds with man- ganese dioxide and 57% sulphuric acid leads to a mixture of benzene polycarboxylic acids some of which are formed normally from the carbon framework of the oxidised substance some indirectly.Trimellitic acid and mellophanic acid (which is confirmed to be the I 2 3 4tetracarboxylic acid cf. Bamford and Simon T. 1910 97 1904) are probably formed normally and are obtained from abietene (mixed with abietin) abietic acid and methylabietin. Pyromellitic acid and benzenepentacarboxylic acid are obtained from abietic acid their formation being possibly due to polymeris- ation of the abietic acid a t a double bond. A number of methods in which this may occur are discussed. Retenequinone and methyl- retenequinone are oxidised to mellitic acid whilst the former also gives pyromellitic acid. Dihydroabietene is oxidised to mellophanic acid without formation of any trimellitic acid and the same is the case when niethylabietin is oxidised first with cold permanganate and then boiled with manganese dioxide and sulphuric acid.The mechanism of the oxidation of the above compounds with manganese dioxide and sulphuric acid consists first in dehydro- genation of the individual hydroaromatic rings followed by dis- ruption to benzenecarboxylic acids. The process is referred to as “ dehydrogenating disruption.’’ The different benzenepolycarb- oxylic acids are best separated by fractional distillation of their methyl esters which crystallise readily. The reduction of ethyl abietate by Bouveault’s method to abietenol which still contains one unsaturated bond indicates that there is no double bond in the ring containing the carboxyl group (A.1922 i 829). The exact position of the double bonds in abietic acid remains uncertain. I kT\ if the carboxyl is in 2. E. H. R. Higher Terpene Compounds. XVII. The Gentle Action of Potassium Permanganate on Abietic Acid. L. RUZICKA and J. MEYER (Helv. Chim. Acta 1923,6,1097-1108).-To obtain a crystalline product by the oxidation of abietic acid with potassium permanganate great care is required. The oxidation is carried out in potassium hydroxide solution using 2 to 3 atoms of available oxygen per mol. and a t a high dilution. After fifteen hours the manganese dioxide is filtered off and unoxidised abietic acid precipitated by a current of carbon dioxide. When part of the oxidation product has started to precipitate the solution is filtered and the main product precipitated with acetic acid.The precipi-ORGAWrO CHEMISTRY. i. 173 tate is filtered dried and digested with a little methyl alcohol which leaves a crystalline residue about 3 4 3 % of the weight of .the abietic acid taken m. p. 106". This is separable by fractional precipitation into an unknown substance C,,H,,O m. p. 154" and a dihydroxyubietic acid CmHm02(OH)2 m. p. 152" which gives a diacetyZ derivative m. p. 163" (decomp.) and it possibly stereo- isomeric diacetyl compound m. p. 240". On separate occasions the oxidation took different courses giving products of m. p. 135" and 360". E. H. R. The Resolution of &I-Tyrosine into its Two Optically Active Components. E. ABDERHALDEN and H. SICEEL (2.physiol. Chem. 1923,131 277-280) .-Formyl-dl-tyrosine obtained from tyrosine by boiling with formic acid for three hours has been separated into its components by recrystallisation from hot water containing four equivalents of brucine. The brucine salt of formyl- d-tyrosine which crystallises out forms four- or six-sided leaflets which decompose a t 145". Formyl-d-tyrosine is obtained from this salt on decomposing it with alkali. Hydrolysis of formyl-d- tyrosine with 10% hydrochloric acid yields d-tyrosine [a]? +8-7". The corresponding h a l t waB not obtained pure from the mother- liquors. The best preparation gave [a] -6.2O. W. 0. K. Dichlorotyrosine [ a - A m i n O - p 3 54lichloro4hydroxy- phenylpropionic Acid]. CHEMISCHE FABRIK RORA (swiss Pat. 99453 ; from Chem.Zentr. 1923 iv 828).-A suspension of tyrosine in acet,ic acid is treated with chlorine. Dichlorotyrosiize hydro- chloride separates out from which the free bme may be obtained in crystalline form. It is optically active. G. W. R. Preparation of Dibromotyrosine [a-Amino-p-3 5-dibromo- 4-hydroxyphenylpropionic Acid]. CHEMISCHE FABRIK FLORA (Swiss Pat. 95300 ; from Chem. Zentr. 1923 iv 663).-A suspen- sion of tyrosine in acetic acid is treated with bromine; from the products of reaction a-amino-p-3 5-dibrmno-4-hydroxyphenylpo- pioiiic acid is obtained. It is crystalline and optically active. G. W. R. Derivatives of a-Naphtho1-2carboxylic Acid. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (D.R.-P. 373736; from Chem. Zeittr. 1923 iv 593).-Additional to Brit. Pat. 195513.4 4'-Di- hydroxydinaphthylketone-3 3'-dimrboxyZic acid is a powder decom- posing a t 259". u-Xuphthol-2 4-dicarboxylic acid decomposes at about 286". G. W. R. a-Naphthol-4-carboxylanilide. SOCIETY FOR CHEMICAL IKDUSTRY IN BASLE (Swiss Pat. 99280; from Chem. Zentr. 1923 ir 829).-h ester of u-naphthol-4-carboqlic acid for example methyl a-naphthol-4-carboxylate is heated with aniline. a-Naphthol- 4-carrbo.zylanilide thus obtained is crystalline and has m. p 203" G. W. R.i. 174 ABSW@rS OF CHEIkfICbL PAPERS. The Constitution of Sparassol. E. WEDEKIND and K . FLEISCKER (Ber. 1923 56 [B] 2556-2663; cf. Falck ibid 2555).-The substance is shown to be methyl 4-hydroxy-2-methoxy I 0-toluate . Sparassol C1JiIl2O4 crystallises from methyl or ethyl alcohc ! in needles m.p. 67-68". It contains two methoxyl groups i I saturated and does not possess a ketonic or a reactive methylen group. Its aromatic nature is established by the isolation 0 ' methyl 3 ( ? 5)-nitro-4-hydroxy-2 -methoxy-o-toluate yellow needles m. p. 168-169" and methyl 3 5-dinitro-4-hydroxy-2-methoxy o-toluate small pale yellow needles m. p. 150". The presence o a phenolic hydroxyl group in sparassol is established by its solubilitj in alkali hydroxide but not in alkali carbonate and by the form ation of methyl 4-acetoxy-2-methoxy-o-toluate small hexagona plates m. p. 63-64' and of methyl 2 4-dimethoxy-o-toluate rhombic plates m. p. 4243.5' ; the isolation of 4-hydroxy-2-methoxy o-toluic acid m. p. 165-166" (decomp.) after slight previous soften- ing as by-product of the action of methyl sulphate and potassium hydroxide on sparassol indicates the presence of the.carbomethoxy- group. When treated with fuming hydrochloric acid under pressure sparassol yields orcinol. A comparison of the properties .of sparassol and the corresponding carboxylic acid with those of the known orcinolcarboxylic acids and their methylated derivatives excludes the poasibility that the constitution of sparassol is other than methyl 4-hydroxy-2-methoxy-o-toluate. It is established that the amount of benzenoid compounds in the culture medium is insufficient to account for the production of sparassol; an example is therefore afforded of the conversion of an aliphatic compound (sugar) into an aromatic substance by a biochemical method. H. W.Preparation of Aryl Hydroxynaphthyl Ketones. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (D.R.-P. 378908 378909 and Swiss Pat. 98559; from Chem. Zentr. 1923 iv 593-594).- @-Naphthol or negatively substituted derivatives of a- or @-naphthol are treated with aryl trichlorides with or without addition of diluents or condensing reagents in the absence of alkali hydroxides. The carboxylic acids and sulphonic acids of 4-hydroxynaphthalene- 1-arylketem are heated at high temperatures preferably in suspen- sion or in the presence of diluents. 1 -Hydroxynaphthalene-2-carb- oxylic. acid when heated with benzotrichloride a t 100-120" until eyolution of hydrogen chloride has ceased or a t 15" in the presence of strong sulphuric acid gives 4-hydroxy-1- benzoy~nccfhthalene-3-carb- oxylic acid small needles m.p. 205". On heating the latter com- pound under pressure with strong sulphuric acid phenyl4-hydroxy- a-naphthyl ketone is obtained m. p. 164-165". 4-Hydroxy- 1 -o-chlqrobenzoylnaphthulene-3-cccrboxylic acid from 1 -hydroxy- naphthalene-2-carboxylic acid and o-chlorobenzotrichloride has m. p. 2 13". 1 -Chloro-4'-hydroxy-2 1 '-dinaphthyl- ketone-3'-cccrboxylic & ~&R.I I-hydroxynaphthalene-2-carboxylic acid and 1-chloro- Z-naph+hofrichloride has m. p. 210-211". The following corn-0IUxmc CHEMISTRY. i. 175 pounds are also mentioned phenyl 2-hydroxy-a-mphthyl ketone rn. p. 175"' from @-naphthol and benzotrichloride ; 2-izydroxy-l- benzoylmphthulene-3-cccrboxyli~ acid from 2-hydroxynaphthalene- 3-carboxylic acid and benzotrichloride ; p7henyl 5-chloro-4-hydroxy- u-mphthyl ketone m.p. 121" from 8-chloro-l-hydroxynaphthalene and benzotrichloride ; 4hydrox y- 1 -benxoylnuphthulene-3 -sulphonic acid a white powder giving phenyl 4-hydroxy-a-naphthyl ketone by elimination of the sulphonic acid group from l-hydroxynaphthal- ene-2-sulphonic acid and benzotrichloride ; 4-hydroxy-l- benzoyl- -naphthalene-5-su~ph~i~ acid ; 1 -hydroxy-2-benxoylnap7~thalene-4-sul- phonic acid ; 1 -izydroxy-:!-benxoylnaphthalene-5-sulphonic acid. By heating the above-mentioned carboxylic acids or sulphonic acids with 5% sulphuric acid under pressure a t 180-190" or in the presence of dimethylaniline at 150" the carboxylic acid or sulphonic acid groups are eliminated. Examples are given of the preparation by fhis reaction of phenyl 4-hydroxy-a-nuphthyl ketone i-chloro-4'- hydroxy-2 1'-dinaphthyl ketone crystals m.p. 213") and 4 4'-di- hydroxy-1 1'-dimphthyl ketone. 3-Methoxynaphthalene-2-ketocarboxylic Acid. W. DIL- THEY and G. LIPPS (Ber. 1923 56 [B] 2443-2445).-3-Acetyl- 2-methoxynaphthalene condenses with benzaldehyde in the presence of alcoholic sodium ethoxide to give 2-cinnamoyl-3-met~ox~pht~~- deep yellow leaflets. m. p. 87" ene7 C6H4<H 6*CO -CH :CHP h ' G. W. R. H:C*OMe which is oxidised by potassium permanganate in the presence of pyridine to 3-rnethoxy-2-mphthoylformic acid c6H4< CH F*OMe CH:C*CO*CO,H ' pale greenish-yellow crystals m p. 162-163' (decornp.). $he presence of the carbonyl group m the latter acid could not be established in the usual manner but it is shown that the gas evolved when it is melted consists of approximately equal volumes of uarbon monoxide and carbon dioxide.Attempts to oxidise it to 3-methoxy- naphthalene-2-carboxylic acid were unsuccessful the substance being either unchanged or transformed into a-naphthyl methyl ether. During the preparation of the acid a second acid; colour- less rhombohedra1 crystals m. p. 142-143" is also obtained the constitution of which has not been elucidated. The follo- wpbstances are also described l-tin-8- 4 - & h ; y n a r p h yellow needles or almost colourless l~affelx.j xn. p. 85" ; 2-meth1xycinna~l-3-~nethoxynaphthalene yellow needles m. p. 99-100" ; l-metbxycinmmoyZ-4-ethoxyna/phthalene greenish-yellow needles m. p. 110-1 11 " ; 2-o-chlorocinnramoyZ- 3-ooadli-o~yrurphthaZene~ pale yellow needles m.p. 121"; l-o-c&o- c i n ~ m o y 1 - 4 - e t ~ ~ p h t h a l e n e 7 pale yellow needles m. p. 97-98". Substituted Salicylic Acids. 111. The React.ion of 7-DG carboxyl Chlorides with Sodium Salicylate. H. P. KAWP- MANN and H. VOSS (Ber. 1923 56 [B] 2508-2514; cf. A. 1922 i 252 ; 1923 i 795).-The condensation of s-o-phthaloyl chloride with sodium or disodium salicylate with the production of salicylic H. W.i. 176 ABSTRBOTIJ OR CHEMICAL PAPERS. phthalidylidene ether ester (annexed formula) has caused the authors to examine the action with other 7-dicarb- oxyl chlorides. The problem is intimately con- n?>O nected with the transformation of symmetrical into \//\ unsymmetrical acid chlorides and the production of 0 9 unsymmetrically constituted derivatives from the I 70 former.s-Tetrachlorophthaloyl chloride reacts with di- '-\ sodium salicylate in the presence of benzene to give '-' salicylic tetrachlorophthalidylidene ether ester colour- less crystals m. p. 199" which is stable towards cold sodium carbonate solution but is hydrolysed when warmed. as-Tetra- chlorophthaloyl chloride prepared by the action of aluminium chloride on the symmetrical chloride a t 150" (cf. Ott A. 1912 i 828) long lustrous needles m. p. 137" is more stable than as-phthaloyl chloride and is only partly transformed into the symmetrical variety when distilled. s-Az.s-Dihydrophthaloyl chloride a pale yellow liquid b. p. 122O/ 13 mm. gives with sodium salicylate in the presence of ether salicglic Az.6-dihydrophthalidylidene ether ester colourless crystals m.p. 165" ; as-A2:6-dihydrophthuloyZ chloride forms pale yellow crystals m. p. 131". s-A2-Tetrahydrophthaloyl chloride a pale yellow liquid b. p. 129"/ 14 mm. is readily converted into salicylic Az-tetrahydrophthulidyl- idene ether ester a colourless substance m. p. (indefinite) 105" (decomp.). The conversion of the symmetrical into the unsym- metrical chloride could not be effected. Pyridine-2 3-dicarboxyl chloride and sodium salicylate in the presence of boiling benzene give salicylic pyridine - phthalylidylidene ether ester (annexed formula) m. p. /f\is!h 168". \/,\ Succinyl chloride and sodium salicylate yield sali- cylic succinidylidene ether ester which exists in two c,H,.co isomeric forms colourless needles m.p. 176" when rapidly heated and m. p. 192" ; the former compound passes into the latter when it is boiled with glacial acetic acid. The isomerism probably depends on keto-enolic desmotropy. Salicylic maleinidylidene ether ester m. p. 204" ia prepared with the aid of fumaroyl chloride. It dissolves in cold sodium carbonate solution from which it is precipitated unchanged by acetic acid. The unusual solubility is attributed to the wandering of a hydrogen atom although the mobility of hydrogen attached to a doubly bound carbon atom is surprising. [With w. DBHN~~~.]-ap-Dibromomaleinyl chloride reacts with sodium salicylate in the presence of ether to give salicylic ap-di- brmomaleinidylidene ether ester needles m. p. 10" which does not dissolve in cold sodium carbonate solution.N 9 9 IF. W. The Diphenic Acid and the Fluorenone Serieq. I. H. W. UNDERWOOD jun. and E. L. KOCRMANN ( J . Amer. Chem. SOC. 1923,4-5,3071-3077).-Diphenic anhydride and phenol react in theOIKIANIC ClHEMISTRY. i. IT7 presence of fuming stannic chloride and from the product phenoldi- phenein colourless rhombic crystals m. p. 250-251" and an amor- phous powder were isolated. The former dissolved in sodium hydr- oxide to a yellow solution whilst the latter gave a deep red colour. The reaction between resorcinol and the anhydride in the presence of zinc chloride gave resorcinol-diphenein colourless crystals m. p. 178-179" soluble in sodium hydroxide without fluorescence and an amorphous powder which gave strong fluorescence when dis- solved in dilute sodium hydroxide (T.1923,123,225). No definite substance was isolated from the product of reaction between diphenic anhydride and pyrogallol in the presence of stannic chloride. Diphenic anhydride was converted into its isomeride diphenylene- ketone-4-carboxylic acid on heating with stannous chloride or zinc chloride and the reverse change was accomplished by heating the ketone acid with acetic anhydride and glacial acetic acid. The ketone acid reacted with phenol and resorcinol to give amorphous substances identical with those obtained in the reactions described above. Fluorenone reacted with phenol and resorcinol to give similar products. None of these products appear to possess quinoid structure . F. B. Certain Cyclic and Fatty-aromatic Bases from Di-o-nitro- benzyl-acetoacetic and -malonic Esters.S. GABRIEL and REINHOLD WOLTER (Ber. 1923 56 [B] 2445-2448).-Ethyl di-o-nitrobemylacetoacetate is reduced by stannous chloride in the presence of glacial acetic and y6H4*CH2\ CH2ev6H fuming hydrochloric acids to the sub- K--cMe/ ''~0 -N H stance (annexed formula) colourless needles m. p. 184" after softening a t 178",- which is transformedb by boiling 0 hydriodic acid into non-homogeneous 3-o-aminobenzyl-2 -methylquinoline (see below). Ethyl di-o-nitrobenzylmalonate is conveniently transformed into di-o-nitrobenzylacetic acid m. p. 149" by treatment with some- what diluted sulphuric acid a t 180-185". Di-o-nitrobenzylacetyl chloride prepared from the acid and phosphorus pentachloride m. p. 91-92" is converted by ethyl sodiomalonate in the presence of benzene into ethyl di-o-nitrobenzylacetylmte ( NO2*C,H4*CH2),CH*CO*CH( CO,Et) .colourless rhombic leaflets m. p. 80" after softening a t 77" from which di-o-nitrobenzylucetone (NO,*C6H,~CH),CH0COMe prisms m. p. 89-89-5" is prepared by the action of boiling hydrochloric acid. The ketone.is reduced by phosphorus and hydriodic acid to 3-o-aminobenzyl-2-methylquinoi?ine (see above) flat needles or oblong plates m. p. 166-167" which yields a crystalline diibydro- iodide and dikydrochloride. The base is converted by phthalic anhydride into the substance C2,H1,0& m. p. 127-128" and by benzaldehyde into the benzylidene derivative m. p. 17O-171". Di-o-nitrobenzylacetylchloride is converted by benzene and aluminium chloride into di-o-nitrobenzylacethenone (N0,*CBH,*CH2),CH.COPh .I - \/i.178 ABSTRACTS OF CHJEMICAL PAPERS. m. p. 108-108-5" which is transformed by hydriodic acid and phosphorus into 2-phenyl-3-o-aminobenxyZquinoline m. p. 177- 178"; the base yields the cmpound C30H2002N2 m. p. 185" when treated with phthalic anhydride. Di-o-nitrobenxylacetmide colourless leaflets m. p. 162" pre- pared by the action of ammonia on a concentrated solution of the corresponding chloride in benzene could not be transformed into the amine by potassium hypobromite. It is converted how- ever by the action of sodium and bromine in the presence of alcohol into the compound (N0,*C6H,*CH,),CH*NH*C02Me needles m. p. 139" which is hydrolysed and decomposed by sulphuric acid a t 120" into di-o-r,itrobenxylmethylamine (NO C 6H4*CH2) ,CH*NH colourless hexagonal plates m.p. 82-83" (the sulphcite is described). Treatment with red phosphorus and hydriodic acid converts t'he base into di-o-aminobenxylmethylamine a glassy solid which yields a trihydroiodide decornp. above 230' and a trihydrochloride which softens above 260". H. W. The Action of Potassium ferricyanide on Quinizarin in Alkaline Solution. R. SCHOLL P. DAHLL and F. HANSGIRG (Ber. 1923,56 [B] 2548-2555).-The oxidation of 1 4-dihydroxyanthra- quinone by potassium ferricyanide in 0 alkaline solution occurs in a similar manner to that of alizarin (Scholl and Zinke A. 1919 i 25 406) and ' ('*c0*cH'cH*co2H leads to the formation of p-2-hydroxy- 1 4-naphthaquinonyl - 3 - acrylic acid (annexed formula).[With P. HASENCLEVER and F. FLEISCHMANN.]-A solution of 1 4-dihydroxyanthraquinone in aqueous potassium hydroxide is rapidly oxidised by six molecular proportions of potassium ferri- cyanide to @-2-hydroxy-1 4-naphthaquinonoyZ-3-ctcrylic acid yellow needles; the acid decomposes rapidly at about 190" and more slowly a t a lower temperature even in solution. The ammonium Salt the potassium salt C,,H,O,K and the silver salt C$&?,& are described. The silver salt is converted by methyl iodide a t the atmospheric temperature in the absence of light into methyl p-2-h ydrox y- 1 4-mphthuquinon yl-3-acr ylate OHC ,H40,*CO*CH:CH*C0,Me pnbh-yellow crystakine needles m. p. 158O the sodium salt of which if3 described. The acid is converted by saturated methyl- almhdio hpogen chloride into @-2-methoxy-1 4-mphthapinonyl- 3-awgZic d m.p. 165' which is transformed by aqueous sodium acetab info the orange-yellow sodium salt; the silver salt a y d b q amorphous substance is also described. The esterification of the naphtholic hydroxyl p u p by alcoholic hydrogen chloride has been observed meviouslv but it is verv remarkable that the \I' .OH \/ / 0 carboxyl group remths unaffvected ; the poss:bility that t,he product is it lactone,ORGAXXO CHEMISTRY. i. 179 disregarded. The phenolic ester m. p. 158" is isomerised by treat- ment with methyl-alcoholic hydrogen chloride to the methosy- acid m. p. 165". Methyl 8-2-methoxy-1 4-mphthaquinonyl-3- wrylate OMe*C1~02*CO*CH:CH*C02Me,MeOH pale yellow needles m. p.130-131" (decomp.) is prepared by the action of a large excess of boiling methyl iodide on the di-silver salt of the hydroxy-acid; the firmness with which the molecule of methyl alcohol is retained suggests that it is attached to a carbonyl group in the form of a semi-acetal. The hydroxy- and methoxy-acids are only very slowly acted on by bromine dissolved in chloroform whereas the phenolic ester m. p. 158" absorbs two atomic pro- portions of the halogen one of which is subsequently lost in the form of hydrogen bromide. The hydroxy-acid and the phenolic ester give reddish-brown or orange-yellow solutions in hot sodium hydroxide solution which rapidly become dark blue and from which a dark violet acid is precipitated by dilute sulphuric acid; this acid has not been obtained in the homogeneous crystalline form but there can be little doubt that it is a chromanone deriv- ative C,H,< Co*?-o*?HeCo2H.The phenolic ester unlike the CO*C*CO* CH hydroxy- or methoxy-acia is converted rapidly at the atmo- spheric temperature by ammonia into a bluish-black compound to which the constitution C,H,< Co*fi*NH*~H*Co2Me is assigned. CO*C*CO-CH Reduction of di-potassium p-2-hydroxy-1 4-naphthaquinonyl- 3-acrylate by sodium hyposulphite in aqueous solution leads to the production of p-1 2 4-trihydroxy-3-mphthoylacryZic acid yellow needles m. p. 208". Bile Acids. .X. M. SCHENCK (2. physiol. Chem. 1923 131 269-276).-( 1) Deoxycholic acid when heated with alcoholic ammonia in a sealed tube at about 220" yields the amide C,H,,O,N m. p.186" which crystallises from a mixture of alcohol and water in needles containing 3H,O. (2) Biloidanic acid obtained from bilianic acid purified by means of a new method through the dioxime has the formula C,H,,O,,. From Gobilianic acid when oxidised by 32-35% nitric acid there is obtained in small yield a triketo- tricurboxylic acid C,H,,O fine six-sided rectilinear plates which froth and turn brown at 230-235". W. 0. K. H. W. Preparation of Deoxycholic Acid. J. D. RIEDEL AKT.-GES (D.R.-P. 374367 ; from Chem. Zentr. 1923 iv 726).-Dihydroxy- cholenic acid is hydrogenated in the presence of catalysts. Deoxy- chdk acid. ia &hind from the products by way of the crystalline acetic acid-deoxycholic acid compound m. p. 141". G . W. R. Preparation of an Unsaturated Bile Acid.J. D. RIEDEL AKT.-GES. (D.R.-P.. 374366; from Chm. Zentr. 1923 iii 726; ef. A. 1922 i 1160).-1n variation of an earlier patent dihydroxy- cholenic acid m. p. 260" is treated with bromine and alkalinei. 180 ABSTRB(ITS OB CEETUICAL PAPEBS. reagents. For example dihydroxycholenic acid is treated with bromine in methyl-alcoholic solution. From the products after boiling with an alkali hydroxide a substance apparently dihydroxy- choladienic acid is obtained m. p. 245-247". G. W. R. Preparation of Benzaldehyde. THE BARRETT Co. (Brit. Pat. 189091).-The catalytic action of the oxides of various metals on toluene in the vapour phase and in the presence of a gas containing oxygen (e.g. air oxygen ozone) is found to differ considerably. Thus vanadium oxide gives benzoic acid benzaldehyde maleic acid and a measurable amount of the products of complete combustion ; the oxides of molybdenum tantalum tungsten and zirconium give relatively high yielh of benzaldehyde and a relatively low degree of combustion ; the oxides of uranium manganese copper nickel chromium and thorium give relatively high yields of benzaldehyde together with relatively high degrees of combustion ; the oxides of cobalt and cerium give relatively low yields of benz- aldehyde and relatively high degrees of combustion whilst the oxides of titanium bismuth and tin give relatively low yields of benzaldehyde and relatively low degrees of combustion.Greatly increased yields of benzaldehyde accompanied by low degrees of combustion are obtained by using as cstalyst mixtures of the above oxides provided that at least one of these oxides is that of a metal of the fifth or sixth periodic group.Particularly efficient is a mixture of oxides of uranium and molybdenum (approximately in the proportion of from three to thirteen of the former to one of the latter) or of oxides of molybdenum uranium and copper. In preparing these oxides the best results are obtained by starting from a solution of the metals in organic acids. * The temperature of the catalyst should be between about 300" and 700". Organomagnesiurn Derivatives. 111. A. GARC~A BAN~S and L. MEDRANO (Anal. Pis. Quim. 1923,21 436-463 ; cf. Garcia BanGs and Vila A. 1922 i 734).-A study of the reaction between benzaldehyde and magnesium benzyl halides. On adding benz- aldehyde (1 mol.) to magnesium benzyl iodide (1 mol.) in ethereal solution the react ion proceeds normally yielding phenyl-o- t ol y 1 - carbinol whilst when magnesium benzyl bromide is used phenyl- benzylcarbinol crystals m.p. 62-65" is formed. In the inverse reaction where magnesium benzyl bromide is added to benzaldehyde in ethereal solution stilbene phenylbenzylcarbinol and diphenyl- isochroman m. p. 90-95" are formed. Using an excess of benz- aldehyde with magnesium benzyl chloride phenylbenzylcarbinol is formed by reaction in the cold. When the reaction is carried out with boiling in a reflux apparatus the reaction proceeds differently. From the products of the reaction dibenzoylphenylmethane m. p. 144-146" stilbene deoxybenzoin benzylidenedeoxybenzoin m.p. lOl-l02" and isobenzylidenedeoxybenzoin m. p. 86" are obtained but no diphenylisochroman. Magnesium bemy1 iodide gives with an excess of benzaldehyde amongst other products dibenzoyl- phenylmethane and a small quantity of diphenylisochroman. The W. T. K. B.ammo cJHEBm3TRY. i. 181 formation of. diphenylisochroman is held to be conditioned by the CHph' presence of excess of benzaldehyde. When heated with hydrochloric and acetic acids diphenyl- /\/\O isochroman @yes diphenylindene. From this and I ICHPh from the fact that a hydroxyl group was shown to \/\/ be absent the annexed formula is suggested for CH2 diphenylisochroman. From t,he formation of diphenylisochroman from benzaldehyde and magnesium benzyl bromide the presence of a conjugated double bond in the latter compound is indicated. G.W. R. Quinonemethides [Methyleneqyinones] and Pseudophenol- halogenides. 11. H. LIXDEMANN and H. FORTH (Annakn 1923 435 219-232).-An attempt has been made to prepare o-quinonemethides (cf. A. 1923 i 686). 3 5-Dibromosalicyl- aldehyde is converted by thionyl Br chloride into a colourless anhydro- Br/\/'H-O\/\ compound (m. p. 243") (annexed I I I IBr formula). The tri- andmono-acetates \/\O-bH/\/ of the aldehyde have m. p. 99-100" and 71" respectively (Simonis and Wenzel A. 1900 i 496 give 103" and No respectively). 3 5- Dibromo-2-methoxybenzaldehyde with phosphorus pentachloride gives the corresponding benzylidene chloride (needles m. p. 76") from which a quinonemethide cannot be obtained. 3 5-Di- brm-2-hydroxybenxylidene ChEoride from phosphorus pentachloride and the corresponding aldehyde (in presence of benzene) forms needles m.p. 97". It is rapidly reconverted into the aldehyde when treated with warm alcohol or acetic acid a cold solution in these solvents when treated with water becoming Erst orange (possibly owing to formation of quinonechloromethide) and then yellow (aldehyde). In the preparation of the last-named chloride a pZymeridz of 3 5-dibromo-1 2-benzoquinone-l-chloromethide m. p. 220-225" is also formed. 3 5-Dibromosalicylaldehyde with phosphorus pentabromide gives together with some anhydro-compound (m. p. 243' above) the corresponding bromide (needles m. p. 99") the latter (or the corresponding chloride) giving an m t y l derivative (m. p. 113-114") and an a d red needles m.p. 105" and imine. 2-Hydroxy-4 6-dimethylbenzaldehyde on bromination in presence of sodium acetate and acetic acid affords the 3 S-dibromo- derivative yellow needles m. p. 190-191" (the a d red needles has m. p. 180-181"). The dibromo-aldehyde which is unaffected by thionyl chloride is converted by phosphorus penfachloride (in presence of phosphorus oxychloride) into the anhydro-derivative (m. p. above 300") or (in presence of benzene) into the corresponding benzylidene chhide (needles m. p. 114-115") the latter with aqueous alkali giving first a transient orange colour (quinone- methide?) and then the yellow colour of the aldehyde. 3 5-Dibromo-2-hydroxy-4-methoxybenzaldehyde (pale yellow needles m. p. 97-98'; triacetute m. p. 98" monoacetate rn.p. 78") Eri. 182 ABSTBbarS OF UEEMIOAL P-. gives an unil (yellow needles m. p. 105") and an k i n e (m. p. 206") $he corresponding benzylidene chloride having m. p. 99". 3 5-Dibromo-4-hyd~oq-2-methoxybenzuldehyde has m. p. 170- 171" (triacetate a. p. 124"; anil m. p. 185') the corresponding benzylidene bromide having m. p. 111". The latter with aqueous alkali or ammonia gives successively a yellow blue and yellow colour whilst with sodium acetate solution 3 5-dibrm-2-methoxy- 1 4-benzoqzcirwne-l-bromomethide is formed (yellow needles m. p. 78-79'). The latter when treated with water gives the origifial aldehyde. The corresponding benzylidene chloride has m. p. 81" and affords the chloromethide m. p. 98-100". 2-Hydroxy- 1 -naphthaldehyde could not be converted into any derivatives of the type under discussion. E.E. T. Compound of Cinnamaldehyde with Arnylene. NEVERKA ALUJEVICH (Atti A. Accad. Lincei 1923 [v] 32 ii 292-294).- Exposure to the action of light in a glass tube of a mixture of cinnamaldehyde with excess of amylene results in the formation of an oily additive compound C,,H,,O which has the normal molecular weight in freezing benzene or acetic acid but was not found capable of purification. The compound unites with bromine yielding a brown dibromide and gives benzoic acid when oxidised by means of permanganate. Reduction of the compound by means of hydriodic acid yields a small proportion of a product not yet identified and treatment with phosphoric oxide gives a crystalline compound m. p. X25" also unidentified.W. BORSCHE (Ber. 1923,56 [B] 2357-2;359).-1t was shown previously (A. 1912 i 180) that both methyl groups of 4 6-dinitro-m-xylene react with benzaldehyde to give 4 6-dinitro-1 3-distyrylbenzene. It is now found that the 4 6-dinitro-m-xylene does not react with nitrous acid to form the expected dialdoxime but does react with p-nitrosodimethylaniline in alcoholic solution in presence of sodium carbonate t>o give 4 6-dinitroisophthalaldehyde-bis-p-dimethylami~ani1 a black crystalline powder m. p. 208". This is readily hydrolysed by nitric acid in benzene suspension to 4 6-dinitroisophthalaZdehyde CgH&CHO),(N02) pale yellow needles m. p. 132". This gives a dzoxzme bright yellow needles m. p. 184" and a bisphenylhydraxone black needles m.p. 251". From benzene solution in sunlight the aldehyde is gradually precipitated in the form of yellow needles m. p. 185;-186" apparently of 4 6-dinitrosoisophthalic m i d . 4 6-Dinit;ro-m-xylene also reacts with mercuric chloride in presence of sodium efhoxide to form 4 6-dinitroisophthalybidenetetramercuri- dioxide C8H406N,Hg4 a heavy yellow powder. Electrolytic Oxidation of isoEugenol. A. LOWRY and C. M. MOORE (Trans. Amer. Electrochem. Xoc. 1922 42 273-284).-The authors have investigated a process for the production of vanillin by the electrolytic oxidation of isoeugenol described in the German patent (D.R.-P. 92007). Experiments carried out with sodium T. H. P. 4 6-Dinitroisophthalaldehyde. CGH2 ( CH:N'C,H4'~e2)2(Nq,) E. H. R.OWANIO CHEBfISTRY. i. 183 hydroxide or sulphuric acid as electrolyte gave in every case negative results. Vanillin itself is found to be readily oxidised electro- lytically and even if formed by the electrolytic oxidation it would be immediately converted into other products.Hence it is concluded that if vanillin is produced by t4he electrolytic oxidation a totally different condition must prevail from that described in the patent. J. F. S. Acetyl Derivative of Deoxybenzoin (Tautomeric Form). C. V. GHEORGIU (Ann. Scient. Univ. Jassy 1923 11 307-308; from Chem. Zentr. 1923 iii 1159).-By treatment of deoxybenzoin with acetic acid and zinc chloride a crystalline precipitate m. p. 102-106" held to be the ncetyl derivative in the enol form is obtained. On hydrolysis however it does not give the corres- ponding alcohol but deoxybenzoin.Electrolytic Reduction of Oximes. I. Benzoinoxime. NASAYOSHI ISMBASHI (Mern. Coll. Xci. Kyoto 1923 7 39-44).- Benzoinoxime is only partly reduced electrolyticalIy in acid solution. A part is hydrolysed before electrolytic reduction occurs and the benzoin resulting from the hydrolysis is reduced to form hydro- benzoin benzoinpinacone and deoxybenzoinpinacone. Optimal conditioiis for the preparation of the amine require that the electrolysis be conducted a t 19" to 20" with a current density of about 0-3 amp. per sq. cm. and that a cathode of tin or lead be employed. The concentration of sulphuric acid in the catholyte should not exceed 5%. In alkaline or neutral solution na appreciable electrolytic reduction or hydrolysis of benzoinoxime is observed.3'. ANGELICO and F RIONFORTE (Gaxsetta 1923 53 800-807; cf. A. 1909 i 318; 1910 i 402 576).-The failure of the action of sodium hypobromite on picrotin ketone to yield bromoform and that of the action of iodine and potassium hydroxide to give iodoform render doubtful Horrmann and Bischof's suggestion that the molecule of this ketone contains the grouping -CH,*CO*CH (A. 1922 i 161). Fusion with potassium hydroxide of picrotinic acid for which formula (I) or (11) may be assumed yields besides products of profound decomposition a CHPh:CPh*OAc G. W. R. J. S. G. T. Picrotin Ketone and Picrotinic Acid. hie CH,*CH,*CH,*CO,H /\CH,*CH,-CH,*CO,H o<CO-/)Me o < q ) (I*) CMe2.?/ (11.) dicarboxylic acid C12H,,0 m. p. 132" of constitution (111) or (IV).On the other hand gradual oxidation of picrotinic acid yields a (111.) /-'CH2*CH2*CH2*C0,H /-\CH2*CH,*CH,*C0,H UV.) series of acids of the formulze C,,H,,O C,,Hl,O and C,,H,,O all HO,C Me C0,H \-/ \-/ Mei. 184 ABS!L'RACTS OW cBtE116ICAX PAPERS. of which give acetone when fused with potassium hydroxide aiid hence confain the phthalide grouping intact (A. 1910 i 404). From ifs formula the acid C,,H,,06 known as picrotinphthaldi- carboxylic acid evidently contains a carboxyl group in place of the methyl group of picrotiiiic acid so that its possible constitutions follow from formulae (I) and (11). Since when fused with potassium hydroxide picrotinic acid loses only acetone and gives a ciibasic acid picrotinphthaldicarboxylic acid should under similar conditions yield a tribasic acid.A crystalline acid m. p. about 153" is indeed obtained in this way but in quantity insufficient for analvsis since. however. it condenses with resorcinol in mesence of s;lph&ic acid to yieid a fluorescent compound it is ;robable HO,C C0,H that its formula is 7-\~H2*CH,*CH2*C02H and that picro- tinic acid is represented by formula (I). Horrmann (A. 1916 i 828) suggests that picrotin ketone and picrotinic acid may be derived from a @-ketonic acid CH,R*CO*CH,*C02H which cannot be isolated possibly owing to the readiness with which it loses carbon dioxide. Neither picrotin nor picrotoxinin has however yet yielded an oxime and the authors find that the action of amyl nitrite on picrotin in preseiice of sodium ethoxide gives principally two nitrogen-free acids. Oximimpicrotin ketone Cl,R,50,N m.p. 215" (decomp.) is readily convertible into the dzoxzme C,4H1404N2 which crystallises in minute needles m. p. 232" (decomp.). The acid C1,H1,05 or c&606 obtained by treating picrotin with amyl nitrite and sodium ethoxide forms minute crystals m. p. 330° and sublimes a t the melting point giving vapours which irritate the mucus. When heated with fused potassium hydroxide it yields acetone and with siilphuric acid and resorcinol it forms a fluorescein. It is accompanied by another acid which cont.aias C 54.29% and H 7.587/ and forms silky white needles m. p. 95". \-/ m n l 3 1. u. L. Anomalous Splitting of Ketimides. F. KROLLPFEIFFER (Ber. 1923 56 [B] 23&2365).-The ketimides obtained by con- densing anthranol methyl ether with nitriles are not as was to be expected hydrolysed by dilute acids to the corresponding ketones but are decomposed into anthrone.Thus 10-methoxy-9-anthryl- methyl-ketimide decomposes with formation of methyl alcohol acetic acid and anthrone. The ketone lO-methoxy-9-a~thryl methyl ketone is only obtained in small yield by boiling an aqueous solution of the hydrochloride of the ketimide; the ketone itself is readily hydrolysed to anthrone. The phenyl derivative 10-methoxy- 9-anthryl-phenyl-ketimide is much more stable than the methyl compound; it is only hydrolysed by boiling concentrated hydro- chloric acid giving anthrone and benzoic acid. The N-methyl derivative of this ketimide is likewise hydrolysed by boiling concen- trated hydrochloric acid forming ant hrone methylamine andORGANIC (3HEMISTRY.i. 185 benzoic acid. The readiness with which the acyl residue is removed in the zanthryl ketones appears to be influenced by the p-methoxy group for p-anthryl phenyl ketone is not hydrolysed by hot hydro- chloric acid in acetic mid solution althoagh with warm concentrated sulphuric acid it gives anthribcenesulphonic acid and benzoic acid. . I IO-Hethoxy-9-anth yLmethyl-kdirnide (annexed formula) is obtained by mixing anthranol methyl ether and acetonitrile with aluminium chloride and passing a current of dry hydrochloric acid through the cooled mixture; it forms a pale yellow crystalline powder m- p. 145-146". 10- Methox y -9 -ant hry Z methyl ketone forms \./\/\/' I pale yeIlow glistening square leaflets m.p. 18% ('J&:NH 183". l0-MetZboxy-g-anthryZ-~hen yl-ketimide forms stout yellowish-green crystals m. p. 147-148O ; its hydrocldoride forms an orange crystalline precipitate. 10-bfehq-9- anthryl-~henyZ-N-methyl-ketimide is obtained by methylating the ketimide with methyl sulphate; it forms gale yellow needles m. p. 127". E. H. R. 2 3-Diaminoanthraquino. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pat. 98312; from Chem. Zentr. 1923 iv 829).-3-Bromo-2-aminoanthraquinone is treated with aqueous or ethyl-alcoholic ammonia in the presence or absence of catlalysts at 170-190" under pressure. 2 3-Diaminmnthrquinone thus obtained is crystalline. OMe G. W. R. Derivatives of p-Methylanthraquinone. 111. The Synthesis of Prungula Emodin.R. EDER and C. WIDMER (Helv. Chim. A& 1923 6 966-981).-1t is known that emodin is a trihydroxy- P-methylanthraquinone and it is highly probable that two of the hydroxyl groups are in the 1 8-positions and the methyl group in the 3-position as in chrysophanic acid. It is also probable that the third hydroxyl is in a P-position and not adjacent to an or-hydroxyl group. These probabilities have now been confirmed by synthesis and the constitution of emodin esfablished as 1 6 8-trihydroxy- 3-methylanthraquinone. The synthesis was accomplished in a manner similar to that of chrysophanic acid (A. 1923 i SSS) starting from 3 5-dinitrophthalic acid and m-cresol. 3 5-Dinitro- p7ithalic anhydride is formed by boiling the acid with acetic anhydride ; it crystallises in white stout hygroscopic needles m.p. 163-164". It condenses with m-cresol in presence of aluminium chloride to give 3 5-dinitro-o-3'-hydroxy-p-toluoylhenzoic acid greenish-yellow leaflets m p. 2364237". This compound is very sensitive to alkalis forming a compound C,H,O,N white needles m. p. 251-252O (decomp.). It corresponds in composition with a nitrohydroxytoluoylbenzoic acid but could not be identifietl as such a compound. It can be reduced to an amino-compound yellow needles m. p. 305-306" (decomp.). 3 5-Dinitro-o- 3'-hydroxy-p-toluoylbenzoic acid is reduced by ferrous sulphate and ammonia to 3 5-diamino-o-3'-hydroxy-p-toZuoylbenz~c mid palei. 186 ABSTRACTS 03' CHEMICAL PAPERS. yellow needles m. p. 233-234". When heated in concentrated sulphuric acid at 160-170" this is converted into 6 8-diamino- ~ - h y d ~ o ~ - 3 - m e ~ ~ ~ n t h r a q u i n e stout red needles m.p. 306-307". This compound is soluble in alkalis separating as a salt on cooling; in concentrated sulphuric acid it dissolves with a yellow colour. It can be tetrazotised in concentrated sulphuric acid solution and when the solution is heated on the water-bath it decomposes forming 1 6 8-trihydroxy-3-methylanthr~u~none orange needles m. p. 256" identical with emodin. It was not possible to condense 3 5-dinit4ro-o-3'-hydroxy-p-toluoylbenzoic acid to an anthra- quinone derivative. E. H. R.. 1 8-Dihydroxy-3-methylanthraquinone. R. EDER (Swiss Pats. 95614 and 95947; from Chem. Zentr. 1923 iv 664).- 1 8-Dihydroxy-3-methylanthraquinone may be prepared from a-nitrophthalic acid (Eder and Widmer A.1922 i 260) and also by condensation of or-aminoacetylphthalic acid with m-cresol in the presence of aluminium chloride t o 3-amino-o-2'-hydroxy-p-toluoyl- benzoic acid from which 1 8-dihydroxy-3-methylanthraquinone is obtained by way of the diazo-compound or by heating k t h strong sulphuric acid a t 1 50 O where by 8 -amino - 1 - hydroxy- 3 -met h y Z - unthruyuime reddish-brown needles m. p. 237-238" is obt,ained. The latter by diazotisation and boiling yields the 1 8-dihydroxy- compound. G. W. R. Intramolecular Displacements of Atoms. I. Addition of Alcohols to Camphene. H. MEERWEIN and L. G~RARD ( A nnnlen. i923 435 174-189).-Semmler (A. 1901 i 90) by treating camphene with alcohols in presence of sulphuric acid obtained as he supposed isobornyl ethers which are similarly obtainable from isoborneol.A precise proof of the constitution of the ethers is now given for the f$mt time. isoBornyl methyl ether is formed by the interaction of camphene methyl alcohol and sulphuric acid or by that of methyl iodide and sodium bornyloxide and is quite distinct from the methyl ether of camphene hydrate obtained from the potassium derivative of camphene hydrate and methyl iodide. The results recorded previously (A. 1920 i 855) in connexion with the action of alcohols on camphene hydrochloride have an interesting sequel If a solution of camphene hydrochloride in an alcohol is kept at 20" the concentration of free hydrogen chloride (cf. A. 1922 ii 751) initially high slowly falls to a minimum (after several days) and then slowly rises to 100% of that present originally. These phenomena are due fo the following processes (1) Reversible interaction of camphene hydrochloride (I) and alcohol fo give hydrogen chloride and an ether (11).This inter- conversion is entirely analogous to that of triphenylchloromethane and triphenylcarbinyl ethers (a little of I1 decomposes into camphene and alcohol). (2) Isomerisation of unchanged camphene hydro- chloride into isobornyl chloride (111). As a result of this the .change I1 +I is promoted until no more ether remains.ORUAXIC UEFAMISTRY. i. 187 (3) Interaction of isobornyl chloride with alcohol to give isobornyl ethers (IV) ' CH,-CH-CMe CH,-CH-CMe I IR'OH --+ 1 CH,/ (1.) I (11.1 HC1+ I CH,/ CH 1 CMe*OR CH 1 CMeCl \CH/' \CH/ W.) (111.) .CH-OR CHCI This scheme was suggested by the results of a determination (against time) of the relative proportions of free hydrogen chloride isobornyl chloride a,nd camphene hydrochloride in such a system starting with camphene hydrochloride and an alcohol. With methyl alcohol a maximum content of isobornyl chloride is present a t the time corresponding with the above minimum concentration of hydrogen chloride. Proof of the explanation given is afforded in the following If an ethereal solution of camphene hydrochloride is slowly added to a methyl-alcoholic suspension of anhydrous potassium carbonate so that the solution never becomes acidic camphene hydrate methyl ether is obtained (in 50% yield) identical with the product from the action of methyl iodide on the potassium derivative of camphene hydrate (this preparation being effected in xylene suspension unchanged camphene being finally removed by means of ozone).Camphene hydrate methyl ether has m. p. 12-14' b. p. 201.5" or 88.5-89"/17 mm. df' 0.947749481 and n 1.47153 (mean constants of the two samples obtained). Active camphene [a] +50.75" when converted through the hydrochloride into the ether gives the latter with [cx~~-12*7lo. When shaken with a solution containing potassium ferrocyanide and hydro- chloric acid the methyl ether aff or& an additive compound 3C ,OMe,H,Fe (CN) 6. Whdst camphene hydrate ethyl ether could not be obtained from camphene hydrate it is readily obtained (although in small yield because of its sensitivity to acids) from camphene hydrochloride potassium carbonate and ethyl alcohol and forms a colourlem oil (b.p. 93"/17 mm. $2' 0.9350) decomposing a t 200" into camphene and alcohol. If camphene hydrochloride is allowed to remain in methyl- alcoholic solution for about fourteen days at 30" or until the con- centration of free hydrogen chloride no longer increases isobornyl methyl ether results; if the above active camphene is used the resulting ether has [a]' -23.4". Semmler's method using active camphene gives the ether with [a]$ -14.82' a rotation decreasedi . 188 ABSTRACTS OR' CEEMICAZ PAPERS. by prolonging the action of the methyl-alcoholic sulphuric acid. (This preparation depends on the initial formation of camphene hydrate sulphuric ester which changes into the isobornyl ester this with alcohol giving the ether.The rate of conversion of camphene hydrate esters into isobornyl ethers is greater with sulphuric and aromatic sulphonic esters than with halogen esters.) Similarly the ether mas obtained from sodium bornoxide and methyl iodide the mean physical constants of the various products being b. p. 191-191.5" 78"/17 mm. or 80°/19 mm. &io 0.9250- 0.9277 n$ 1.46252-1-46282. The unstable additive compounds described by Bertram and Walbaum (A. 1894 i 204) could not be obtained. It was found that isobornyl methyl ether was readily converted by hydrogen bromide into isobornyl bromide hydrogen chloride acting similarly but more slowly. When treated with hydrochloric acid and potassium ferrocyanide the ether gives an additive compound 3C,J3,,0Me,H4Fe(CN) 6 decomposing a t 170" whilst on heating with anhydrous zinc chloride it gives camphene and methyl alcohol stannic chloride effecting the same change more slowly whilst other metallic chlorides are without action.isoBornyl methyl ether is also formed by warming camphene hydrate methyl ether with methyl-alcoholic hydrogen chloride or by treating isobornyl chloride with methyl alcohol. Camphene hydrate methyl ether is rapidly decomposed whereas isobornyl methyl ether is unaffected by glacial acetic acid a t 80". The camphene produced (through the first-formed camphene hydrate acetate) is readily estimated by titration with perbenzoic acid so that mixtures of the two ethers may readily be analysed.Camphene hydrate ethyl ether affords camphene even when shaken 'for a few hours with 1% sulphuric acid the methyl ether being practically unaffected by the latter. The methyl ether is rapidly converted by traces of zinc stannic aluminium ferric and mercuric chlorides or antimony pentachloride into camphene and methyl alcohol (cf. isobornyl methyl ether) whilst hydrogen chloride and bromide decompose both hydrate ethers to give camphene hydrochloride (hydrobromide) this passing rapidly into isobornyl chloride (bromide). E. E. T. Camphor dichloride. [2 2-Dichlorocamphane]. H. MEERWEIN and R. WORTNANN (AnnaZen 1923 435 190-206).-The conversion CMe,-CHNe*OAcyl CMe,( OAcyl)*CHMe may be regarded as a result of ionisation followed by intra-ionic rearrangement (CMe,*CHMe)O*Acyl (CMe,*CHMe,)O-Acyl free radicals not being involved.The ordinary pinacone-pinacolin change may similarly be written (CMe,*CMe,*OAcyl) O*Acyl-+ ( CMe3*CMe*OAcyl)0*Acyl the reverse change not occurring owing to the instability of pin- acolin esters other than those with halogen acids. Pinacolin dichloride [n-dichloro- P P-dimethylbutane] and pinacone dichloride [Intramolecular Displacements of Atoms. J ,II. f - + - + - + -ORQANIO OHEndIgTaY. i. 189 [&diohloro- &dimethylbutane] cannot be interoonverted but if the vapours af the first substance be passed over barium chloride heated a t 400-.450" a little py-dimethylbuhdiene results probably owing to the intermediate formation of pinacone dichloride. Greater powers of isomerisation would be expected from 2 2 4 - chlorocarnphane which possesses a similar structure to pinacolin dichloride.The substance described as dichlorocamphane by previous authors (e.g. Bredt A. 1901 i 217; Marsh and Gardner T. 1897 71 290; Marsh and Hartridge T. 1898 73 852) is now shown to be a mixture of substances. If however a mixture of camphor (200 g.)? hosphorus trichloride (170 g.)? and pure phos- phorus pentachloriz (294 g.) is left a t 0" for a month pure a-cam#wr dichlom.de (2 2-dichZorocccmpkne) (I) is obtained m. p. 146-148" (decomp.). Occasional preparations fail and it is always necessary to test the product by studying its interaction with sodium ethoxide (boiling alcoholic solution) or with methyl alcohol (at 60") which proceeds in a characterbtic manner. When heated with a mixture of phenol and potassium acetate 2 2-dichlorocamphane affords a-chlormmphene (111) (colourless setting point about 20" b.p. 193-197") this on reduction with sodium and alcohol affording camphene (setting point 44.5" b. p. 156.5-158") and on ozonolysis giving a-chlorocamphenilone. The latter compound (in which CO replaces the hemi-cyclic CH group in 111) has setting point 14.5" b. p. 116-118"/18 mm. gives a semicarbaxone m. p. 206-207" (mixed with a little p-chlorocamphen- done semicarbazone 1 ) and an oxime m. p. 210-211". Phacolin dichloride with phenol and potassium acetate gives P-chloro-ry-dimethyZ-Aa-butene no intramolecular change occurring. The conversion of 2 2-dichlorocamphene into a-chlorocamphene occurs according to the scheme 3 CrCH (111.) the intermediate a-chloroeamphene hydrochloride (11) being obtain- able by combining a-chlorocamphene and hydrogen chloride.Thk hydrochloride is leess easily decomposed than camphene hydro- chloride but is completely decomposed by methyl alcohol at 50" in half an hour. This shows that the dichlorocamphane of previous authors contained at most traces of a-chlorocamphene hydro- chloride. The bomerism between pinacolin dichloride and pinacone dichloride is now seen to be similar to that between dichloro- oamphane and a-chlorocamphene hydrochloride CMe,*CMeC1 + CMe,Cl*CMe,Cl so that the present work affords a first confirmation of the authors' views with regard to the pinacoh change (above). Moreover 2 2-dichlorocamphane may undergo the retrogradechange.If in ifs preparation the temperature is^ allowed to rise or if impure phosphorus pentachloride is used an isomeride p-cumpk dichloride (colourless crystals m. p. 178-179*) is the main product. This substance is easily distinguished from its a-isomeride by its much smaller rate of reaction with 0.2N sodium ethoxide (or methyl alcohol) and is best prepared by treating a-camphor dichloride in toluene solution with stannic chloride until the product no longer reacts rapidly with sodium ethoxide (or methyl alcohol). On reduction p-camphor dichloride affords camphane and on warming with phenol and potassium acetate gives a mixture of 8-chtopocamphene (V) and chlorotricyclene (VI) as waa proved by the fact that this mixture on reduction with sodium and alcohol afforded tricyclene and camphene.The latter but not tricyclene is oxidised by ozone and the mixture can thus be identified. Again the mixture of p-chlorocamphene and chlorotricyclene on treating with ozone gave a mixture of chlorotricyclene (m. p. 13&135" b. p. 194-196") and p-chlorommphenilone needles m. p. 162-163" (semicarbazone m. p. 244-245'). p-Camphor dichloride is there- fore trans-2 6-dichlorocamphane (IV) the above reactions being expressed H. .. C l 2 CH2-yH-CH2 'v') CH-~!!!?~~(J I t CCH CMe-Cl \ p-CUormmphene hydrochloride (VI) may be obtained from p-chlorocamphene and hydrogen chloride. The conversion of a- into p-camphor dichloride is effected under conditions causing the change of camphene hydrochloride into ieobornyl chloride. The conversion is rapid in phenol solution but very slow in most solvents unless stannic chloride or antimony pentaohloride is resent.The dielectric constant of the solvent is of far gre&x d e n c e than the nature of the catalyst the change being very S~OW in light petroleum more rapid in benzene and still more rapid in the ionising solvents chlorobenzene and nitrobenzene. The case is evidently one of the intra-ionic isomerisation of esters no tricyclene compounds being necessarily involved. Into the same clasr~ of change may be put the relationships (hitherto unex- plained) between fenchyl alcohol a-fenchene hydrate isofenchyl alcohol and p-fenchene hydrate (these relationships being shown schematically in the paper). E. E. T.ORGIANIO CHEMlSTRY. i. 191 [Intramolecular Displacements of Atoms.] 111. Racemis- ation Phenomena in the Camphor Series. H. MEERWEIN and F. MONTBORT (Annden 1923 435 207-218).-0ptically active isobornyl esters undergo racemisation under conditions specially favouring the rapid conversion of camphene hydrate esters into isobornyl esters (A. 1922 ii 751). isoBorny1 chloride undergoes complete racemisation in three hours'in cresol solution a t 20". In most solvents racemisation is too slow to follow and the use of catalysts is to be avoided owing to their tendency to form additive compounds with the solvent with resulting decay of activity. To overcome this difficulty the velocity of racemisation has been measured in cresol and in mixtures of this solvent with nitromethane nitrobenzene bromobenzene chlorobenzene ethyl bromide benzene light petroleum benzonitrile anisole aceto- nitrile and ether.It is found that except in the cases of aceto- nitrile benzonitrile and anisole which form additive compounds with cresol the order of solvents from the point of view of decreas- ing racemisation velocities is the same as that of the velocity of conversion of camphene hydrochloride into isobornyl chloride (loc. cit.) which in turn is (approximately) the order of decreasing dielectric constants. In the three cases where additive compounds are formed the velocity constant tends to decrease. If however the solvent-mixture is left for some time before use a good constant is obtained somewhat smaller than that otherwise observed. The parallelism between the two above types of change suggests that the racemisation change like that of camphene hydrochloride into isobornyl chloride is due fo ionisation ; two alternative schemes are suggested for the actual mechanism of the former change (1) By analogy to the behaviour of a-camphor dichloride (this vol. i 188) the chlorine atom in &-isobornyl chloride (I) may be assumed to wander from position 2 to position 6 when I-isobornyl chloride (11) results (2) The second suggested scheme is self-explanatoq (I to V being respectively d-isobornyl chloride the isoborn Lion (plane formula) I-isobornyl chloride and d- and I-bornyl ohyorides) :i.192 ABSTRAOTg (up C?HEl¶IW PAPER% This wonld account for the observed formation af b0rny-l chloride during the Facemidion of iaobornyl chloride (loc.eat.). E. E. T. The Rotation-dispersion of some Homologo~s Methylene- camphor Derivatives. H. RUPE and C. COURVOISIER (Hdv. China. A& 1923 6 1049-1071).-The method described by Rupe and Burckhardt for the synthesis of p-camphorylidenepro- pionic acid from chloromethylenecamphor and ethyl sodioaceto- acetate (A. 1917 i 141) is a general one and has now been used for the synthesis of a number of homologous acids from chloro- methylenecamphor and ethyl alkylacetoacetates. Since the acids readily lose carbon dioxide when heated giving alkylmethylene- camphors a general method is provided for the synthesis of these compounds. It was found that the optical rotations of these alkylidenecamphors changed when the substances were repeatedly distilled. This phenomenon is to be attributed to cis-tram-iso- merism and in the case of ethylmethylenecamphor it is probable tlpt at least one isomeride was obtained in the pure form.This isomeric change during distillation accounts for the difTerent values €or the optical rotation of methylmethylenecamphor recorded by Gff erent observers. The rotations of the compounds described were measured for four Werent wave-lengths and all showed normal rotation-dispersion. ~ 8 ~ 1 4 < X $ ~ ~ c H ~ e - c o 2 ~ t ~ obtained from c~loromethylenecamphor and ethyl methylaceto- acetahe by the action of sodium ethoxide distils a t 164-167"/ 12 mm. It is hydrolysed by boiling in a mixture of glacial acetic acid and fuming hydrochloric acid. The free P-mmphorylidene- a-methylpropionic acid is purified through its calcium salt and by distillation.It forms an oil which crystallises slowly in bunches of needles m. p. 109-110". It decomposes at 160' giving a quantitative yield of ethylmethylenemmphor (n-propylidenemm&oam23hor) b. p. 113-llS" [a] +l4943lo d 0.9497 (prepared from non-crystal- line acid) or [a]; +73.26' dzo 0.9533 (from the crystalline acid). The latter product partly crystalliqed in white needles m. p. 41- 43' giving in benzene [a] +22.67" [a]F/[ct]c 2-16'. The crystalline product is probably a pure isomeride but whether cis or tram it is impossible to say. Ethyl P-cam~horyl~dene-a-ethyZ~rop~o~te from ethyl ethylacetoacetate and chloromethylenecamphor is a pale yellow bitter liquid b. p. 169'112 mm. The free acid forms silky white needles rn.p. 118" ; the calcium salt forms bunches of short white needles. The free acid begins to decompose at 125" giving a quantitative yield of n-butpZidenemmphor b. p. 130-131'/12 mm. [a] +94-58" di0 0.9389 [alp/[ aIc 2.36. Ethyl p-camphurylidene- a-propyEpropionate from ethyl n-propylacetoacetate and chloro- methylene camphor has h. p. 176-179'/9-5 mm.; the free acid has m. p. 95-96'. n-Valerylidenecamphor has b. p. 139-141'J 12 mm. [a]; +ll648" di0 0.9333 [alF![aIc 2.36. The condensation of ethyl sodioisopropylacetoacetate with chloromethylenecamphor Et&yl Q-ca~phorylidene-a-ntethylpropionate,ommc CHEMISTBY. i. 193 was unsatisfactory but ethyl sodiobutylacetoacetab condensed normally forming ethyl P-camphorylidene-#-n-butyl~opionc~ yellow oil b. p. 191-193"/11 mm.; the free acid can be crystallised with difficulty in white needles m. p. 76". The acid decomposes at 170" giving n-hexylidenecump7wr b. p. 147-149"/13 mm. [ a x + 141*13" $? 0.9252 [aIP/[alo 2-37. Ethyl p-cctmphorylidene- a-isobutylprqionate is a viscous pale yellow oil b. p. 183-185"/ 10 mm. ; the free acid forms white needles m. p. 97-98'; it has [a]; + 108.74" in benzene. CsH14'~~H*[CH212*CHMe ' is a viscous oil b. p. 144-146"/12 mm. [a] +133-84" dp 0.9202 [ a]p/[a]0 2.35. p-Camphorylidene-a-allylpro23ionic acid (annexed formula) has m. p. 95"; its ethyl ester is a mobile oil b. p. 183- 185"/11 mm. The acid loses carbon dioxide normally when heated giving CsH14<&CH*~€€*C02H a-camphorylidene-Aa-pentene a pale CH,.CH:CH~ yellow mobile oil having an odour of camphor and garlic b.p. 136-137°f 11 mm. [a]' +144.23" i-ZF 0-9475 [aIp/[alC 2-37. p-Camphorylidene- a-benzylpropionic mid forms white silky crystals m. p. 127"; the ethyl ester is a pale yellow viscous oil b. p. 226-228"/12 mm.; the sodium salt is very sparingly soluble. Distillation of the acid gives phenylpropylidenemmpamphor a pale yellow viscous oil b. p. 204-206" [ a ] g +126.92" &J" 1.0104 [alP/[aJc 2-36 Camphorylidene- methylsuccinic acid c,H,,< co I (?H2*Co2H crystttllises in bunches of small white needles m. p. 158" ; the ethyl ester is a yellow viscous oil b. p. 214-222'112 mm. Distillation of the dicarboxylic acid a t 190-215"/12 mm. gives y-camphorylidenebutyric acid a viscow yellow oil b. p. 210-213"/10 mm. [a] +32.31" in benzene d? 0.9078. In the course of the work a number of by-products were obtained.In several cases the cis-form of dicamphoethandiene (A. 1919 i 335) was isolated from the reaction product. Another qlw of by-product resulkd from the fact that the p-camphorylidepepro- pionic acid and its derivatives form sodium derivatives which can react with a second molecule of chloromethylenecamphor forming dicamphorylidene derivatives. The following compoundb of t b type were identified. Ethyl di (mmphorylidenemeth yl) -pl'opioncce (C,Hl~<~~H)2:CMeoC02Et m. p. '118" ; ethyl di(mmphqZ&ne- methyl)-n-butyrate m. p. 161" ; ethyl di(carnphory1idenemethyZ)- n-valerate m. p. 175" ; ethyl di(campamphorylidenemethyl)allylcccetate m. p. 148" and ethyl di(camphurylidenemthyl)succinute m.p. 105'. Action of Ferric Chloride on Hydroxymethylenecamphm. If. RUPE and M. SCH~~RER (Helv. Cliim. Acta 1923,6,1072-l076).- When hydroxymethylenecamphor is boiled for some hours in alooholic solution with ferric chloride z-chlorocamphor is formed ; isoAmylmethylenecarnphor co C:CH*CH*CO,H E. H. R. VOL. CXXVI. i. 73i. 194 ABS!FBA65 OB UEEMIaAL PAPEES. in the same manner ferric bromide gives a-bromocamphor. To explain the reaction it may be assumed that hydrochloric acid combines with the hydroxymethylenecamphor forming hydroxy- methylchlorocamphor which reacts with water forming chloro- cttmphar and formic acid. Prolonged action of ferric chloride on hydroxymethylenecamphor results in the formation of camphoric anhydride probably with camphorquinone as an intermediate stage.E. H. R. Preparation of Menthyl Diethylaminoethylcarbarnate. from Chem. Zentr. 1923 iv 829).-Menthyl halogen formates are treated with at least the molecular quantity of diethylethylene- diamine NH,*CH,-CH,*NEt,. Menthyl diethylaminoethylcurbamte thus prepaxed from an ethereal solution of menthyl chloroformate and an aqueous solution of diethylethylenediamie with agitation and cooling is an oil having b. p. 142"/0.015 mm. The Action of Phenylhydrazine on Pinene Nitrosochloride. R. E. KREBEERS ( J . Amer. Pharm. ASSOC. 1922 11 604-606).- Phenylhydrazine and pinene nitrosochloride when allowed to react ih 95 yo ethyl alcohol yielded phenylhydrazine hydrochloride an unidentified substance yellow crystals m. p. 147-148" and a substance C,,H,lN faintly yellow hard prisms m.p. 148-150". Stick-hc. A. TSCHIRCH and F. LUDY jun. (Hdv. Chim. Acta 1923 6 994-1008; cf. Tschirch and Farner A 1899 i 446).- A systematic investigation has been made of Indian stick-lac the resin formed by a species of louse Tachardia h c a parasitic on certain trees in the East. The aqueous extract contains one of the dyes! present in the stick-lac; this is precipitated by lead acetate as d violet lake. The filtrate contains dextrose and laevulose besides albumin ; the ash from the evaporated filtrate contains nitrogen sulphur potassium and calcium. The lac appears to contain invert-sugar probably formed enzymatically by the insect from the sucrose of the tree. The red dye laccaic acid is obtained from the lead acetate precipitate by extraction with alcohol con- tkining hydrochloric acid; it crystallises in stout red prisms.Dimroth and Goldschmidt (A. 1913 i 981) failed to prove that the dye is an anthraquinone derivative; this has now been done by distillation with zinc dust. In dilute alcohol laccaic acid shows absorption bands at X 0-545-0*520 p and 0-510-0*488 p. Since the dye-is formed in the Tachardia by a yeast-like organism it is interwting to find that its absorption bands are very similar to thme ehown by the colouring matters from red yeasts and bacteria. In concentrated sulphuric acid laccaic acid dissolves with a carmine- red colour showing the bands A 04XkO.560 p 0*540-0.520 p and 8*MM-o-490 p and in sodium hydroxide solution its colour is reddish4olet ~ t h the three bands A 0-6104.575 p 0.555-0-533 p and 0*510-0*490 t. The dye is a good indicator the change from yellow (acid) to violet (alkali) being sharp.Alkaline solutions of the dye are unstable. Dyeings on silk and wool from an acid bath SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (swiss Pat. 99625; G. W. R. CHEMICAL ABSTRACTS.ORQANIO CHEMISTRY. i. 195 are very fast to light. The constitution of the dye is as yet unknown. Although it is probably a glucoside no sugar could be obtained from it by hydrolysis. Extraction of the residue from the aqueous extraction of the stick-lac with cold alcohol removes the resin the perfume and a second dye erythrolaccin. The alcoholic extract is poured into dilute hydrochloric acid and the precipitate filtered off dried and extracted with ether.The ethereal extract is evaporated and from the residual resinous oil the erythrolaccin crystallises in yellow leaflets. The crystals can be freed from resin by means of chloroform. The dye can be sublimed forming red felted crystals. Its yellow solution in an ether-alcohol mixture has a band at X 0.510-0.485 p ; with sodium hydroxide there are two bands at X0-6154.59Op and 0-572-0-548p. The bluish- violet solution in concent,rated sulphuric acid shows four bands at X 0.680-4.640 p 0.6104.590 p 0.560-0.540 p and 0625- 0.300 p. It forms a tetra-acetyl derivative green oblique tablets and is probably a tetrahydroxymthylunthraquinme. From an alkaline solution of the resins after separation of the erythrolacoin ether extracts the perfume which crystallises in tablets having the characteristic shellac odour.The portion of the resins soluble in ether contains besides aleuritic acid shown by Harries and Nagel to #be a trihydroxypalmitic acid (A. 1922 i 522) a monohydroxy- palmitic acid m. p. 76.5-77" and probably other fatty acids. These are probably present as lactides. The resin insoluble in ether is soluble in hot alcohol and can also be hydrolysed giving aleuritic acid. Ethyl aleurate crystallises in long needles m. .p. 57-58". The residue from the stick-lac when extracted mth boiling alcohol gives a wax crystallising in colourless leaflets m. p. 82" from which by hydrolysis an alcohol tuchrdiucerol C,H,O m. p. 81-82' and an acid m. p. 74-76" were obtained. The remainder of the wax was extracted by boiling benzene; this fraction has been examined by Gascard (A.1914 i 1045). After these extractions the residue of the stick-lac consists only of the skeleton of the Tnchardia with a little adsorbed laccaic acid. E. H. R. Scission of Potassium Atractylate. F. ANGELICO and F. MONFORTE (Gazzetta 1923 53 808-812; cf. A. 1907 ii 122; 1910 i 403).-Potassium atractylate the glucoside of AtradyZis gummif era or either of its decomposition products atrwtyliretin and atractyligenin serves aa an excellent colour reagent for aromatio hydroxy-aldehydes in general. The reagent is treated first with a little concentrated sulphuric acid and after a few minutes with a drop of an aqueous solution of the hydroxy-aldehyde; a red color- ation similar to that of rosolic acid is obtained the exact tint varying somewhat with the aldehyde employed.Estimation of the sulphur and potassium present in and of the raleric acid and dextrose formed on hydrolysis of it sample of potassium atractylate gives results in agreement with the fckula C&,,O,,S&,. Atractyligenin c14H&4 obtained by hydro- lysing the glucoside and aiterwards acidifying the liquid forms h 2white crystals m. p. 168" and does not reduce Fehling's suh&ion. Atractyliretin prepared by prolonged boiling of the glucoaide with normal sulphuric acid is obtained as a white compound which hardens when it is triturated with water and then forms a white powder m. p. about 190" (decomp.) ; like the isomeric atractyligenin it exhibits acid properties and does not react with hydroxylamine or phenylhydrazine. T.H. P. M. BRIDEL (Bull. SOC. Chim. biol. 2923 5 801-805).-The work of Rosenthaler recently has shown that the glucoside loganin originally described by Dunstan and Short (A. 1885 395) is a mixture of meliatin (A 1910 i 692) and another substance not identified. The name loganin has therefore no longer any significance. The Saponins of the Sarsaparilla Root. H. P. KAUFMANN and C. Fums (Ber. 1923 56 [B] 2527-2533).-A.n investigation of the saponins of sarsaparilla root imported from Honduras in 1918 ; the date of harvesting is uncertain. The ash contains the following substances expressed as per- centages of the dried root SiO 1.25; A1,0 0.79; CaO 0.57; MgO 0.50; G O 1.51 ; C1 0.46. The finely divided root is extracted successively with chloroform light petroleum benzene ether anhydrous alcohol and aqueous alcohol (50%).The light petroleum extract contains cetyl alcohol. The saponins are isolated as a form soluble in absolute alcohol (saponin A) and an insoluble form (saponin B). Saponin A is purified by dialysis against running water whereby it is obtained as a fawn-coloured powder which cannot be caused to crystallise. The presence of considerable amounts of dextrose in the sarsaparilla root considered in conjunction with the ready hydrolysis of the saponins by acids justifies the conclusion that the primary crystalline glucosides are partly changed by fermentative fission to amorphous secondary glucosides ; the contradictory results of previous investi- gations are probably due to the use of fresh or stored material. Saponin B is similarly purified by dialysis which however does not remove a considerable content of aluminium magnesium and calcium which are probably present in combination with galac- turonic acid.These can be eliminated by solution of saponin B in alkali and precipitation with acid. The purified material then closely resembles saponin A. The composition of the products vmies somewhat in d8erent preparations ; it appears that a loosely combined saccharide component is removed during the protracted extract ion. The saponins are hydrolysed by sulphuric acid (3-5y0) whereby possibly galacturonic acid glucose pentoses and methylpentoses are obtained. The presence of galactose arabinose or rhamnose could not be established. The sapogenin is freed from dark coloured impurities by solution in alcohol and precipitation with sodium ethoxide whereby ultimately sarsapogenin CB6H4203,HT0 slender colourless needles m.p. 183" (corr.) [a]a -58.68" m absolute methyl alcohol is isolated; the substance is identical with that Loganin or Meliatin? C. R. H.ORGANIC CHEMISTRY. i 197 obfahed by Power and Solway (T. 1914,105 201) from Jamaica sarsaparilla. The substance contains one hydroxyl group since it yields a monoacetate colourless needles m. p. 127" [a] - 57.1" when dissolved in chloroform (Power and Solway loc. cit. give m. p. 137"). The acetyl compound is hydrolysed by barium hydroxide to a substance C,6H4203,H20 m. p. 122"; possibly racemisation or intramolecular transformation takes place. The monobenxoyl derivative forms colourless crystals m.p. 124". The presence of a carboxyl carbonyl alkyloxy- or lactonic group could not be established in the usual manner.. The remaining two oxygen atoms must therefore be present in the molecule as a stable bridge. Distillation with zinc dust and treatment of the Willate with steam gives a diterpene C,&, b. p. 204-206"/748 mm. The Influence of Oxalic Acid on the Formation of Aniline- black. J. PICCARD (Elelv. Chim. Acta 1923 6 1029-1032).-The oxidation of a solution of aniline hydrochloride by sodium dichromate is accelerated about forty times by the addition of a small quantity of oxalic acid to the solution. The mechanism of the accelerating action has not been elucidated. The printing of Aniline-black on cotton or silk is facilitated by impregnating the material with aniline oxalate.[Cf. B. 91.1;' E. H. R. Platinum Oxide as a Catalyst in the Reduction of Organic Compounds. IV. Reduction of Furfuraldehyde and its Derivatives. W. E. KAUFMANN and R. ADAMS ( J . Amer. Chem. When furfuraldehyde in alcoholic solution was reduced with hydrogen under 1-2 atm. pressure in the presence of platinum black the first molecular equivalent of hydrogen absorbed gave a quantitative yield of furfuryl alcohol. The latter then reacted with hydrogen in four different ways to produce tetrahydrofurfuryl alcohol n-amyl alcohol pentane-a€-diol and pentane-a@-diol. The last-named substance CH,Me*CH,*CH(OH).CH,.OH; boiled a t 210-5-21 1*5"/ 751 mm. n'," 1.4412 ~$2 0.9802. Its diucetate boiled a t 219-220"/ '748 mm.ng 1.4202 di! 1.0148. The catalyst made from spectro- scopically pure chloroplatinic acid was very inefficient and the addition of ferrous chloride increased the rate of reduction to a maximum beyond which the rate decreased rapidly. This decrease in the case of the reduction of the aldehyde group was much less than that of the subsequent reduction of the ethylene double bonds. After the absorption of each molecular equivalent of hydrogen the catalyst was reactivated by shaking with air or oxygen. Pyromucic acid gave fetrahydropyromucic acid m. p. 21" and ethyl pyro- mucate gave ethyl tetrahydropyromucate b. p. 82"/11 mm. p-furylacrylic acid gave @-tetrahydrofurylpropionic acid b. p. 135-1 37 "/4 mm. f uroin gave a@ -dihydroxy- ap-ditetrahydrofuryl- ethane C,H,O*CH( OH)*CH( OH)*C,H,O furfurylideneacetone gave 01 -tetrahydrofurylbutan - y - one and a - tetrahydrofurylbutan - y - 01 b.p. 93-94"/2 mm. furfurylideneacetophenone gave y-phenyl- (slight decomp.). 33.- W. SOC. 1923,45,3029-3044 ; cf. A. 1922 ii 558 ; 1923 ii 310,773).-i. 198 ABSTRACTS OF CHEMICAL PAPERS. tetrahydrofurylpropan-7-one b. p. 153-154"/2 mm. and y-phenyl- tetrahydrofurylpropan-7-01 b. p. 167-168"/2 mm. F. B. Hydroxymethylfurfuraldehyde from Cellulose and its Derivatives. E. HEUSER and W. SCHOTT (Cellulosechemie 1923 4 85-89) .-The h ydroxymethylfurfuraldehyde which is formed on heating cellulose with 5% oxalic acid solution in an autoclai-e at 180" for half an hour has been shown to be identical with the isomeric modification described by Kiermayer.The following derivatives were prepared for this identification Semicarbazone m. p. 235-236"; phenylhydrazone m. p. 140"; anhydride m. p. 112"; anti-aldoxime m. p. 76"; syn-aldoxime m. p. 106". The normal modification prepared by Erdmann from bromomethyl- furfuraldehyde (from lmulose) gave a semicarbazone melting a t 216". This modification is converted into the isomeride by heating with 0.3% oxalic acid in it sealed tube. The hydroxymethyl- furfuraldehyde is extracted from the filtered digestion liquor by shaking with ethyl acetate. The quantity of the aldehyde increases with the degree of hydrolysis of the cellulose; thus normal cotton yielded 15.36% of dextrose and only 0.82% of the aldehyde viscose cellulose gave 63.21% of dextrose and 5.16% of the aldehyde whilst hydrocellulose prepared from viscose according to the prescription of Knoevenagel and Busch yielded 68.47% of dextrose and 10*840/ of hydroxymethylfurfuraldehyde.The presence of the aldehyde does not interfere with the estimation of the dextrose by the ferment- ation method. J. P. B. Preparation of Chromans. L. CLAISEN (D.R.-P. 374142 ; from Chem. Zentr. 1923 iv 725; cf. Claisen and Tietze A. 1921 i 263-264).-Phenols are treated with butadienes in the presence of acid condensing reagents. Phenol and isoprene gim 2 2-dimethylchroman. p-Cresol and isoprene give 2 2 6-tri- methylchroman a colourless oil with a strong odour b. p. 244- 244.5" ; ell, 0.9920. p-Cresol and py-dimethylbutadiene gire 2 2 3 6-tetramethylchroman an oil b. p.257-258" ; 4 0.9813. m-Xylenol and py-dimethylbutadiene give a pentamethglchrornan b. p. 263-265". G. W. R. The Reduction of Chrysin. J. PICCARD and E. OPPENHEIM (HeZw. Chim. Acta 1923 6 1009-1011).-Chrysin is reduced by magnesium in glacial acetic acid solution forming a compound which is probably the hydro1 of chrysin CI6Hl2O4. It forms an amorphous red powder m. p. 210-226" soluble in concentrated sulphuric acid and in alkalis with a yellow colour. It does not appear to be analogous to the violet substance obtained by Baeyer and Piccard by the reduction of dimethylpyrone (A 1911 i 901). E. H. R. Dipyrylenes. F. ARNDT and P. NACHTWEY (Ber. 1923 56 [B] 2406-2409).-When ethyl acetonedioxalate or ethyl chelidonate is boiled in benzene solution with phosphorus pentasulphide a com-ORGANIC CHEMISTRY.i. 199 pound is formed probably having the constitution ethyl 4 4'-di- pyrylene-2 6 ; 2' 6'-tetracarboxylcte O<C(CO2Et) :CH/ c:c<,:C( C0,Et) It forms slender cinnamon to carmine-red needles m. p. 203- 204". In concentrated sulphuric acid it dissolves with a deep red colour changing slowly to deep green but the ester is recovered from the green solution unchanged. 4 4'-Dipyrylene-2 ; G 2' 6'- tetracarboqkic acid forms a brownish-red infusible powder ; the sodium salt Cl,H,010Na,,3H,0 is brownish-red. The formation of the above tetracarboxvlate IS meceded bv that of an intermediate C( C0,Et) :CH\ CH :C( C02Et)> 0 .I I CH:C( CO,Et)> compound ethyl thiochelidonate S:C<CH:C(CO,Et) 0 bluish- green needles m.p. 51" which on heating dec6mposes into the et,hyl dipyrylenetetracarboxylate and free sulphur. The thio- chelidonate is conveniently isolated in the form of an additive compound with mercuric chloride a deep yellow precipitate m. p. 135-137". E. H. R. A Molecular Compound of Caffeine and Salicylic Acid. A. REGENBOGEN and N. SCHOORL (Phrm. Weekbkad 1924 61 34-36).-The melting-point curve for mixtures of the two sub- stances shows the existence of an equimolecular compound- with melting point about 135". By fusing together equal molecular proportions of the components and recrystallising from water the compound is obtained as fine needles m. p. 137" ; it is unaltered by recrystallisation from chloroform but decomposes in alcoholic solution. Its existence explains the solubility of caffeine in aqueous Strychnos Alkaloids.XXXXI. Various Observations on Derivatives of Brucine. H. LEUCHS W. GLADKORN and E. HELLRIEGEL (Ber. 1923 56 [B] 2472-2477).-Dihydrobmcinonic acid is decomposed by prolonged treatment with methyl-alcoholic ammonia at 100" into isobrucinolone an amorphous substance and aminodihydrobrucinolone. The conversion of isobrucinolone by 5N nitric acid into the red quinone C,,H,,O,N decomp. about 300" is described in detail; the substance is reduced by sulphur dioxide to the corresponding qtiinok C19H1805N2 needles or prisms m. p. 325-328" (decomp.) after darkening a t 320". The oxidation of acetylisobrucinolone dissolved in acetone by pofassium permanganate does not take place smoothly and gives dihydroxyucetyldihydroisobrucindone C,,H,,O,N slender needles m.p. 245" as sole crystalline product in yield which does not exceed 12%. The acidic products of the oxidation are amorphous but show the expected properties such as the red coloration with ferric chloride the loss of carbon dioxide when heated the decomposition by acidic hydrolysis into a hydrochloride (probably curbine hydro- chloride in place of the expected isocurbine salt) and a nitrogen-free acid apparently malonic acid. It therefore appears probable that iso- solutions of sodium salicylate. s. I. L.i 200 ABSTRACTS OF GHEMICAL PAPER& brucinolone conhins the same oxidisable group NCO*CH,*CH:C:C as brucinolone-b and yields a substance which is a semi-amide of malonic acid and a ketone. The study of the oxidation of benzoyl- isobrucinolone C2,H2,O6N2 very slender needles m.p. 250" after darkening at 240" when rapidly heated [a]! +99" in glacial acetic acid solution did not lead to more favourable results. Brucinolic acid is converted by methyl-alcoholic ammonia at 100" into brucinolone glycollic acid and aminodihydrobrucinolone. Brucinolone-b is converted by benzoic anhydride and sodium benzoate at 100" into benxoylbrucinolone-b c2sH2606N2 prismatic aggregates m. p. 235-236" [a] -148" in glacial acetic acid solution and by phosphorus pentachloride in the presence of chloro- form at -20" and treatment of the product with ethyl alcohol into brucinolone diethyl phosphate PO(OEt),*O~C21H2,04N large colour- less leaflets m. p. 232-235". Brucinolone hydrate I and phenylcarbimide yield the com- pound C,,H,,O,N,,H,O coarse domatic prkms m.p. 191-192" (decomp.). Dihydroxydihydroacetylbrucinolone is converted by acetic anhydride and anhydrous sodium acetate a t 100" into diacetyldi- h~~ro~~~ihydrobrucinolone-b C2,Hls0,N2 colourless crystals m. p. about 280" (decomp.) after darkening and softening at 240P [a] -149.2" in glacial acetic acid solution. The oximation of ON-diacetylcurbin by a boiling alcoholic solu- tion of hydroxylamine causes the loss of the 0-acetyl group and formation of N-acetylcurbinoxime C20H2306N2 lustrous rectangular prisms m. p. 185-187". The attempted isomerisation of the oxime by acetyl chloride at 100" leads to the production of triacetylcurbin- oxime C,H2,0,N3 double pyramids m. p. 275" (decomp.) after becoming yellow a t 250".The Behaviour of Eucupine and Uric Acid Gels during Dialysis. The Distribution of Ions. P. RONA and W. B. MEYER (Biochem. Z . 1923 143 161-178).-In dialysing eucupine dihydrochloride ( C~H3,02N2,2HC1 +2H,O) considerable membrane adsorption occurs. This is greater with collodion membranes than when Schleicher-Schull shells are used but diminishes with increasing acidity and disappears a t pH 4. The adsorption may be overcome by previously saturating the membrane with eucupine. Eucupine dihydrochloride forms a true solution. Eucupine acetate gel and lithium urate gel are partly colloidal (60 %) and partly true solutions. In dialysing the urate gel lithium and uric acid pass into the external fluid in equimolecular concentrations. The transition between super- saturated uric acid solution in lithium hydroxide and lithium urate gel is sharp the former behaving as a true solution.On dialysing mte against potassium chloride the potassium diffuses inwards and the lithium outwards in proportional amounts whilst the external uric acid concentration diminishes with increasing amounts of potassium chloride. The system illustrates the unequal dis- tribution of electrolytes on the two sides of a membrane with a non-diffusible colloidal ion on one side. H. W. J. P.ORGANIC CHEMISTBY. i. 201 Some New NSubstituted Pyrrole-aldehydes ; and Oxindole-aldehyde. HANS FISCHER and K. SMEYKAL (Ber. 1923 56 [B] 2368-2378) .-The Gattermann aldehyde synthesis (cf. Pischer and Zerweck A. 1922 i 758) has been applied to the synthesis of a number of N-substituted pyrrole-aldehydes. Ethyl 1-phenyl-2 5-dimethyl-4-aklehyd~pyrrole-3-mrboxylate CMe:c*CO,Et NPh<CMe:&CHO ' from ethyl 1-phenyl-2 5-dimethylpyrrole-3-carboxylate forms colourless crystals m.p. 82"; the free acid has m. p. 240". The ethyl ester forms a phenylhydmzone colourless crystals m. p. 156-160" and an oxime m. p. 150". Ethyl 1-p-tolyl-2 5-dimetltyl- pgrrole-3-carboxylate from p-toluidine chloroacetone and ethyl acetoacetate forms colourless crystals m. p. 55"; the free acid forms large crystals m. p. 240". By Gattermann's synthesis with hydrocyanic acid the ester gives ethyl 1-p-tolyl-2 5 - d i d y l - 4-akEehydopyrrole-3-mrboxylate white glistening crystals m. . p. 133" ; the phenylhydrazone forms colourless strongly refractmg crystals m.p. 92-96"; the oxime forms glistening leaflets m. p. 138" and the free acid forms colourless needles m. p. 212O. The semicurbaxone forms colourless needles m. p. 240". Ethyl 1 2 5- trimeth yl-4-aldeh ycZupyrrole- 3 - curbox y lat e forms long white needles m. p. 97" ; the phenylhydrazone forms fine needles m. p. 159-161". It has been suggested by Alessandri (A. 1915 i 452) that a number of a-pyrrole-aldehydes have a hydroxymethylene structure since they do not react with dihydroxyammonia whilst the corre- sponding N-substituted a-pyrrole-aldehydes do so react. It is now found that neither ethyl 2 5-dimethyl-4-aldehydopyrrole-3-carb- ox ylat e ethyl 2 4-dime t h yl- 3 -aldeh ydopyrrole - 5 -car boxylate nor the new N-substituted pyrrole-aldehydes reacts with benzenesulpho- hydroxamic acid.Probably all are true aldehydes although not giving all the typical aldehyde reactiom. There may be an equili- brium between the two forms. The N-substituted pyrrole-aldehydes react with nitroacetic acid with loss of carbon dioxide forming nitrovinylpyrroles and with ethyl cyanoacetate to give substituted vinylpyrroles. Ethyl 1-phenyl-2 5-dimethyl-4-nitrovinylpyrrole-3-carboxyktte forms yellow crystals m. p. 130-132" ; the corresponding 1-p-tolyl compound forms glistening yellow leaflets m. p. 125-133". Ethyl 2 6-di- methyl - 4 - [W - cyano - w -carbethoxyvinylJpyrroZe - 3 - mrboxyhte forms white needles m. p. 139". The 1-phenyl derivative forms colourless needles m. p. 110" and the 1-p-tolyl derivative white needles Oxindole-3-aldehyde condenses with hippuric acid to form an axlactone which forms an acetyl derivative stout prisms m.p. 185". It may have the annexed formula. -CH=$!-N> Cph Hydrolysis experiments failed to give an unsaturated acid but merely re- moved the acetyl group which may therefore be attached to the nitrogen. The hydrolysed product had m. p. 260". N-Methyloxindole- In. p. 121". / /OAc CO.0 (1 NH ' h'lci. 202 ABSTRACTS OB CHEMICAL PAPERS. 3-aldehyde slso formed an acetyEcszlactone glistening red needles m. p. 205" which when hydrolped gave the axlactone red needles 113. p. 287". The acetyl group cannot in this case be attached to nitrogen but it is still doubtful what positions are occupied in the molecule by the acetyl and benzoyl groups.Oxindole-3-aldehyde gives by Perkin's reaction a compound C,,H7O2N yellow tablets m. p. 247" probably having the (\m/NYH annexed coumarin formula. It forms a crystal- co line molecular compound with 1 mol. of aniline \/"/H\o/ m. p. 160". Oxindole-3-aldehyde forms an ucetyl derivative m. p. 185" and a benmyl derivative m. p. 196" ; N-methyloxindole-3-aldehyde gives an acetyl derivative yellow needles m. p. 135" and a benzoyl derivative greenish-yellow needles m. p. 147". W. KUSTER and H. MAURER (Ber. 1923 56 [B] 2478-2481).-A new synthesis of haernatic acid starting from ethyl 4-aldehydo-3 5-dimethylpyrrole- 2-carboxylate (cf. Fischer Weiss and Schubert A 1923 i 703) is recorded. The preliminary work is carried out with the more accessible ethyl 2-aldehydo-3 5-dimethylpyrrole-4-carboxylate.Ethyl 2-aldehydo-3 5-dimethylpyrrole-4-carboxylate is con- densed with ethyl malonate in the presence of acetic anhydride at a temperature not exceeding 150" t o ethyl 4-mrbethoxy-3 5-dimthyl- p yrrok-2-uinyZ- o w -d icarboxy lat e small yellow needles m . p . 86" which is reduced and partly hydrolysed by sodium amalgam to 4-carbethoxy-3 5-d~rnethylpyrrole-2-ethyl-~~-dicarboxylic acid C13H1,06N a colourlesa powder m. p. 218". The acid loses carbon dioxide when heated and passes into 4-carbethoxy-3 5-dimethyZ- pyrrole-2-pqionic acid slender colourless needles or rectangular prisms m. p. 120"; the iron and copper salts are described. Et hy 1 4-a ldehy do - 3 5-dime thylp yrrole-2 -carboxylat e and e thy1 maJonat e yield ethyl 2 -carbethoxy-3 5-dimeth ylp ywole-4-vinyl- ww -d i- curboxylate Co2Et*y :c"e>C*CH:C(C0,Et)2 colourless needles m.p. 99-100" which is transformed by sodium amaIgam into 2-arb- ethoxy- 3. 5-dimethylp yrrole-4- ethyl - ww-dicurboxp?ic acid CH E. H. R. A New Synthesis of Haematic Acid. HN*CMe Co2Et*(? 'cMe,>C*CH2*CH(C02H)2 HNCMe colourless leaflets or thick needles m. p. 184-185" (decomp.); the ferric and calcium salts are described. The acid passes when heaced above its melting point into 2-carbethoxy-3A 5-dimethyl- pyrrole-4-propionic acid co2E 'C'*e>CCH2*CH2*C02H colour- H N*CMe less leaflets m. p. 152" the silver and ferric salts of which are described. Oxidat ion of 2 - carbethoxy- 3 5-dime thylp yrrole -4-pro - pionic acid by chromic acid in glacial acetic acid solution gives the imide of hEmatic a,cid I o*cRI">C*CH2*CH2*C02H which is NH-CO characterised by hydrolysis by means of barium hydroxide t o the anhydride m.p. 97". H. W.ORGANIC OHEMISTBY. i. 203 Pyrroles. F. AKGELICO and F. MONFORTE (Gazzetta 1923 53 795-800).-1t has been shown (A. 1905 i 938; 1909 i 122; 19lO,-i 444; 1911 i 1032) that when boiled with dilute aulphuric acid diazotriphenylpyrrole yields szinetriphenylpyrrole. Further experiments show that diazotriphenylpyrrole is a highly stable compound and is not altered by iodine sodium thioaulphate alcohol or organic acids. With mineral acids it yields salts and with nitric acid also nitro-derivatives. Energetic oxidising agents cause pro- found decomposition of the molecule.Reducing agents mcb as zinc dust and acetic acid zinc dust and ammonium chloride am- monium sulphide or hydroxylamine convert it into the amino- compound whilst by the action of hydrogen in presence of palladium black it is converted into ammonia and triphenylpyrroline ; the latter reduction resembles that of diphenyldiazomethane which yields principally diphenylmethane and nitrogen (cf. Staudinger Gaule and Siegwart A. 1921 i 323) but it has not been found possible to convert diazotriphenylpyrrole by reduction into the corresponding hydrazine although this is possible with certain of the aliphatic diazo-compounds. Like both the corresponding indole derivative and various aromatic diazo-compounds diazotriphenyl- pyrrole is extremely sensitive to the action of light this causing it to darken and to undergo transformation into a compound which has a lower melting point and a diminished proportion of nitrogen but has not yet been identified.2 5-Diphenylpyrrole-3-carboxylic acid readily yields the corre- sponding oximino-compound but in the passage to the amine the csrboxyl group is eliminated in the cold. Hence to prepare the diazo-compound it is not necesszry to convert the carboxylic acid into 2 3-diphenylpyrrole itself. The compound C,,Hl,O,NS obtained by the action of concen- trated nitric acid in the cold on diazotriphenylpyrrole forms crystals iu. p. 185". If a mixture of nitric and sulphuric acids is employed the product forms crystals m. p. 110" and contains rather more nitrogen than is represented by the above formula.Oximino - 2 5 - diphenylpyrrole - 3 - mrboxylic m i d C,,H,,O,N crystallises in golden-yellow scales m. p. 212" (decomp.) and yields aminodiplienylpyrrole m. p. 186" when reduced in alcoholic solu- tion by means of ammonium sulphide. T. H. P. A Complex Silver Fluoride. A. BURADA (Ann Sci. Uniu. JCWUJ 1923 12 33-34; from Chem. Zentr. 1923 iii 1225).-By addition to a solution of silver fluoride of the theoretical quantity of pyridine and evaporation in a vacuum over sulphuric acid with exclusion of light a compound is obtained of the composition AgF,2C,H,N,5H20 ; it forms colourless t,ransparent crystals unstable m air and light. When heated it is decomposed completely leaving a residue of metallic silver. G. W. R. Preparation of Amino-substitution Products of pSridine and Quinoline Series.A. E. TSCHITSCHIBABIN (D.R.-P. 374291 ; from Chem. Zentr. 1923 iv 726; cf. A. 1923 i 112l).-]eyridine h* 2i. 204 ABS!CBACTS OB CHEMICAL PAPERS. quinoline their homologues or derivatives or other bases containing the pyridhe ring or natural organic bases such as alkaloids are treated in the absence or presence of indifEerent solvents with sodamide or compounds of the general formula R-NHNa where R=aryl alkyl or a heterocyclic basic residue such as pyridyl or q d y l or mixtures of sodium with primary amines. After tredjzwrit of the products of reaction with water the amino- unds obtained are separated by distillation or other suitable ze%. The reactions are shown by the following equations (i) C5R N+NH2Na=C5H4NNHNa+H2 (ii) C5H,N*NHNa+H,0i C5H4NkH2+NaOH (ni) C5H4N*NHNa+C5H,N=(C5H4N)2Nha +H (iv) (C5H4N),NNa+H20= (C5H4N),NH+NaOH.The amino- group goes into the ortho-position relatively to the pyridine nitrogen. 2-Aminopyridhe has m. p. 56". Other compounds mentioned are 6-arnino-2-methylpyridine a deliquescent substance m. p. 36.5" b. p. 208-209" ; 2-aminoquinoline leaflets m. p. 129" ; 2 6-diamino- pyridine obtained by heating pyridine and sodamide in the presence of vaseline oil at 125" and then a t MOO leaflets m. p. 121.5"; 2-anilinopyridine from pyridine and sodium anilide crystals m. p. 108"; 2 2-dipyridylamine small needles m. p. 95" (stable form) m. p. 86-87" (labile form) ; aminonicotine crystals m. p. 125-126" ; 6-amino-2-hydroxypyridine ; 2 6-diaminopyridine couples with aromatic diazo-compounds with formation of colouring matters. Nitration of 2-aminopyridine yields 5-nitro-2-aminolry7idine yellow leaflets m.p. 188" and 3-nitro-2-aminopyridine yellow needles m. p. 164". From 5-nitro-Z-aminopyridine 2 5-diaminopyridine UI obtained by reduction. The Synthesis of Ricinine. E. SPATH and G. KOLLER (Ber. 1923 56 [B] 24&2460).-The constitution assigned previously to ricinine (Spath and Koller A. 1923 i 594) is confirmed by its synthesis from 4-chloroquinoline. Ricinidine is converted by a molecular proportion of bromine in aqueous solution into a mixture of bromo-compounh which is transformed by boiling potassium carbonate solution into a product m. p. 287"; it is not identical with ricinic acid. 4-Hydroxy-l-methylpyrid-%one reacts with a molecular proportion of bromine in aqueous solution to give a homogeneous bromo-derivative m.p. 219-219.5" ; attempts to replace- the halogen atom of this compound by the cyano-group were unsuccessful . 4-Chloroquinoline is oxidised by potassium permanganate in boiling aqueous solution in the presence of carbon dioxide to 4-chloropyridine-2 3-dicarboxylic acid coarse pale yellow crystals m. p. 173" (decomp.) when rapidly heated. The acid is fairly smoothly converted by acetic anhydride into the corresponding anhydride colourless needles m. p. 200-202" (slight decomp.) in an evacuated tube which is converted by ammonia in the presence of benzene into 4-cMoro-2-carbamidopyn'dine-3-carboxylic acid lustrous needles m. p. 148-150' (decomp.) when rapidly heated.The latter acid is converted by bromine and potassium hydroxide into G. W. R.ORQANICJ OHEMISTRY. i. 205 4-chloro-2-aminopyridirrae-3-earboxyl~c acid slender colourless crystals decomp. 173" which is conveniently purified through the ammonium salt; it is transformed by nitrous acid in sulphuric acid solution info 4-chloro-2-hydraxy~~dine-3-~rboxyl~c mid colourless needles m. p. 220" (decomp.). The constitution of the hydroxy- acid is established by its conversion by hydrogen in the presence of palladised barium sulphate into the previously described 2-hydroxy- pyridine-3-carboxylic acid and thence into 2-hydroxypyridhe. Attempts to effect the complete methylation of 4-chloro-2-hydroxy- pyridine-3-carboxylic acid with diazomethane or by the action of methyl iodide on the di-silver salt mere not successful.The acid is therefore converted by the successive action of phosphoryl chloride and phosphoms pentachloride and of ammonia into 2 4-dz'chloro~rz'dine-3-carboxylamide colourless crystals m. p. 181-182" (decomp.) which is transformed by phosphoryl chloride into 2 4-dichloro-3-cyanopyridine m. p. 112-113". When t+reated with boiling methyl-alcoholic sodium methoxide solution both chlorine atoms are replaced by methoxy-groups with the production of 3-cyano-2 4-dimethoxypyridine coarse colourless crystals m. p. 145-146" and a substance m. p. 221-222" which has not been examined completely. The conversion of 3-cyano-2 4-dimethoxy- pyridine into ricinine m. p. 197" could not be effected by heating it at 300" but occurs readily when it is treated with methyl iodide in an evacuated tube a t 120-130". H.W. Keto-mils. V. The Formation of Quinolines from Ketones and Aromatic Amines. E. KNOEVENAGEL [with E. WAGNER and H. BAHR] (Ber. 1923 56 [B] 2414-2418).-The production of derivat,ives of quinoline from aniline and ketones or aldehydes has been ascribed to the intermediate formation of alkylidene ketones and aldols respectively. Evidence is now brought forward however in favour of the view that in the formation of 2-methyl- or 2 4-dimethyl-quinolines an alkylidene- or a ketylidene-amine derivative is essential which passes into a dimeride and thence into a quinoline compound. It is quite possible that the formation of aldols from aldehydes ketones or mixtures occurs under the condensing influence of hydrogen chloride but compounds of this type are decomposed hy aromatic amines with formation of alkylidene- or ketylidene-amines and liberation of the equivalent quantity of aldehyde or ketone.The preparation of methylisopropenylaniline (cf. Bahr A. 1922 i 750) from acetoneanil and methyl sulphate is described. It is converted by cyanoacetic or chloroacetic acid (but not by the dichloro- or trichloro-acid) into dimeric methylisopropenylaniline in. p. 148" which is identical with the by-product isolated by Biihr (Zoc. cit.) during the preparation of methylisopropenylaniline by means of methyl iodide. The dimeride is transformed by dry hydrogen chloride a t 180-200" into 2 4-dimethylquinoline. The action of mesityl oxide on aniline in the presence of a little iodine leads to the formation of acetoneanil and acetone.The condensation of mesityl oxide with aniline hydrochloride at 180"i. 206 ABSTRACTS OR' m C A L PAPERS. takes place with liberation of methane and not of methyl chloride as stated by Beyer. In the presence of iodine phorone and mesityl oxide yield acetone unchanged phorone and acetoneanil. In the absence of iodine condensation does not appear to occur. Under the in3uence of iodine and water phorone does not appear to yield acetone. H. W. Amino-alcohols of the Quinoline Series. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pats. 98482 98712 and 98713 ; from Chem. Zentr. 1923 iv 829-830; cf. A. 1923 i 148 149).- 6-Ethoxy-2-phenyl-4-quinolyl methyl ketone is halogenated in the methyl group and the resultant halogen derivative allowed to react with dimethylamine diethylamine or piperidhe. The N-sub- stituted 6-ethoxy-2-phenyl-4-quinolylamino-ethanone thereby obtained is then reduced to the corresponding aminoalcohol.6-E~7wxy-2-phenyl-4-quinolyt methyl ketone forms yellow crystals m. p. 107"; the hydrochloride yellow crystals has m. p. about 220" (decomp.). It is obtained by condensation of ethyl 6-ethoxy- 2-phenylquinoline-4-carboxylate with ethyl acetate and elimination of carbon dioxide from the ethyl 6-ethoxy-2-phenylquinoline-4-aetafe m. p. 98-99' thereby formed or from 4-cyano-6-ethoxy-2-phenyl- quinoline by the Grignard reaction. By acting on the above- mentioned ketone with bromine in hydrobromic acid solution 6-ethoxy-2-p~nyl-4-qui~lyl brornomethyl ketoze hydrochloride yellow qystals m.p. 207" (decomp.) is obtained; the free ketone forms yellow crystals m. p. 129". By acting on the bromomethyl ketone with dimethylamine G- ethoxy-2 -phenyZ-4-quinolyl dimethyl - aminomethyl ketone OEt*CgNH4Ph*CO*CH2*NMe2 is obtained as the hydrobromide yellow crystals m. p. 230" (decomp.). The latter by reduction with hydrogen in the presence of a catalyst gives 6-ethoxy- 2-phenylquinolyl-4-dimethylamin&hanol OEf. CgNH,Ph*CH (OH)*CH,*NMe which forms colourless rosette-like needles m. p. 95' ; the dihydro- chloride forms light yellow crystals m. p. about 210" (decomp.). 6-Ethoxy-2-phenyl-4-quinolyl diethylaminomethyl ketone monohydro- bromide yellow crystals m. p. about 210" (decomp.) G-eth0.q- 2-phenyl-4-quinolyl piperidinomethyl ketone a yellow powder m.p. 82" (indef.) the hydrochloride m. p. about 260" (decomp.) and the hydrobromide m. p. 235-240" (decomp.) of the latter are similarly obtained. The corresponding amino-alcohols are obtained by reduction. 6- Ethoxy-2-phenyl-4-quinolyldiethylaminoethanol forms crystals m. p. 89" after softening ; the dihydrochloride yellow cr tals has m. p. 205". 6-Ethoxy-2-phenyl-4-quinolylpiperidi?m- G. W. R. yellow crystals has m. p. 218". Preparation of a 2-Phenylquinolinedicarboxylic Acid. NEUMANN & Co. and J. ZELTNER (D.R.-P. 373285; from Chem. Zentr. 1923 iv 664-665) .-Acetophenone-o-carboxylic acid prepared for example from phthalic anhydride acetic anhydride and potassium acetate is condensed with isatin by heating in the presence of potassium hydroxide solution at 100'.On acidifying ef E noZ forms colourless crystals m. p. 110"; the dihydrochloride,ORUNI(3 CHEMISTRY. i. 207 2-phenylgrcinoline-4 7-dicarboxylic acid is obtained; it is a yellow crystalline powder m. p. 200". Preparation of Tetrahydrocarbazoles. CHEMSCHE FABBIKEN VORM. WEILER-TER MEER (D.R.-P. 374098 ; from Chem. Zenlr. 1923 ivy 724).-2-HalogencycZohexanones are condensed with primary or secondary aromatic amines unsubstituted in the ortho-position to the amino-group. The reaction takes place in the presence of such basic substances as potassium carbonate or anhydrous potassium acetate and is represented by CH,/\CO CH,(,!CHX + /-NHR- - H O + H S T 2 CHZ CH,NR The following compounds are mentioned tetrahydrocarbazole from aniline and chlorocyclohexanone ; 3-methyltetruhy&rocarbazole m.p. 142" from o-toluidine and chlorocyclohexanone ; 1-mthgltetrahydro- carbuzole m. p. 98" from p-toluidine and chlorocyclohexanone ; N-ethyltetrahydrocarbaxole a viscous oil b. p. 220"/40 mm. from ethylaniline and 1 2-chlorocycZohexanone. G. W. R. R. Sii DERQUIST (Suensk Kern. Tidskr. 1922 34 189-192; from Chem. Zentr. 1923 iii 1082-1083) .-Aromatic a-ketonic acids are prepared by condensation of aldehydes with 4-oxo-2-thio-3-phenyloxazolidine. After oxidation and fission of the substituted oxazolidine ring aromatic a-ketonic acids are obtained together with phenyl thio- carbimide. The condensation proceeds readily in acetic anhydride solution in the presence of anhydrous sodium acetate.Fission of the aryldihydroxyoxazoles obtained by oxidation takes place a t the ordinary temperature on treatment with sodium ethoxide. The compounds may be separated by fractiomtion or by way of their hydrogen sulphite compounds. Anhydro-acids are also obtained from the elimination of a molecule of water from two ketonic acid molecules. 4-0xo-2-thio-3-phenyZ-5-benz~Zi~e~coxa~~ol- idine from benzaldehyde and 4-oso-2-thio-3-phenyloxazolidine has m. p. 185-185*5O. On oxidation if yields 2 4-dihgdroxy- 3 - p hen y 1 - 5 - b enz ylideneoxaxolidine m . p . 23 8-2 3 9 " whilst among the products of reaction with sodium ethoxide is phenylpyruvic acid. 0 ther compounds mentioned are 4-0~0-2-thio-3-ph.en yl-5-o-chloro- benxylideneoxazolidine fine thread-like or prismatic crystals m.p. 14 1.5" ; 2 4-d ih ydrox y -3 -phen yl-5-0 -chloro benz ylideneoxaxolidin e m. p. 152"; o-chlorophenylpyruuic acid colowless leaflets rn. p. 145" (m. p. 152-152-5" when heated quickly) ; semicurbaxone of the latter m. p. 167-5" ; phenylhydraxone m. p. 141" ; 4-oxo-2-fhio- 3-phenyl-5-m-chlorobenzylideneozaxolidine light yellow prisms m. p. 192" ; m-chlorophen ylpyruvic mid prisms ; semicarbazone of the latter m. p. 176" ; phenylhydraxone m. p. 141" ; 4-0x0-2-thio- 3-phen yl-5-p-chlorobenxylideneoxazolidine m. p. 237-237.5" ; p-chlorophenylpyvic acid platelets ; semicurbaxone of the latter G. W. R. CHZ CH CH2/\-A CH1!?\? 3 Preparation of Aromatic a-Ketonic Acids.i. 208 ABSTRACTS OR' CHEXKIOffi PAPERS. m. p. 184" ; phenylhydrazone m.p. 164" ; 4-oxo-2-thio-3-p&enyL 543' 4')mthylenedioxybenzylideneoxazolidine m. p. 240" ; 2 4-~thylenedioxyphenylpymvic acid colourless leaflets ; semi- curbaxone of the latter m. p. 197"; phenylhydrazme m. p. 144"; 4- 0x0-2 -t&io- 3 -phen y 1 - 5 - m - nit ro benx y lidenwxazolidine m . p . 20 7 " ; 4-oxo-2-thio-3-phenyl-5-o-acetoxybenx ylideneoxazolidine yellow prisms m. p. 1624%-163". Action of Hydroxylamine and of Hydrazine on the Aryl Monothioamides of Carbethoxyethylmalonate. D. E. WORRALL (J. Amer. Chem. Soc. 1923 a 3092-3095; cf. A. 1022 i 874).-isoOxazoles and pyrazoles were obtained by the action of hydroxylamine and hydrazine respectively on carbethoxy- ethylmalonate monothioamides. Thus carbethoxyethylmalonate monothioanilide gave ethyl 3-anilino-5-oxo-isooxazole-4-carboxylate srnaaU needles m.p. 166" and the corresponding pyraxole ester fluey white needles m. p. 194-195". Ethyl 3-o-toluidino-5-iso- oxazole-4-carboxykcte flat needles m. p. 165-167" (decomp.) and the corresponding pyraxole ester white needles m. p. 215" (decomp.) ; e th y 1 3 - p- toluid ino- 5 - oxoisooxuxol e - 4 - curbox y Zat e needles and plates m. p. 172-173" (decomp.) and the corresponding pyrazole ester feathery needles decomp. above 200" ; ethyl 3-p-brommnilino- 5-o~o~sooxaxoZe-4-carboxyZute slender needles,. m. p. 163-170" (decomp.) and the corresponding pyrazole ester needles m. p. 217" were obtained. F. B. 4'-Amino-l-phenyl-5-methylbenzthiazole and its Bromin- ation in Glacial Acetic Acid. The Dibromo-product of Gatterman.The Fluorescence of some Benzthiazoles. R. F. HUNTER (Chem. News 1923 127 385-386).-An alcoholic solution of dehydrothiotoluidine (4'-amino-l-phenyl-5-rnethylbenz- thiazole) exhibits a green fluorescence in the light of a mercury lamp; its dibromide shows a blue fluorescence in glacial acetic acid solution and the acetyl derivative is also strongly fluorescent. The dibromide is decomposed by nitrous acid and consequently cannot be diazotised. Absorption Colours of the Second Order. J. PICCARD and F. DE MONTMOLLIN (Helu. Chim. Acta 1923,6,1011-1019).-1t was shown previously that meri-quinonoid salts of tetraphenylbenzidine have a yellow colour of the second order (A. 1913 i 895). It is now shown that Nietzki's rule also applies to such second order colours ; the second absorption band can be moved further into the visible spectrum by increasing the molecular weight changing the colour of the compound from yellow to red.This has been demons- trated by preparing a meri-quinonoid salt of diphenyldi-p-diphenylyl- benzidine C6~4~hoNPh~C,H4~C6H40~Ph*~6H4Ph. Diphenyl-p-di- phenyZyZumine C,H,Ph*NPh is formed by heating diphenylamine with p-iododiphenyl in nitrobenzene in presence of potassium carbonate and a little copper; it forms long nearly colourless crystals m. p. 114". It forms a yellowish-green compound with chloranil and gives a greenish-blue coloration with concentrated G. W. R. E. H. R.ORGANIC CHEMISTRY. i. 209 sulphuric acid. When oxidised in glacial acetic acid with sodium dichromate it gives a red colour changing to green; the green solution is reduced with zinc dust and from the diluted solution diphenyldidiphenylylbenx8dine can be extracted with chloroform in 20% yield.It forms a brown powder m. p. 135-140". The same substance can be obtained in an impure form by condensing s-diphenylbenzidine with p-iododiphenyl. All solutions of the compound show a strong violet fluorescence which is excited by ultra-violet light a t the limit of the visible spectrum. This benzidine derivative is oxidised by sodium dichromate in glacial acetic acid solution into a meri-quinonoid salt which can be precipitated by picric acid as meri-diphenyldi-p-diphenylyldiphenoquinonedi- immonium picrate a red powder. Further oxidation gives the green hob-quinonoid salt. E.H. R. H. P. KAUFMANN and J. LIEPE (Ber. 1923 56 [B] 2514-2520).-Attempts have been made to estimate enols by titration with solutions of thiocyanogen in t'he hope of thereby avoiding secondary disturbances such as may be caused by the liberated hydrogen bromide in Meyer's bromine titration method. It is found however that the reagent can be applied only under definite conditions ; in general applicability and rapidity of execution the method is not equal to Meyer's process. Quantitative experiments with solutions of thiocyanogen are rendered very difficult on account of the ease with which it becomes polymerised particularly on exposure to sunlight or to an elevated temperature . Thiocyanogen reacts with antipyrine in the presence of chloroform to give a mixture of antipyrine thiocyanate colourless lustrous needles m.p. 125' (which is also obtained from antipyrine sulphate and potassium thiocyanate) and 4-thiocyano-1-phenyl-2 3-dimethyl- pyrazoZ-5-one K(scN)*co >NPh colourless crystals m. p. 147- 148"; the constitution of the latter substance follows from its preparation from 4-bromoantipyrine and potassium thiocyanate in boiling aqueous solution. 4-Thiocyanoantipyrine thiocyanate has m. p. 84". 4-Thiocyanoantipyrine is very readily hydrolysed by alkali hydroxide t o potassium cyanide potassium cyanate and his- 1 -phen yl-2 ; 3 -dimethyl-5-p yrazolonyl4-disul'hide rph-c*>cs *sKme.bMe CO-NPh NMe*CMe rery pale yellow hexagonal plates m. p. 256"; the compound ca.n also be prepared by means of aqueous alcohol. 4-Thiocyanoanti- pyrine is reduced by zinc and hydrochloric acid in the presence of alcohol to the additive compound of zinc chloride and 4-thiolanti- pyrine C,,H,,ON,S,ZnC~ a white precipitate from which the thiol could not be isolated.[With 'M. !FHOMAS. J-Addition and substitution of free thio- cyanogen occur much more slowly than in the case of bromine. Thus ethyl hydrocollidinedicarboxylate reacts with seven atomic pro- portions of chlorine and four of bromine but not with iodine; with Additive Reactions of Thiocyanogen. CMe-NMei. 210 ABSTRACTS OF CHEMICAL PAP-. thiocyanogen it gives a di-thiocyano-derivative Cl6HI9O4N3Sz m. p. 115' (decomp.). Ethyl coWi&inedicarboxykcte thiocyanute crystallkes in colourleas monoclinic plates m. p. 133". [With M. THous.]-Reactions with free cyanogen depend greatly on the solvent used addition occurring particularly rapidly in the presence of nitromethane (as example of a solvent of high dissociating power).The action of sunlight and of certain catalysts notably iron is advantageous. Thus whereas salicylic acid is indifferent towards thiocyanogen under the usual conditions it is converted in nitromethane solution in the presence of iron powder into 2-hydroxy- 5-thiocyarwbenzoic acid monoclinic leaflets m. p. 167-168'. H. W. New Methods of Splitting Pyrimidines. 11. Decom- position of Pyrimidines by means of Ferrous Salts. M. H. PFALTZ and 0. BAUDISCH ( J . Amer. Chem. Soc. 1923 45 297%- 2980; cf. A. 1921 ii 337).-The splitting of pyrimidines under conditions closely resembling those in the metabolism of plants and animals was accomplished by the action of the syst'em ferrous sulphate-sodium hydrogen carbonate-air and the system sodium pentacyanoaquoferroate-oxygen or air (A.1900 i 591) on uracil and thymine. In each case the pyrimidine ring was partly hydrolysed with the formation of highly coloured intermediate substances which were completely hydrolysed by warm sodiuin hydrogen carbonate with the production of carbamide. The action mas retarded by hydrogefiation of the pyrimidine ring as in hydro- uracil and by the presence of a methyl group in the 5-position as in thymine and by the addition of any substance possessing a strong affinity for iron e.g. ammonia potassium cyanide. H. BILTZ and T. KOHLER (Ber. 1923 56 [B] 2482-2489).-1n continuation of the work on 5-acylbarbituric acid (cf.Biltz and Wittek A. 1921 i 4M) 5-benzoylbarbituric acid has been examined in detail. The position of the benzoyl group is placed beyond doubt by t.he observed ketonic properties of the compound by the existence of similar derivatives of 1 3-dimethyl- and 1 3-diethyl-barbituric acids and by the inability of alkalis to effect hydrolysis. pale yellow aggregates of prisms m. p. 275" (decornp.) is prepared by heating barbituric acid with benzoic anhydride a t 175" during five hours; it cannot be prepared from barbituric acid benzoyl chloride and sodium hydroxide or from barbituric and benzoic acids. The potassium salt rhombic leaflets decomp. about 315" is described. It is stable towards sodium hydroxide solution or concentrated hydrochloric acid.It is decomposed by hot fuming nitric acid into alloxan and benzoic or nitrobenzoic acids and by bromine in aqueous solution a t the atmospheric temperature into hnzoic and 5 5-dibromobarbituric acids. It gives a hydrazone C H ,,03N4 slender pale yellow needles decomp. 260° and a phenyZhydrazone C,,H,,O,N small pale yellow needles decomp. 218"; a semi- F. B. 5-Benzoylbarbituric Acids. 5-Benxoylbarbituric acid CO<m.CO>CHB~ NH*COORGAN10 CHElldISTRY i. 211 carbazone could not be obtained. It is decomposed by thiosemi- carbazide in boiling aqueous-alcoholic solution info barbituric acid and 2-amino-5-phenylthiodiazole (cf. Young and Eyre T. 1901 79 57); 5-acetylbarbituric acid yields in a similar manner barbituric acid and 5-amino-2-methylthiodiazole. The action of hydroxyl- amine on 5-benzoylharbituric acid in boiling alcoholic solution gives a substance colourless lustrous hexagonal platelets m.p. 261 " which is regarded as the oxime of 5-amino-5-benzoylbarbituric acid CO<m.Co>C(NH2)*CPh:NOH NH*CO ; it is converted by hot concen- trated nitric acid into alloxan by highly concentrated hydriodic acid into benzoylbarbituric acid and by bromine water into alloxan and benzaldehyde. 5-Benzoylbarbifuric acid is converted by sodium hydroxide and methyl sulphate into the methyl ether of the colourless lustrous prisms decomp. 105" ; the corresponding phenylhydrazone C,,H,,O,N decomp. 225" is described. The ethylation of 5-benzoylbarbituric acid could not be effected by ethyl sulphate or ethyl bromide magnesium oxide and carbon tetrachloride at 140".1-Methylbarbituric acid and benzoic anhydride react a t 130-140" to give 5-benzoyl-1 -meth?/Zbarbituric acid small pale brown prisms decomp. 225" (phenylhydrazone slender yellow needles decornp. 205"). 5-Benzoyl-1-ethyzbarbituric acid flattened prisms m. p. 205" (decornp.) and its phenylhydrazone slender needles decomp. 190" after darkening at 175" are described. 1 3-Dimethylbarbituric acid reacts with benzoic anhydride at 130" but the expected 5-benzoyl-1 3-dimethylbarbituric acid could not be isolated from the product of the reaction in the homogeneous condition; it is characterised as the phenylhydrazone CI9Hl8O3N4 colourless quadratic leaflets decornp. 218". 5-Benzoyl-1 3-diethylbarbituric acid could not be caused to crystallise ; the phenyzhydraxone C21H2,0,N4 forms long yellow leaflets decornp.164". Attempts to cause interaction between barbituric acid and oxalic acid oxalyl chloride oxalyl bromide or phthalic anhydride were not successful. Thiobarbituric acid does not react smoothly with acetic or benzoic anhydrides. The acetyl group of 5-acetyl- barbituric acids does not appear to be capable of condensing with aldehydes. H. W. Alkylisopropylbarbituric Acids. F. HOFFMANN LA ROCHE & Co. (Austr. Pat. 92386; from Chem. Zentr. 1923 iv 665).-In modification of an earlier patent (A. 1922 i 872) other alkyl halides are used in place of ally1 bromide. 5-MethyZ-Ei-iso- propylbarbituric acid from isopropylbarbituric acid and methyl iodide forms crystals m.p. 186-187". 5 5-Diiso2rropyZbarbitziric acid forms crystals m. p. above 230" (decomp.). Preparation of New Barbituric Acid Compounds. CHEMISCHE FABRIK AUF AETIEN VORM. E. SCHERINQ (Brit. Pat. 198379 ; addn. to 158558 ; cf. A. 1922 i 582).-New compounds enolic form of 5-benzoylbarbituric acid CO<NH.c(oMe)/ NH-co> CBz G. W. R.i. 212 ABSTRAflTS OF C7HEMICIu PAPEBS. similar in properties to that previously described (Zoc. cit.) are obtained by replacing the diethylbarbituric acid in the original process by dipropyl- diallyl- or phenylethyl-barbituric acid. The products of these three fusions melt respectively at 82-86' 85-88' and 106-120". P. I ~ R E R C. G-NACHER and A. SCHLOSSER (Helv. Chim. Acta 1923 6 1108-1112).- Benzyl chloride reacts with the silver salt of glycine anhydride to give 2 5-dihydroxydihydropjraxine dibenxyl ether crystallising in white leaflets m.p. 164". The reaction therefore follows a difEerent course from that of methyl iodide on the anhydride (A. 1922 i 235). The new compound is readily hydrolysed by- boiling dilute acids to benzyl alcohol and glycine and in this respect difEers markedly from its isomerides N N'-dibenzylglycine anhydride and dikefo-2 5-dibenzylpiperazine. New Syntheses in the Quinoneimide Dye Group. I. Syntheses with 1-Chloro-2 4-dinitronaphthalene. F. KEHRMANN (with A. VAN BAERLE) (Ber. 1923,56 [B] 2385-2390). -A number of known and some new quinoneimide dyes have been prepared by condensing 1-chloro-2 4-dinitronaphthalene with different bases. In many cases the toluene-p-sulphonic ester of Martius's yellow (2 4-dinitro-or-naphthol) can also be used.0-2 ; 4-Dinitronaphthylaminodiphenyla.mine is obtained by con- densing the dinitrochloronaphthalene with o-aminodiphenylamine in alcohol ; it forms large brownish-red prisms containing benzene from that solvent which lose benzene and turn black at 70" m. p. 140". With 5-chloro-2-aminodiphenylamine the corresponding 5-chloro-2- (2 4-dinitronaphthylamino)diphenylamine is obtained dark brown leaves m. p. 110". Both these compounds are reduced smoothly by stannous chloride to rosinduline and chlororosinduline respectively. The rosindones are obtained by fusing the dinitro- compound with benzoic acid. By condensing 2 4-dinitro-1 -naphthyltoluenesulphonate with o-aminophenol 0-2 4-dinitronaphthylaminophenol is obtained which by careful treatment with aqueous A sodium hydroxide is converted into 5-nitro-7 12- NH I I naphthaphenoxaxine (annexed formula) a violet A/\/\/ precipitate which decomposes when heated.An I I INO acetyl derivative could not be obtained but (/\/\/ instead the known phenonaphthoxazone was formed. With 00'-diaminodiphenyl disulphide 0 the above toluenesulphonate condenses to give 0-bis-2 4-dinitro- naphthylaminophenyl disulphide (annexed formula) orange-yellow leaflets m. p. 169". With o-aminothiophenol it gives ' I NO,\,NO I I 1 captan a lemon-yellow crystalline powder c \/ 12 m. p. 198" which by careful treatment with alkali gives 5-nitro-7 ; 12-naphthuphenthiaxine nearly black needles with a brassy reflex m.p. 156" (decornp). It is much W. T. K. B. Diketopiperazine Derivatives. E. H. R. r A 1 \/\/ 0-2 ; 4-dinitronaphthylaminophenyl rner- ' I IORGANIC CHEMISTRY. i. 213 more stable than the corresponding oxazine. A by-product of the last condensation yellow glistening crysta,ls m. p. 150° appeared to be 2 4-dinitronaphthyl-o-aminophenyl sulphide. E. H. R. New Syntheses in the Quinoneimide Dye Group. 11. Steric Influence in the Condensation of Hydroxyquinones with o-Diamines. E". KEHRMANN [with c. BUFFAT] (Ber. 1923 56 [B] 2390-2394).-1t has long been known that substituted quinones such as chloranilic acid and 3-chloro-4-hydroxy-1 2- naphthaquinone react with difiiculty or not at all with o-diamines but it is now found that these reactions proceed under suitable conditions.Thus when chloranilic acid is heated with o-phenylene- diamine hydrochloride and a large quantity of benzoic acid a t the boiling point 1 4-dichloro-2 3-dihydroxyphenaxine is formed dark brownish-red metallic crystals blackening a t 310". It gives a dichroic sulphuric acid solution brown in thick greenish-yellow in thin layers. With o-aminodiphenylamine chloranilic acid gives 1 4-dichlwo-2-hydroxyapafranone dark reddish-brown crystals with a weak brassy lustre decomposing a t 285". 3-ChIoro-4-hydr- oxy- 1 2-naphthaquinone with o-phenylenediamine gives 6-chloro- 5-hydroxy-a@-naphth~phenuzine (formula I) dark red brassy crystals decomposing a t about 280". It gives a dirty yellowish-green colour with concentrated sulphuric acid ponceau-red with hot alkali.With o - aminodiphenylamine 3 - chloro-2-hydroxy - 1 4 - naphthaquinone gives 6-chlorwosindone (formula 11) red needles with golden lustre m. p. 255" giving a dark yellowish-green colour in sulphuric acid. With 2-amino-5-chlorodiphenylamine 6 9-dichlmorosindone is formed red needles with strong gold reflex m. p. 242-243" giving a dirty violet-red colour in sulphuric acid. (1.1 (TI.) (111.) \/ When the above 5-hydroxy-6-chloronaphthaphenazhe is fused with o-phenylenediamine a new dihydrtmuphthudiphmzine (formula 111) is formed golden-yellow leaflets with brassy reflex m. p. 263". Its hydrochloride forms dark red metallic needles and it gives a pure green colour in concentrated sulphuric acid. E. H. R. New Syntheses in the Quinoneimide Dye Group. IIL Syntheses of Induline-3B and -6B.F. KEHRMANN [with w. COPFENSTEIN] (Ber. 1923 56 [B] 2394-2397).-The Con-i. 214 ABSTRACTS OE OEEMICcbL PAPERS. stitutional formulae assigned to Induline-3B and -6B have now been confirmed by synthesis of these dyes from. dianilino- o-quinone gf);:. When this is condensed with 2-amino- 5-chlorodiphenylamke hydrochloride in alcohol 3-cMmo-8-aniZin o- phenylaposafranine (annexed formula) is NHph/\// /\ formed crystallising in needles with a green I ) Icl reflex. The free base forms brownish-red NHPh(/\\N(\/ needles m. p. 258". The colour in con- Ph,/ c1 centrated sulphuric acid is violet-blue be- coming violet and then Bordeaux-red on dilution. When this is boiled with aniline and aniline hydrochloride the ring chlorine is replaced by the anilino-group forming 8-anilino- 3 7-di~henyl~~nosafranineY identical with Induline-3B.The free base forms nearly black leaflets with Induline-3B is converted lnto Indu- phenosafranine (annexed formula) by boiling with aniline and aniline hydro- chloride in presence of 1 mol. of mercuric oxide. The free base forms greenish-black metallic crystals m. p. 286-288" ; the hydro- chloride and hydrobromide both form crystals with a coppery lustre insoluble in water. N a weak green reflex m p. 242". line-6B 2 8-dianilino-3 7-diphenyl- E. H. R. New Syntheses in the Quinoneimide Dye Group. IV. The Colour of the Simple Quinoneimines. F. KEHRMANN [with B. CORDONE] (Ber. 1923,56 [B] 2398-2405).-1n a previous paper (A. 1922 ii 333) the rule was established that the effect of salt formation on the colour of basic nitrogen compounds is to intensify the colour if the unsaturated condition persists.This rule has IIOW been found to apply to compounds of the quinoneimine series of which several new members have been pre- 9 pared. Th~moquinonemonoimine (annexed formula) was /\prs prepared by oxidising p-aminothymol with silver oxide in ethereal solution; it crystallises in bright yellow silky leaflets m. p. 74-75'. It is stable for some time in the dark at low temperatures and is much less sensitive to light than p-benzoquinonemonoimine. Its salts are deeper yellow in colour than the compound itself; the hydro- chloride is obtained as a voluminous yellow precipitate from ether ; the p'crate which is stable for some time in water forms bright yellow sparingly soluble crystals.The monoimines of benzo- and tolu-quinone were prepared afresh to confirm their yellow colour. Benzoquinonechloroimine 0 /-\:NU is also yellow but benzo- quinonedi-imine is colourless whilst its dihydrochloride is yellow. Benzoquinonedichlorodi-imine CNr\:NC1 is colourless ; it Me{) NH .. \-/ \-/ORGANIU CHEMISTRY. i. 215 gives a salt only with concentrated sulphuric acid and this is yellow. Duroquinonedi-imine (annexed formula) wits obtained by oxidising diaminodurene with silver oxide in ether ; it forms colourless crystals not very sensitive to light m. p. 136135". It dissolves in dilute mineral B',l!''e acids giving bright yellow solutions which soon de- NH compose with deposition of duroquinone.The salts which can be obtained in crystalline form from ether are bright yellow. The results show that the carbonyl group is a stronger chromophore than the iminocarbonyl group *C:IW. This is also shown by the fact that whilst tetramethyldiaminobenzophenone is yellow auramine base is colourless. Determination of the Constitutional Form& of Colouring Matters from their Absorption Spectra. V. F. KEHRMANN and &It SANDOZ (Helv. Chim. Acta 1923 6 982-994).-The absorption spectra of the mono-acid and di-acid &\ salts of phenyl-ap-benzophenazonium (an- nexed formula) and of the mono- di- and t)\p\A$ tri-acid salts of nine of its monoamino-deriv- 1s 1 I atives have been measured. The mono-salt of v/?bx(xy/ the parent substance is yellow with orange fluorescence the di-salt violet; both have an ortho-quinonoid structure.The amino deriv- atives 1- 2- 3- and 4- form a group. Their mono-salts are bluish-green except that of the 3-amino-derivative which is brown ; their di- salts are yeilow similar to bhe mono-salt of the parent substance and their tri-salts deep red comparable with the di-salt of the parent. The 1-amino-compound does not form a tri-salt probably on account of steric hindrance. All these salts are given an ortho-quinonoid structure. The mono-salt of the 10-amino-derivative (violet) is probably also ortho-quinonoid. The 9- and 5-amino-compounds form another group; they behave similarly to aposafranine (A. 1920 ii 142). The mono-acid salt (scarlet) and the di-acid salt (green) are para-quinonoid whilst the tri-acid salt (violet) has the ortho-quinonoid structure.The fact that the di-acid salts can be diazotised indicates that the solutions contain a small amount of the yellow ortho-quinonoid di-acid salt in equilibrium with the para-quinonoid form. Two amino-derivatives the meta- and para- were prepared having the amino-group in the external benzene ring. Here the auxochromic effect of the amino-group is reduced to a minimum and there is little difEerence between the colours of the mono-acid salt and of the di-acid salt both being yellow in solution; the tri-acid salt is violet and all three are ortho-quinonoid. Curves are given showing the absorption spectra of all the salts examined. Spirans. XII. Heterocyclic Dispirans and the Nature of the Basic Properties of the Imino-group.D. RADULESCU (Bul. fw. ytiinfe Cluj 1922 1 356-360; from Chem. Zentr. 1923 iii 1081 ; cf. this vol. i 58).-Heterocyclic dispirans have NH E. H. R. I I 1 \/ ('\ E. H. R.i. 216 ABSTRACTS OF CHEMICAL PAPERS. been prepared by the author by the action of o-diamines on dichloro- bisdiketohydrindene (I). Piperazinebis-3-1 S-diketohydrindene- 2 2 3 2-diqiran CaH,,O4N2 (11) f o m yellow prisms m. p. 249" (corn.). The spiran (111) CHH140+N2 forms microcrystalline brown prisms m. p. 272" (corr.). Splran I11 is scarcely basic whilst the dispiran I1 is moderately basic. This is explained by Thiele's theory of partial valencies which is also applicable to the slight basicity of pyrrole and indole. Spirans with tertiary nitrogen are more basic.N N'-Dipiperidylbis-1 3-diketohydrindene (IV) forms orange prisms m. p. 174". The diethylamino-derivative of the latter forms yellow prisms 111. p. 129" and the dibenzylamino- derivative yellow needles m. p. 178". The author concludes that the hydroxy-derivatives corresponding with the amines must be strongly acid. The compound described by Gabriel and Leupold (A. 1898 i 481) as bisdiketohydrindene oxide (V) is really a spiran pinacone (VI). It is hydrolysed by weak acids and alkalis to diketohydrindene and its decomposition producfs and phthalonic acid. G. W. R. Reactions of certain Substituted Guanidines with Sulphur. G. BRUNI and T. G. LEM (Atti R. Accd. Lincei 1923 [v] 32 ii 313-316).-When heated together in a sealed tube a t 260- 270° s-diphenylguanidine and sulphur give a good yield of mer- captobenzthiazole.In aniline solution subjected to prolonged boiling in a reflux apparatus the reaction gives rise to little or no mercaptobenzthiazole but to anilinobenzthiazole (cf . Hofmann A. 1880 388; Jacobson and Frankenbacher A. 1891 1048; Hugershoff A. 1903 i 865; and Rassow and Diihle A. 1916 i 747) NIIPh:C(:NH)*NHPh+S=C,H,<~~C*~Ph+NH~ ; the wet$ derivative of anilinobenzthiazole has m. p. 162-163". Mercaptobenzthiazole k formed in good yield when phenyl- guanidine and in poor yield when s-triphenylguanidine is heatedORGAlUC CHEMISTRY. i. 217 in a sealed tube with sulphur a t 270" (cf. SebrelI and Bord this vol. i 89). T. H. P. Tetrapyrrlethanes. I. HANS FISCHER and M. SCHUBERT (Ber. 1923 56 [B] 2379-2384; cf.A 1923 i 707).-Glyoxal can be condensed with ethyl 2 4-dimethylpyrrole-3-carboxylate in alkaline or better in acid alcoholic solution to form tetra(3-curbethoxy- 2 4 -dimethyZ-5-pyrryZ)ethane (annexed formula) which crystallises in colourless leaflets m. p. EtO,C*fi-fiMe Mefi-fi*CO&t 282". It gives an intense MeC C-YH-C CMe green solution in acetic acid. Oxidation with ferric chloride gives 2 mols. of bis-2 4-di- " 1 2 methyl - 3 - carbethoxyppyl - methene whilst reduction with hydriodic acid in acetic acid solution gives a mixture of pyrroles containing 2 4-dimethyl- and 2 4 5-tri- methyl-pyrrole. Potassium methoxide converts the ethane com- pound into tetramethylpyrrole. It can also be hydrolysed to tetra(3-curboxy-2 4-dimethylpyrryl)ethaney small tetrahedral crystals m.p. 233" (decornp.) but this product is not identical with that obtained by condensing glyoxal with 2 4-dimethylpyrrole-3-carb- oxylic acid. The relationship of tetrapyrrylethane derivatives with blood- and bile-pigments is discussed the conclusion being that there is a closer relationship with the latter. This conclusion is supported by spectroscopic examination of copper and zinc salts of a number of dipyrrylmethene derivatives. E. H. R. ;.d Diallylxanthine. SOCIETY FOR CHE~CAI INDUSTRY IN BASLE (Swiss Pat. 97978; from Chem. Zentr. 1923 iv 830).-By heating 4 5-dianaino-2 6-dioxo-l 3-didlylpyrimidine obtained by con- densation of diallylcarbamide with cyanoacetic acid or ethyl cyanoacetate treatment with nitrous acid and reduction with formic acid 5 -form ylamino - 4 - amino-2 6 - dioxo- 1 3 - diallylpyr- imidine is obtained. This is heated with N sodium hydroxide solution at 100" and then acidified whereby 1 3-diallylxunthine m.p. 155-156" is obtained. The intermediate compound 4-amino- 6-0x0-5-oximino-1 3-diallylpyrimidine can also be obtained by direct condensation of s-diallylcarbamide with ethyl oximinocyano- acetate. G. W. R. 1 3 7-Triallylxanthine. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pat. 97979; from Chem. Zentr. 1923 iv 830; cf. preceding abstract).-1 3-Diallylxcanthine is alkylated for example by treatment with ally1 benzoate in the presence of ethyl- alcoholic potassium hydroxide a t 80". 1 3 7-TriaZlyZxanthine has m. p. 57-58'; b. p. 17G0/5 mm. G. W. R. Oxidation of Uric Acid with Ferrous Salts.I. M. H. PFALTZ (J. Amer. Chem. Soc. 1923 45 2980-2984; cf. this vol. i 210).-Cleavage of the uric acid molecule was accomplished by the systems ferrous sulphate-sodium hydrogen carbonate- air and sodium pentacyanoaquoferroate-air or oxygen but not m \/ I NHi. 218 ABSTRACTS OR' OHEMICAL PAPERS. by the system ferrous sulphate-oxygen. The action was similar to .that which occurred with pyrimidines. Action of Alkali on Substituted Uric Acids. I. 9-Phenyl- 1 3-dimethyluric Acid. E. S. GATEWOOD ( J . Amer. Chem. Soc. 1923 45 3056-3064; cf. A. 1923 i 253).-Thk substituted uric acid waa decomposed instantaneously a t 100" with 4N sodium hydroxide with the elimination of methylamine. On acidifying fhe solution carbon dioxide was evolved and crystals m. p.249-250"; of 3-phenylisohy~ntoin-5-~rboxyl-o-methy~mide separated. This was further decomposed by alkali into phenylcarbamide methylamine oxalic acid and formic acid whilst oxidation with hydrogen per- oxide in alkaline solution yielded 5- hydroxy- 3-phenylhydantoi n 5-mrboxyZ-o-methyZamide large thin rectangular plates m. p. 195-196:. This was further decomposed by alkali into methyl- lamine phenylcarbamide and meso-oxalic acid. 9-PhenyZ-1 7-di- methyluric acid was synthesised. It did not melt below 280" and was not affected by boiling with 4N sodium hydroxide for ten minutes. F. B. F. B. The Activation of Halogen and Methyl in Aromatic Com- pounds by the Azo-group *N:NR. W. BORSCHE and I. Exss (Ber. 1923 56 [S] 2353-2357).-Experiments with 4-chloro- 3-nitroazobenzene and 6-chloro-3-nitro-4'-methoxyazobenzene show that the azo-group in ortho- or para-posit,ion to the halogen imparts to it increased activity.These compounds react more readily with hydrazine ammonia aniline or sodium ethoxide than 0- or p-chloro- nitrobenzene although not so readily as chloro-2 4-dinitrobenzene. On the other hand benzeneazo-2-nitro-p-toluene does not react with benzaldehyde to form a stilbene derivative as does 2 4-dinitro- toluene. 4-ChZoro-3-nitroaxobenxene from 4-chloro-3-nitroaniline and nitrosobenzene forms brown needles m. p. 84". 6-Chloro-3-nitro- 4'-hydroxyazobenxene from diazotised 6-chloro-3-nitroaniline and phenol forms red needles m. p. 218"; it is methylated by methyl sulphate to 6-chloro-3-nitro-4'-methoxyuzobenzene deep yellow leaflets m.p. 103". Benzeneuxo-2-nitro-p-toZuene from 2-nitro-p-toluidine and nitrosobenzene forms brown needles m. p. 106". 3-Nitro-4-hydruzinmaxobenxene Ph*N,*C,H,(NO,)*NH*NH forms red needles m. p. 206" (decomp.); with acetophenone it forms the corresponding hydrazone Ph*~~*C,H,(NO,);~*~:CMePh red needles m. p. 195". 2-Nitro-4-benxeneo-4 -hydroxyazobenxene Ph*N,*C,H,(NO,)*N,*C,H,*OH obtained from the above hydrazine and p-benzoquinone forms brown needles m. p. 203" (decomp.); with quinoneoxime the hydrazine forms an oxilnehydrazone Ph.N,*C,~~(NO,).~=N:C,H,:N*OH a red crystalline powder m. p. 235" (decomp.). 3-Nitro-4-aminaczobenzene forms red needles m. p. 173-5". 3-Nitro-4-~.~eri&i~zobenxene7 by condensing 4-chloro-3-nitroazo- benzene with piperidhe forms orange-red tablets m.p. 64". 3-Nitro- 4-uniZinoaxobenzene Ph*N,*C,H,(NO,)*NHPh forms brown needles,ORGANIC CHEMISTRY. i. 219 m. p. .124". 3-Nilro-4-methoxyazobenxene crystallisea in orange-red needles m p. 107". 3 - N i t r o - 4 ' - m e t h - 6 - h ~ d ~ ~ z i n ~ z ~ e ~ e n e forms red needles m. p. 173" ; with panisaldehyde it gives the corresponding hydruzone red needles m. p. 208". 5-Nitro-2-amino-4'-methoxyazobenzene forms brownish-yellow needles m. p. 136". 3-Nitro-6 4'-dimethoxy- mobenzene form orange-yellow needles m. p. 123". Thiophenols. V. Salts and Additive Compounds of 00'-Azophenyl Methyl Sulphide and 00'-Azoxyphenyl Methyl Sulphide. K. BRAND and P. GROBEL (Ber. 1923,56 [B] 2563- 2567).-An extension of the work of Brand and Wirsing (A.1912 i 666; 1913 i 406) on the para-compounds to the ortho-series. SMe*C,H,*N:N*C,H,*SMe are described the perchlwute C14H14N2S2,HC104 bluish-violet needles which are very sensitive to moisture m. p. 154" ;. the sulphate C14HI N2S2,2H2S04 dark violet needles ; the very unstable hydro- chlori$e blue needles and its additive cornpotmds with stannic chloride C14H14N2S2,HCI,SnC1 blackish-violet needles with ferric chloride Ci~4H14N2S2,HCI,FeC1 dark violet almost black needles and mercuric chloride an unstable blue compound. 00'-Dimethylthiolazobenzene is transformed by methyl sulphate into the met hosu lphte N2(C 6H*4*SMe2*O*S O,*OMe) coarse crystals m. p. 189" (decomp.) which IS converted into the corresponding iodide Cl4H1,N2S2,2MeI long red needles m.p. 154" which readily loses methyl iodide when preserved the bromide m. p. 154" and the unstable thiocyanate decomp. 102-105". o-Nitrophenyl methyl sulphide ia reduced by sodium and methyl alcohol to 00'-dimethylthiohzoxybenzene crystals m. p. 72" from which the corresponding methsulphate C14H140N,S2,2Me2S04 yellow leaflets m. p. (indefinite) 167-169" (decomp.) after becoming red at 160-162" and the methiodide C,,H,,ON2S2,2MeI m. p. 103" (decomp.) are obtained. 00'-Dimethylthiolazobenzene and the azoxy-compound combine with iodine in chloroform solution to give the compounds m. p. 155" after evolving iodine at 140° and C14H,4.0N2S2,21 dark green needles m. p. 11 3-1 14" ; the corresponhg sulphonium methosulphates when treated in aqueous solution with iodine and potassium iodide yield the compounds C14H14N2S2,2MeI,212 m.p. 113-115" (decomp.) and C14H140N2S2,2~~eI,212 m. p. 193" (decomp.) after darkening a t 100". The following additive compounds are described the stibstance Cl4Hl4N2S2,AgNO3 from the components in boiling aqueous- alcoholic solution orange-coloured needles which is completely decomposed into its components by hot water ; the salt yellow needles ; oo'-diethylthiohzobenxene silver nitrate E. H. R. The f ollo wing s alfs of 00'- dimethyl t hiolazo benzene c14H 1dN2s2 2MeBr 14H 14N2s2,212 C14H 140N2s2Y AgNO CH 1 8N2S2,AgN03,i. 220 ABsTqAms or CKEMICBL PAPERS. orange-coloured leaflets ; o-nitrophenyl methyl sulphide silver nitrade N0,*C,H4-SMe,AgN0 yellow leaflets m p. 122'. H. W.The Influence of Sulphonic Groups on the Colour of ,Azo- dyes. W. M E ~ Y (Helw. Chim. Acta 1923 6 931-935).-To determine the influence of the num%er and position of sulphonic groups on the colour of azo-dyes spectroscopic comparison was made of a large number of secondary bisazo-dyes in which the first component was an aniline mono- or di-sulphonic or a naphthyl- amine mono- di- or tri-sulphonic acid the middle component was cresidine (3-amino-p-cresol ether) and the end component an a- or p-naphthol mono- di- or tri-sulphonic acid. In every case an additional sulphonic group in either the first or the end component deepens the colour but the effect diminishes as the number of sulphonic groups increases. In the naphtholsulphonic acids the effect of changing the position of the sulphonic group is smaller than the effect of an additional group. Similar results were obtained with a number of monoazo- and trisazo-dyes. As an example of the effect of additional sulphonic groups the dye from sulphanilic acid 3-amino-p-cresol ether and 1 4-naphtholsulphonic acid is red whilst the corresponding dye using 1 3 6 8-naphtholtrisulphonic acid is violet. An absorption band may be shifted 10 to 20 p~ by a single sulphonic group the influence being generally greater m the end component than in the first component. These results apply both to aqueous and to .alcoholic solutions; in sulphuric acid and formic acid solutions the absorption bands are shifted in the opposite direction by sulphonic @oups.[Cf. B. 86.1 E. H. R. Certain Double Salts of Diazo-compounds with Lead Tetrachloride.E. SAKELLARIOS (Ber. 1923 56 [B] 2536- 2541) .-A series of double salts of the general formula (ArN,Cl),PbCl has been prepared. They are generally yellow in colour and insoluble in water. They are decomposed when heated with water with production of phenols. Thermal decomposition in the presence of inert solvents such as carbon tetrachloride or benzene gives p-chloronitrobenzene from the p-nitrodiazonium compound and mixtures of chlorinated benzenes from the benzenediazonium salt. The p-tolyl- m-nitrophenyl- and p-chlorophenyl-diazonium compounds are remarkably stable towards heat. The double salts dissolve in concentrated sulphuric acid with separation of lead tetrachloride and production of the diazonium sulphate.They couple immediately with an alkaline solution of p-naphthol and retain this power after being preserved during many months in a desiccator ; an exception is however provided by the benzene- diazonium salt which undergoes rapid decomposition. Direct sunlight and increased temperature facilitate the decomposition in a remarkable degree. The lead tetrachloride solution is prepared by dissolving lead carbonate in concentrated hydrochloric acid and passing chlorine into the mixture a t 10" until the suspended lead chloride is dissolved ; exces8 of chlorine is removed in a current of air. The solution thusORGANIC CHEMISTRY. i. 221 prepared is added to the requisite diazonium solution a t -6' when the double salts separate. The following individual substances are described the salt (PhN,Cl),PbC14 straw-yellow leaflets and the similarly constituted compouotds from p-toluidine (a yellow crystalline powder) p-chloroaniline (yellow leaflets) p-nitroaniline (yellow leaflets) and m-nitroaniline Ethylamine hydrochloride and lead tetrachloride give the compound (EtNH,*HCl),PbCl yellow leaflets which is decomposed by water with formation of ethyldichloroamine b.p. 89'. H. W. Characterisation of Aminoazo-derivatives. G. CHARRIER and A. BERETTA (Gaxxettu 1923 53 729-760).-!l!he authors find that the reaction suggested by Nietzki and Ernst (A. 1890 11 14) for charactmising the primary aromatic amino-group (cf. Reitzenstein A. 1903 i 815; Meigen A. 1908 i 580; Kiichel Diss. Giessen 1N9) and based on the action of 1-chloro-2 44%- nitrobenzene in alcoholic solution and in presence of sodium acetate followed by reduction of the resulting 2 4-dinitrodiarylamino- derivative to nitroaminodiarylamino-compound by meam of sodium sulphide is general for all aminoazo-derivatives irrespective of the position of the amino-group to the azo-group.The yield of the condensation product is moderately good from the p- and m-arninoazo-compounds but less from the ortho-compounds especially those of the naphthalene series. However no resin is formed and the product is usually almost insoluble in alcohol so that purification is easy. [With A. NANI L. ALBANI A. DE LEONIBUS G. DRISALDI P. PAVESI and 0. ~~v~zz~~1.]-2'-Benxeneaxo-2 4-dinitrodiphenyl- amine ~h:N*C6H4*NH0C6H~(NO,) obtained by the action of 1-chloro-2 4-dinitrobenzene on 0-aminoazobenzene forms slender orange-yellow needles m.p. 206' dissolves in concentrated sulphuric acid with a green coloration and resists boiling acetic anhydride. When suspended in alcohol and treated with sodium sulphide it yields 2'- benxeneuxo-4-nitro-2-aminodiphenylumine NPh:N*C,H,*NH*C 6H3( NH,)*NO which crystallises in slender deep red needles m. p. El0 and gives a benmyZ derivative C,,H,,O,N crystallising in slender yellow needles m. p. 199". C ,H,Me*N:N*C ,H,Me*~*C,H,( NO,) prepared from o-tolueneazo-p-toluidine forms lustrous red needles m. p. 232" gives a green solution in concentrated sulphuric acid and on reduction with sodium sulphide yields 2'-p-toluenmxo- 4-nitro-2-amino-4'-methyldi~henylamineY CtH4Me*N:N*C,H3Me*NH*C6H3( NH,)*NO which crystallises in reddish-brown needles m.p. 166' and gives a benzoyl compound C2,H2303N5 separating in yellow needles m. p. 206'. m-Aminoazobenzene m y be obtained in satisfactory yield by benzoylating m-nitroaniline reducing the m-nitrobenzanilide to m-aminobenzanilide and converting the latter by means of nitroso- 2' -p-Tolueneam-2 ; 4-dinitro -4'-meth yldiphen ylumine,i. 222 ABSTRACTS OR' m C A L PAPEW. benzene into the benzoyl derivative of m-aminoazobenzene. The melting point of m-aminoazobenzene given by Mills (T. 1895 67 917) as 56-57" is found to be 62". NPh:N*C ,H,*NH*C sH3( NO,) 2 prepared from m-aminoazobenzene crystalllses in orange-yellow leaflets m. p. 162" and dissolves in ooncentrated sulphuric acid giving a red coloration.4'-Benzeneazo-2 4-dinitrodiphenylamine prepared from p-amino- azobenzene has m. p. 176" (cf. Walther and Lehmann A. 1904 i 352). 4' - Benzeneam - 4-nitro-2 -aminodiphen ylamine C *HI ,Q2N obtained by reducing the preceding compound forms minute deep red crystals m. p. 164"; its acetyl compound crystallises in slender yellow needles m. p. 153" and its benxoyl derivative in yellow needles m. p. 226". prepared from o-tolueneazo-o-toluidine forms deep red needles m. p. 186" dissolves in concentrated sulphuric acid to a reddish- violet solution and on reduction with sodium sulphide and alcohol yields 4'-Q -tolueneuxo-4-nitro-2-amino-2'-methyldiphen ylamine which separates in reddish-brown needles m. p. 159". 4'-p-Toluewxo- 2 4-dinitro-2'-methyldiphenylamine prepared from p-tolueneazo- o-toluidine crystallises in slender lustrous red needles m.p. 151" and dissolves in concentrated sulphuric acid giving a violet -red coloration. The actioa of I-chloro-2 4-dinitrobenzene on m-diaminoazo- benzenes results in the replacement by 2 4-dinitrophenyl of a hydrogen atom of the amino-group situate in the para-position to the azo-group. The amino-group in the ortho-position to the azo-group does not enter into the reaction even when the chloro- dinitrobenzene is taken in large excess; this appears to be due to the fact that the mono-condensation product is insoluble in alcohol and is hence removed from the sphere of reaction. The resulting diphenylamine derivatives have constitutions analogous to (I) and on oxidation yield the corresponding triazole compounds (11) 3'-Benxeneam-2 4-dinitrodiphenylamine 4' -0 - Tolueneazo -2 4-d initro-2' -methyldiphen ylamine C,H4Me*N:N*C,H3?le =NH*C,H3( NO,) 2 /-\-NH-/-\-N:Nph + (1.) L/ NO2 NH2 (11.1 N 0 2 ~ > - N H - r ~ ~ > N P h .\-/ N They readily yield monoacetyl and monobenzoyl derivatives the substituent groups entering the amino-group in the ortho-position to the azo-group. By sodium sulphide in alcoholic solution they are reduced to benzeneazonitrodiaminodiarylamines of the general formula NO2<:>-NH-<3-N:NPh. NO2 NHZ NHZOBGANICl cYHEMrsTBY. i. 223 4'- Benxeneaxo-2 4 -dinit TO- 3'-aminodiphenylami n e NPh:NS?*H3( NH2) *NH*C,H,( NO,) obtained by the action of 1-chloro-2 4-dinitrobenzene on 4-benzene- azo-1 3-diaminobenzene (chrysoidine) crystallises in bright red needles m.p. 187" and gives a violet solution in concentrated sulphuric acid ; its acetyl compound forms slender orange-red needles m. p. 218" and its benzoyl compound silky red needles m. p. 241 ". N-Phenyl-2' 4'-dinitrophenylamino(3)benztriaxole (formula 11 above) crystallises in slender yellow nedes m. p. 188" and dissolves in concentrated sulphuric acid giving a reddish- yellow coloration. c ,H4C1*N:N*C6H3( NH,)*NH*C,R,( NO,) prepared from 4-p-chlorobenzeneazo-1 3-diaminobenzene forms lustrous reddish-brown leaflets m. p. 220" and gives a blue solution in concentrated sulphuric acid. ( p-chlorochrysoidine) CGH4Cl*N:N*C61rT,(NH,) prepared by the interaction of p-chloro- phenyldiazonium chloride on m-phenylenediamine hydrochloride erystallises in lustrous yellow needles m.p. 140" and its hydro- chloride in slender red needles m. p. 225". 4-p-Brmbenzeneum- 1 3-diaminobenxene (p-brmchrysoidine) C,,H11N4Br similarly prepared forms lustrous golden-yellow needles m. p. 155" and its hydrochloride red needles m. p. 213". 4'-p-Bromobenzeneum- 2 4-dinitro-3'-aminodi~enylamine C18H.1304N6Br prepared from the preceding compound forms lustrous brick-red needles m. p. 218" and dissolves in concenkrated sulphuric acid giving a blue coloration. ~ h ~ * C 6 H ~ e ( N H 2 ) * ~ o C 6 H 3 ( N 0 2 ) forms deep red needles m. p. 273-274" and dissolves to an emerald-green solution in concentrated sulphuric acid ; its acetyl derivative forms orange-yellow needles m. p. 196" and its benzoyl derivative orange-red needles M.p. 252". 4'-Benxenmz0-4-nitro- 2 3'-diamino-6'-methyldiphenylamine C,,H180&Y6 formed on reduction of the preceding compound by means of sodium sulphide and alcohol crystallises in lustrous garnet-red prisms with metallic reflection m. p. 244". 4 - p - Chhobenxeneam - 1 3 - diamino-6-methylbenzene (p - chloro- meth ykhrysoidine) C ,H4ClaN:N*C ,H&e ( NH,) 2 prepared from p-chlorophenyldiazonium chloride and m-tolylenedismine hydro- chloride forms lustrous golden-yellow leaflets m. p. 169" and its hydrochloride lustrous red needles m. p. 235". 4'-p-chloro- benzeneam-2 4-dinitro-3'-amino-6'-~thy~iphenylamine prepared from the preceding compound crystallises in reddish- brown lustrous needles m. p. 286" and dissolves in concentrated sulphuric acid giving a green coloration ; its acetyl compound forms slender orange-yellow needles m.p. 248" and its benxoyl com- pound orange needles m. p. 285". On reduction with sodium sulphide in alcoholic solution it gives 4'-p-chlorobenxeneum-4-nitro- 4'-p-~~lorobenxeneaxo-2 4-dinitro-3'-amimdiphenylamine 4-p- Chlorobenxeneaxo- 1 ; 3-diaminobenzene 4'- Benzeneam -2 4 -din itr0-3'-amino- 6'-methyldiphen ylama'ne c19H1504N6c1,i. 224 ABSTRACTS OF c,xiElmCl& PISPEBS. 2 3'-diamim-6'-methyZdiphenylamine C,,H,,O~,,Cl whicth forms slender reddish-brown crystals m. p. 262". 4-p-Bromobenzeneaxo- 1 3 -& iamino- 6-mth ylbenxene ( p- b romometh yhhrysoidine) crystallises in lustrous golden-yellow leaflets m. p. 177" and its hydrmhhide in lustrous red needles m.p. 236". 4'-p-Bromo- benzeneurn-2 4-dinitro-3'-amino-6'-methyl&iphenykcmine prepared from the preceding compound crystallises in brownish- red leaflets m. p. 290" and yields a green solution in sulphuric acid ; its acetyl derivative forms orange needles m. p. 242" and its benmyl derivative orange-yellow needles m. p. 275". 4'-p-Bromo- benzeneam-4-nitro-2 ; 3'-diamir~-6'-methyldiphenylamine forms reddish-brown leaflets m. p. 265". CloH7*N:N-C,H$fe( PU'R,) prepared from a-naphthyldiazonium chloride on m,tolylenediamine hydrochloride crystallises in brown needles with green metallic reflection m. p. 148". 4'-u-Naphthaleneuxo-2 4-dinitro-3'-amino- 6'-meth yMiphen y kcmine C,H ,ON :N*C sH2Me (NH,)*NH-C 6H3( NO,) obtained from the preceding compound forms reddish-brown needles with violet metallic reflection m.p. 286"; its acetyl compound forms red needles m. p. 268" and its benxoyl compound yellow needles m. p. 246". 4'-a-NaphtbZeneam- 4-nitro-2 3'-diamino-i3'-methyldiphenylamine C,H,O3 forms reddish-brown needles m. p. 214". 4-p-Napht7uzkneaxo-1 3-di- amino- 6-meth ylbenzene ( (3 -mphth ylrneth ylchr ysoidine) c17H16N4 crystafises in yellow needles m. p. 242". 4 - p - N a p h M w z o - 2 4-dinitr0-3'-amino-6'-~thyMiphen~kcm~ne forms a reddish-brown crystalline powder chars without melting above 300" and gives a green solution in concentrated sulphuric acid ; its acetyl compound sepmtes in slender yellow needles m. p. 272" and its benxoyl compound in orange needles m. p. 267O. 4-p-Naphthaleneam-4- nitro-2 3'-diamino-6'-methyldiphenylamine C,H,Oa forms minute reddish-brown crystals m.p. 261" a - Benzeneax0 - p - nuphthyl - 2 ; 4 - dinitrophenylumine (annexed formula) prepared by the action of 1-chloro- 2 4-dinitrobenzene on a-benzeneazo- p- naphthylamine crystallises in slender red needles m. p. 285" and gives a greenish- / \-N:NPh \- &H.c,H,(NO,) blue solution in concentrated sulphuric acid. a- Benzeneam- -naphth yl-4-nitro-2- amimphenylumine Nph :N~ClooH,*NH*C,H,(NH,).N02 forms reddish-brown needles m. p. 147 . a-o-Tolueneam-~-~phthyl-2 4-dinitrophenylumine7 c&~704~5 obtained from a-o-tolueneazo-P-naphthylamine crystallmea m slender red needles m. p. 223" and dissolves in Concentrated sulphuric acid to a greenish-blue solution. a-m-ToZzcemm- ~-nuphi?hykcmine has m.p. 103-104°. a-m-Tolueneaxo- p-naphthyl- 2 r4-dinitrophenylamine forms slender red needles m. p. 845" C13H 13N4Br9 '1gHl 5°4N6Br 1f+H170$ 6Br 9 4- U- Naphthaleneaxo- 1 3-diamino-6-methylbenzene c>ORQAWIO OHEMZSTBY. i. 225 and 'VW a greenish-blue solution in concentrated sulphuric acid. a-m-!f&ueWzo- p - ~ ~ h t h y l - 4 - n i t ~ ~ - ~ - ~ ~ i ~ ~ h is obtained as a dark red microcrystalline powder m. p. 116'. a-p-Tolueneaxo-p-~phthyl-2 ; 4-dinitrodiphenylamine crystabes in slender red needles m. p. 280" and dissolves in concentrated sulphuric acid to a green solution. a-p-Tolueneazo- p-mphthyl- 4-nitro-2-aminophenylamine forms microscopic reddish-brown crystals m. p. 155". crystallises in slender bright red needles m.p. 278" and dissolves in Concentrated sulphuric acid to a deep blue solution. a-p-Brm- benxeneaxo- p-nuphthylamine C,H4Br*N:N*CloH,-~2 forms red crystals m. p. 135-136". a-p-Bromobenxeneazo-p-mphthyl-2 4-di- nitrophenylumine crystallises in slender red needles m. p. 263" and gives a deep blue solution in concentrated sulphuric acid. 4-Benzeneum- a-nuphth yl-2 4-dinitrophen ylumine obtained from 4-benzeneazo- a-naphthylamine forms long bright-red silky needles m. p. 200" and colours concentrated sulphuric acid bright blue. 4 - Benxeneaxo - a - nupht h y 1-4- nitro - 2 - amimphen ylurnine se ar at es in slender red needles m. p. 216". 4-0-Tolueneaxo-U-naphthyl-2 4-dinitrophenylamine C,H,Me*~:N*CloH,~NH*C,H,(NO )2 forms lustrous reddish-brown crystals m. p. 824' and dissolves in concentrated sulphuric acid to a deep blue solution.4-p-Tohem- am-a-nuphthyl-2 4-dinitrophenyhmine crystauses in lustrous bright red needles m. p. 207" and gives a blue solution in concentrated sulphuric acid. 4-p-Tolueneaxo-a-naphthyl-4-nitro-2- amimphenylumine separates in reddish-brown crystals m. 4-o-Nitrobenzeneam-a-nuphthyluntine N0,*C,H4*N:NClo s a M l [ e crystafises in slender metallic green needles m. p. 165". 4-a-"ttPo- benxeneuxo- a-mphthyl-2 4dinitrophenylumine forms a reddish-brown microcrystalline powder m. p. 212" and yields a blue solution in concentrated sulphuric acid. 4-p-Nitro- benxeneum-a-nuphthylumine crystallises in deep red needles with metallic reflection m. p. 252". 4-p-Nitrobenxeneaxo-a-~~AthyZ- 2 4-dinitrophenylamine separates in slender brownish-red needles m.p. 263" and dissolves in concentrated sulphuric acid giving a violet coloration. c23H190a5 a-p-Chlorobenxeneaxo-p-mphthyl-2 4-dinitrophenylamine C!22H1404N5C1 minute reddish-brown crystals m. p. 181" and its acety P compound I$* 2ooo* NO,*C,H4*N:N*Cl,H,'NH0C,H,(NO,) 4-p - Chlorobenzeneuxo - a - napht h y 1 - 2 4 -dinitrop henyhmine C22H1404N5c1 forms slender orange needles m. p. 258" and gives a peen solution in concentrated sulphuric acid. 4-p-Chlorobenxeneaxo-a-nccphth2/1- 4-nitro-2-aminophenyhmine separates in slender deep red crystals m. p. 228". crpfrtllises in slender brownish-red needles m. p. 203" and dia- 4- a-Naphthaleneuxo- a-mphthyl-2 4-dinitrophenyhmk 'w*. q. 1 C,H,*N:N*C~oH,.NH*C,H,(NO2) VOL. OXXVI.i. ii. 226 ABSTRA@IS OF CHEMICAL PAPERS. solves to a blue solution in concentrated sulphuric acid. 4-8- Na~hthaleneaxo-a-nalpht~yl-2 4dinitrophenylamine forms reddish- brown needles m. p. 241" and dissolves in concentrated sulphuric acid giving a blue solution. E. J. POTH and J. R. BAILEY (J. Amer. Chem. Xoc. 1923 45 3001-3008; cf. A. 1922 i 880).- Semicarbazones were reduced to $he corresponding semicarbazides under a pressure of 1+-23. atm. of hydrogen in the presence of colloidal platinum. The minimum proportion of platinum necessary for efficient reaction varied considerably and when the reduction produced a basic substance the yield was increased by the addition of acid ; the amount of acid required varied greatly. The following semicarbazides were prepared.~enchylsemicarbazide short needles m. p. 181". Benxoylfenchylsemicarbaxide a crystalline powder decomp. 226". a-Phenylcarbamylfenchylsemicarbazide thin plates m. p. 192". Car~ome~zthylsemica~~bazide thin plates m. p. 126" (decomp.) and its hydrochloride short needles decomp. 186". Benxoylcarvomenthylsenzicarbazide m. p. 235". a-Phen ylcarbanzyl- carvomenthylsemicarbaxide clusters of radiating needles m. p. 205". cycloHexylsenzicarbazide needles decomp. 185" and its hydro- chloride m. p. 176-178'. Benzoylcyclo7~exylsemicarbazide fine needles m. p. 267" (decomp.). a-Phenylcarbamylcyclohexykemi- curbazide microscopic short needles decomp. 236". Benzylsemi- carbazide. Benzoylnzenthylsemicarbazide a crystalline powder m. p. 2 16" (decomp.). u- Phenylcarbamylment hylsemicarbazide radiating needles decomp.184". In the preparation of isopropyl bornyl and menthyl semicarbazides the proportion of colloidal platinum may be considerably reduced with advantage. The following triazoles were obtained by boiling the corresponding acyl semicarbazide with caustic alkali. 3-Hydroxy-5-phenyZ-l-fenchyltriazole thick triangular plates m. p. 234". 3-Hydroxy-5-phenyl-l-carz;omenthyl- triazole thin plates m. p. 187". 3-Hydroxy-l-cyclohexyl-5-phenyl- triaxole slender prisms m. p. 232-234". T. H. P. Reduction of Semicarbazones. F. B. Behaviour of Semicarbazides at Elevated Temperatures. E. J. POTH and J. R. BAILEY ( J . Amer. Chem. Soc. 1923,45,3008- 3012 ; cf. preceding abstract).-cycloHexylsemicarbazide when heated a t 200" during twelve minutes yielded dicyclohexylcurbaxide (I) CO(NH*NH*C,H,,) plates m.p. 187" and unchanged semi- carbazide. When the semicarbazide was heated for one and a half hours at 180-185" the products were cyclohexyluraxok (11) ~H-co>N*c6H11 thin prismatic plates m. p. 271" and c 0.m prisms m. p. 197"; (I) was obtained in good yield when the semi- carbazide was mixed wit'h half its weight of urethane and heated at 160° (11) was prepared by heating the semicarbazide and carbamide in molecular proportions and (111) by decomposing the hydro- chloride of the corresponding semicarbazide. F. B.ORGANIC CHEMISTRY. i. 227 Arylazides. I. Conversion of p-Methylarylazides into Homologues of Quinol in Presence and Absence of Phenol. E. BAMBERGER and J. BRUN (Helw. Chim.Acta 1923,6,935-941).- Some further experiments on the conversion of arylazides into homologues of quinol (cf. A. 1921 i 716) are described. p-Tolyl- azide (5 g.) boiled with dilute sulphuric acid (1 3 by volume) gives about 1 g. of toluquinol with some p-toluidine a strong odour of cresol but no aminocresol. From 25 g. of m-4-xylylazide boiled for nine hours with dilute sulphuric acid there mere obtained 1.8 g. 1 3-dimethylquinol,O*2 g. as-m-xylenol 4.2 g. as-m-xylidine and a considerable quantity of amorphous acids bases and resin. When p-tolylazidc was boiled as before in dilute acid in presence of excess of phenol from 6 g. of azide 4.27 g. of p-hydroxyphenyl-p-tolyl- amine was obtained and about 0-32 g. of toluquinol. The theory of the reactions involved has been previously discussed (Em.cit.). E. H. R. Arylazides. 11. The Conversion of p-Methylarylazides into Imino-tpquinols and q-Quinols. E. BAMBERGER and J. BRTTN (HeZv. C'him. Acta 1923 6 942-951).-Practical details are given of experiment,s previously reported (A. 1921 i 716). E. H. R. Partial Decomposition of Proteins. E. ABDERHALDEN (2. physiol. Chem. 1923 131 284-295) .-A general description is given of the method of isolating the products of the partial hydrolysis of proteins. The protein is treated with 70% sulphuric acid at a low temperature e.g. a t the ordinary temperature or at blood heat and the course of hydrolysis is followed by estimating the amino-nitrogen and comparing it with the total nitrogen of which an estimation is made on the original protein.The sulphuric acid is removed as barium sulphate and the filtrate is concentrated in a vacuum. If the prdduct is a solid it is extracted directly with ether in a Soxhlet apparatus ; if it is a syrup it is mixed with sand to a thick consistency and t'hen extracted. It is afterwards extracted in turn with ethyl acetate acetone or methyl alcohol and if necessary with other solvents such as chloroform or butyl alcohol. It is usually possible after evaporation of the solvent to obtain the fractions in a crystalline form and they are purified according to their particular composition. In particular cases variations a t any stage may be advisable. In an attempt to obtain the maximum yield of d-alanylglycine anhydride from silk clippings the residue after hydrolysis removal of sulphuric acid and concentration was treated with alcohol and hydrogen chloride evaporated to dryness arid the residue dis- solved in alcohol.The ammonium chloride separating at once on saturation with ammonia was filtered off. On keeping a t 37" a series of crystalline fractions was obtained which were extracted in a Soxhlet apparatus with ethyl acetate. Eighty-five g. cf pure glycylalanine anhydride was obtained from 1 kg. of silk clippings. Small quantities of glycyl-Z-tyrosine anhydride and of d-alanyl anhydride (dimethylpiperzzine) were also obtained i2i 228 ABSTRACTS OF UHEMICAL PAPERS. One kg. of casein was hydrolysed with 10% sulphuric acid at 80° and the product extracted with ethyl acetate when 2.5 g. of crystals were obtained decomp.280° and this compound proved to be I-Ieucyl-d-valine anhydride. On extracting the residue from the ethyl acetate extraction with acetone crystals were obtained which on hydrolysis yielded leucine valine and glutamic acid but there was no guarantee that the compound was pure. On further extraction with methyl alcohol d-alanyl-Z-leucine was obtained along with a crystalline compound C,,H,O,N m. p. 192" [01] -183" which yielded proline I-leucine and d-alanine on hydrolysis. It is apparently an anhydride formed from these acids by the elimination of 3 mob. of water. The Formation of Carbon Dioxide during the Breakdown of Proteins in the Autoclave. V. S. SADIKOV (Biochem. Z. l923,143,492495).-The method used for the catalytic hydrolysis of proteins by dilute hydrochloric acid under pressure (A.1923 i 867) leads in the case of gelatin to a slight formation of carbon dioxide amounting to 2% of the protein. It is suggested that this arises by decarboxylation of the amino-acids under the conditions used. Increasing pressure favours carbon dioxide formation. Nitrogen is also present in the residual gas in the autoclave and oxygen is largely absorbed during the process. V. 8. SADIKOV (Biochem. Z. 1923 143 496-503).-Arising from the author's work on the catalytic hydrolysis of proteins under pressure (cf. preceding abstract) it is found that a retention of nitrogen results when this is carried out in an atmosphere of the gas. Dextrose gives negative results but a fixation is observed in the case of aspartic acid and to a less extent in the case of glycine.Similar treatment of fumaric and succinic acids in the autoclave leads to a notable retention of nitrogen which is ascribed to the unsaturated compounds arising from these acids. Separation of Proteins of White of Egg by the Acetone Method. M. PIETTRE (Compt. rend. 1924,178,91-93).-Details are given for the separation of the proteins of white of egg into a globulin ovalbumin (coagulating at 52-5-53" and having uD -41*25") and a glucoprotein. The latter (aD -62.47") reduces boiling Fehling's solution and a t a moderate temperature mercury and bismuth salts (in presence of alkali) and ammoniacal silver nitrate. E. E. T. A Furtber Method of Determining the Isoelectric Point of Proteins and its Application to the Serum-albumins of Various Animals.L. WCHAELIS and T. NAKASHIMA (Biochem. Z. 1923 143 484-491).-The optimum precipitation point of a mixture of mastic and gelatin in the presence of an acetate buffer approaches the isoelectric point of the latter as its relative amount is increased. This observation is made the basis of it method of determining the isoelectric points of various serum-albumins. To a series of tubes containing mastic sol and an acetate buffer at W. 0. K. J. P. Hydrolysis in an Autoclave containing Nitrogen. J. P.ORGANIC CHEMISTRY. i. 229 varying known m increasing amounts of the albumin are added and the p H of the zone of optimum precipitation is observed to rise to a constant value beyond which addition of the albumin produces no further shift. This maximum p~ corresponds with the koelectrio point.The following values for the albumins examined were found ox and guinea-pig 4.65 ; dog 4.66 ; puppy 4.67; turtle and man 4-68. J. P. Nature of the Reaction between Carbophosphide and Blood- serum. G. CTJNEO (Atti R. A d . fincei 1923 [v] 32 fi 294- 298; cf. this vol. i loo).-The interaction of carbophosphide and blood-serum yields a phospho-albumin which contains phosphorus in organic combination and either in the most highly oxidised state or as metaphosphoric acid. Since further nuclein bases occur among its products of hydrolysis this phospho-albumin probably owe8 its existence to a hydrolytic process coupled with atmospheric oxidation as a result of which the phosphorus of the carbophosphide enters the protein molecule as phosphoric oxide or as a hydrate of the latter.Nature of the Reaction between Carbophosphide and Blood- serurn. G . CUNEO (Atti R. A d . Lincei 1923 [v] 32 ii 353- 357; cf. this vol. i 100 and preceding abstract).-The author has now investigated the behaviour of blood-serum towards a number of d8erent compounds some free from and others con- taining phosphorus. Certain of these compounds do not denature the serum albumin molecule which remains phosphorus-free normally digestible by gastric juice and without hindering effect on putrefactive processes. On the other hand phosphorus di- iodide ethylphosphine and sodium hypochlorite effect denaturation of the protein molecule the reaction like that produced by carbo- phosphide being probably of the nature of an auto-oxidation. The reaction of the serum-albumin with hypochlorite is complex but the principal product is devoid of iron and phosphorus and exhibits the chemical and biological properties of the nucleic acids.Formation of Methaemoglobin. 11. W. HEUBNER and H. RHODE. 111. R. MEIER. IV. W. HEUBNER and R. MEIER. V. W. HEUBNEE R. MEIER and H. RHODE (Arch. mpt. Puth. Phrrn. 1923 100 117-127 128-136 137-148 14&161).- I. A comparison of various substances which convert oxyhaemo- globin into methsmoglobin shows that the actions of potassium ferricyanide and of p-benzoquinone are almost identical in this respect. Although the compound of haemoglobin with nitric oxide is resistant to the aotion of reducing agents it may be decomposed by means of indifferent gases and also by dialysis. IL Optical and gasometric observations show that by the use of ferricyanide or of p-benzoquinone in varying proportions it is possible to produoe a mixture of oxyhzemoglobin and me-1110- globin with bhe two conetituenfs in any desired propartiOnS.The T. H. P. T. H. P.i. 230 ABSmACTS OF CHEMICAL PAPERS. last traces of oxyhaemoglobin are converted into methaemoglobin more easily by ferricyanide than by p-benzoquinone. 111. In the presence of haemogfobin quinol p-aminophenol and hydrazobenzene are rapidly oxidised by atmospheric oxygen. Whereaa the oxidation products of the first two of these substances are active in forming methaemoglobin that of hydrazobenzene is not ; the formation of methzemoglobin by hydrazobenzene there- fore must be due to an activation of the atmospheric oxygen in the process of oxidation of this substance.Nitrosobenzene converts oxyhaemoglobin in part into methaemo- globin and in part into reduced haemoglobin. IV. Phenylhydroxylamine converts oxyhzemoglobin into methaemoglobin and is itself simultaneously converted into azoxybenzene ; excess of phenylhydroxylamine in this reaction reduces the methaemoglobin first formed t o haemoglobin. Reduced haemoglobin is unaltered optically by phenylhydroxylamine. m-Nitrophenylhydroxylamine reacts similarly to phenylhydroxyl- amine but not so strongly. The Natural Porphyrins. IV. Ooporphyrin. HANS FISCHER and F. KOGL (2. physiol. Chem. 1923 131 241-261).-Three hundred g. of gull's egg-shells were extracted with methyl alcohol containing hydrogen chloride the extract was concentrated made alkaline with sodium carbonate and the precipitate washed and dried a t 100".The material was extracted with chloroform which was then distilled off and the residue dissolved in a little chloroform precipitated by the addition of light petroleum collected on a filter and dried. It was then again dissolved in a little chloroform and boiling methyl alcohol was added. Oopor- phyrin dimethyl ester C,H,,O,N,( OMe) was obtained as leaflets grouped in rosettes m. p. 225-230'. The absorption bands of this compound are described at length. They resemble those of Kammerer's porphyrin. When ooporphyrin methyl ester from the shell of the gull or of the plover egg is treated with powdered iron in boiling acetic acid crystals are obtained which although similar are not identical crystallographically and spectroscopically.The absorption bands of solutions of ooporphyrin froin the egg-shells of various species of birds are described. The Precipitation of the Lactoproteins by Copper Salts. A. J. J. VANDEVELDE (Bull. SOC. chim. Belg. 1923 32 376-386). -The lactoproteins have been precipitated by the addition of various salts of copper (sulphate chloride nitrate and acetate) and the effect of washing the precipitates by water has been examined. With the sulphate chloride and nitrate the results obtained are practically identical. Apart from the case of the .acetate pre- cipitate washing by water appears to have no influence on the composition of the precipitate and its copper content. A second series of experiments was carried out to determine the composition of the solid and liquid phases forming the primitive complex The results obtained show that the quantity of copper in the pre- cipitates increases as the initial concentration of the copper increases C. R.H. W. 0. K.ORGANIC CHEMISTRY. i. 231 whilst the ratio of the quantity of copper precipitated to the total quantity of copper employed diminishes generally in proportion as the initial concentration of the copper increases. The anion present is shown to have a visibly marked effect on the precipitation of the metallic kation. Galeotti's conclusions (A 1904 i 355) as to the equilibrium between the proteins and sulphate of copper are not upheld. F. G. P. S. J. THANN- HAUSER (2. physiol.Chem. 1923 131 296-303; cf. Feulgen and Rosenbeck A. 1923 i 618 and Feulgen ibid. i 964; al80 Thann- hauser and Sachs A 1920 i 201).-The author has found that after hydrolysing triphosphonucleic acid by alkali the adenosine may be precipitated as picrate and has obtained almost the theo- retical yield of this picrate. He does not admit the validity of the criticism of Feulgen (Zoc. cit.) who doubts the existence of the acid but he considers that triphosphonucleic acid is with great probability a pure substance. The author also criticises the results of Feulgen (cf. loc. cit.) regarding thymic acid. Influence of Time on the Physico-chemical Properties of Gelatin Solutions. R. DE IZAGUIRRE (Kolloid 2.' 1923 33 337-347) .-The effect of time on the viscosity multi-rotation and the action of electrolytes on gelatin solutions has been examined.It is shown that in the presence of hydrochloric acid the influence of time on the viscosity of gelatin solutions passes through a minimum with increasing concentration of hydrochloric acid. This minimum corresponds with the initial viscosity of the solution. The same regularity is found with the time change of the osmotic pressure whereby the change with time is smaller the larger the osmotic pressure. Since the maximum of the viscosity and the osmotic pressilre is closely connected with the swelling it follows that the time change takes place in the opposite sense to the swelling that is the greater the degree of swelling the smaller the time change. Since the viscosity serves as a measure of the gelatinisation this must be regarded as an " unmixing " process and not as the form- ation of a hypothetical new modification of the gelatin.The optical rotation of gelatin solutions increases with time in such a way that a curve plotted between the logarithm of the angle of rotation and the logarithm of the time is a straight line. The multirotation is expressed by the formula [.ID =RP in which for a 1% solution of gelatin K=209 and n=0.082. 0. GERNGROSS and S. BACH (Biochem. Z. 1923 143 542-552).- The isoelectric points of various preparations of gelatin have been found t o range from p H 4.45 to 5.55 according to their source. [Cf. also B. Feb.] The Displacement of the Isoelectric Point of Gelatin by Formaldehyde. 0. GERNGROSS and S. BACH (Biochem.Z. 1023 143 533-542) .-The isoelectric points of two preparatians of Triphosphonucleic Acid and Thymic Acid. W. 0. K. J. F. S. The Isoelectric Point of Gelatin from Hide and Bone. J. P. i"i. 232 ABSTRAW OF (3HICMTOAL PAPERS. gelatin were lowered from p H 5-05 to 4.6 and from p~ 4.76; to 4.3 respeotively by the presence of formaldehyde. J. A. WZSON and E. J. KERN (J. Amer. Chem. Soc. 1923 45 3139- 3140; cf. A 1923 i 68).-The two points of minimum in the curve showing the degree of swelling of gelatin as a function of the p H value namely a t 4.7 and 7.7 were confirmed when using ash free gelatin. The points coincide with those at which minimum values for the wave-length of maximum absorption in the ultra-violet are observed. 3'. B. J. P. Points of Minimum Swelling of Ash-free Gelatin.Diffusion of Arsenic [Trioxide] in Gelatin. R. SCHAEFER (KoZZoid Z. 1923 33 286-289).-A clear transparent gel con- taining arsenious oxide and suitable for dental purposes may be prepared by adding a few C.C. of hot 30% gelatin aolution to a hot solution of arsenious oxide with vigorous stirring. The solution is evaporated slowly on a water-bath and every Bteen minutes a quarter of the evaporated water is replaced by gelatin solution. This process is continued until the concentration desired is reached and the whole allowed to cool to a clear gel. In this way a gel containing 12-15% of arsenious oxide and 20-30% of gelatin is obtained. The diffusion of arsenious oxide in gelatin has been investigated by laying small portions of the above described gel and a paste of the powdered oxide and water on a large piece of gelatin and after sufficient time has elapsed examining the gelatin by exposing it to hydrogen sulphide.In the case of the arsenic gel it is found that the amount of arsenic diffused falls off quite regularly as the distance travelled increases but with the paste there is no apparent diffusion beyond the surface of the gelatin although this has undoubtedly taken place. The author is of the opinion that in the paste simple molecules are present but in the gel more complicated molecules are present and these move more slowly but the total amount of arsenic diffused is greater in the latter case than in the former. J. F. S. Reaction of Alkaloids with Gelatin [Solutions] containing Iodine.H. HANDOVSEY and E. DU BOIS-REYMOND (KoZZoid Z. 1923,33,347-348).-Liesegang rings are produced when a solution of 1 1000 pilocarpine hydrochloride is placed on a gel containing 3% of gelatin 0.6% of potassium iodide and 0.4% of iodine. The rings are alternately reddish-yellow and dark brown and are about 1-2 mm. apart. Similar but differently coloured rings are produced with strychnine nitrate 1 1000 and papaverine hydro- chloride 1 100. J. F. S. The Composition of Spinning Silk. E. ABDERHALDBN (2. phzpiol. Chem. 1923 131 281-283).-From the product of the hydrolysis of spinning silk by 70% sulphuric acid a t 37" there has been isolated glycyl-Z-tyrosine anhydride m. p. 2$2" and glycyl- d-alanine anhydride m. p. 245". W. 0. K.ORGIANIC CHEMISTRY. i.233 The Influence of Temperature on the Action of Amylase. The Action on the Saccharifying Power of b y l a s e . T. CHRZ~ZCZ (Biochem. Z . 1923 142 417439).-The influence of temperature on the activity of the amylases of various cereals a t the optimum p H of 4-9 is not uniform. The optimum ranges found are for barley amylase 49-54" for rye and wheat amylases 49-55" for oats amylase 51-53" and for buckwheat amylase 50-55". In the cases of maize (56-57") millet (58-59') and African millet (62-64') the optima quoted in brackets lie above the temperatures a t which destruction of the enzyme begins. In aqueous solutions barley amylase is inactivated a t 61-62" rye and wheat amylases a t 63-64" and the other varieties a t 65- 66". In general plant amylases are completely destroyed in one hour when exposed to a temperature of 75".Amylases from the same genera but of different varieties show the same susceptibility to alteration of temperature a t the optimum p ~ . Aqueous malt extracts prepared by shaking for at least one hour give a precipitate when heated at 50° but if the shaking be of shorter duration (thirty minutes) precipitation does not commence below 55-60'. The precipitate does not affect the activity of the enzyme. Rye-malt extract is exceptional in giving at most a slight opalescence even at 80". J. P. H. HAEHN and H. SCIIWEIGART (Biochem. Z. 1923 143 516-526).-Potato amylase is activated by sodium chloride and fluoride and by potassium calcium barium and magnesium chlorides. It is inhibited by the salts of the heavy metals.Amino-acids have an activating effect (cf. Doby Biochem. Z. 1914 67 166). Potato amylase after being freed from most of its salts by dialysis or ultra-filtration loses much but not all of its activity but is reactivated by the addition of the salts of the alkali or alkaline-earth metals. A method of combined dialysis and ultra-filtration yields inactive salt -free preparations of the amylase which are reactivated by salts. It is concluded that potato amylase consists of an inactive organic constituent together with an indispensable activating mineral salt. The Hexose Monophosphatase of Takadiastase. J. NOGUCHI (Biochem. Z. 1923 143 190-194).-A phosphatase is present in takadiastase which hydrolyses barium and sodium hexose mono- phosphates a t 37". In the former case barium phosphate separates as a gel and in the latter the extent of the hydrolysis which may be practically quantitative is dependent on the concentration of the enzyme.J. P. C. NEWERG and 0. ROSENTHAL (Biochem. Z. 1923 143 399401).-Takadiastase contains a cellase which at 37" completely hydrolyses cellobiose to dextrose in five days. J. P. Potato Amylase. J. P. The Cellase of Takadiastase. Hemicellusose. IV. Cellobiase and Lichenase. H. PRING SHEIM and J. LEIBOWITZ (2. physiol. Chem. 1923,131,262-268).- Gohenin which is hydrolysed to dextrose by malt exbact has i* 2i. 234 ABSTRACTS OF CHEMICAL PAPERS. been acetylated and then hydrolysed to octoacetylcellobiose (Karrer and Joos A. 1923 i 541). It ought therefore to be possible to show that malt extract hydrolyses it first to cellobiose by means of a lichenase and then to glucose by cellobiase i.e.to show that both lichenase and cellobiase are present in malt extract. This is verified as cellobiose is hydrolysed to dextrose by malt extract a t 37" and pH 5 and on the other hand malt extract after being kept for three months hydrolyses lichenin only to cellobiose as the cellobiase apparently disappears on keeping. The presence of cellobiose was determined by the determination of the reducing power and of the rotation of the solution and also by the formation of the osazone. Synthetic Action of a-d-Mannosidase in Presence of some Monohydric Alcohols. H. HBRISSEY and J. CIIEYMOL (Compt. rend. 1924 178 123-125).-cc-d-Mannosidase effects a partial conversion of mannose in presence of ethyl propyl isopropyl and n-butyl alcohols into the corresponding d-mannosides (cf.A. 1923 i 497). The Separation of the Anti-neuritic Vitamin by Means of its Picrate. G. BERTRAND and A. SEIDELL (Bull. Xoc. Chim. biol. 1923 5 79&796).-The crude extract containing the active material is separated from inorganic substances as far as possible dissolved in 60% alcohol and treated with a solution of picric acid in methyl alcohol. The crude picrate thus obtained is active in amounts of 2 mg. per diem when added to a diet of polished rice and administered to pigeons. On recrystallisation of the picrate from water two separate substances are obtained ; one crystallises in needles m. p. 202" and is inactive ; the other forms a crystalline powder m. p. 160" and is active. C. R. H. M. MASRIERA (Anal. Fis. Quim. 1923 21 4 1 8 4 3 5 ; cf. Staudinger and Hauser A. 1922 i 68).-The constitution of the additive products formed from phosphineimines and alkyl or acyl chlorides is discussed. Triphenylphosphinephenylimine reacts with acetyl chloride' in ethereal solution giving a white compound to which the formula PPh,:NPhAcCl is assigned. It is unstable and gives on decom- position acetanilide and triphenylphosphine oxide. The additive cmpound of triphenylphosphinephenylimine with methyl iodide is a white substance having m. p. 235". Attempts to obtain addition of a second molecule of methyl iodide were unsuccessful. The additive cmpound of toluene-p-sulphonyl chloride with triphenyl- phosphineimine is a white crystalline substance which decomposes when heated forming resins. On keeping a mixture of triphenyl- phosphinephenylimine and toluene-p-sulphonyl chloride in ethyl- alcoholic solution for three months two substances are obtained name1 y trip hen y lp hosphin e - p - t oluenesulpbn y lp hen y lummonium h y d r - oxide PPh,:NPh(SO,*C,H,Me)*OH a white crystalline substance m. p. 191" and its ismeride for which the formula i s suggested ; it is crystalline and has m. p. 115". W. 0. K. E. E. T. Additive Products of the Phosphineimines. OH*PPh,*NPh*S0,*C,H4Me G. W. R.OBQANIO OHEMISTBY. 1. 235 The Syntheses of Arsenic Acids by Means of Diazanium Salts. Z. FOLDI (Ber. 1923 56 [B] 2489-2498).-Evidence is adduced in favour of the view that the diazonium arsenife is the primary product of Bart's arsinic acid synthesis (cf. Schmidt A. 1920 i 897). The transformation of the arsenious ion into the arsinic group is simply explained in accordance with Werner's theory if the constitution HHO-AsOH or H OAsOH is assigned to arsenious acid and it is regarded as functioning as a monobasic acid as is generally the case towards alkali kations including the diazonium-ion. I n arsenious acid the arsinic group exists there- fore preformed. The production of the arsinate can therefore be explained by assuming that the diazonium kation present in the second sphere of the central arsenic atom enters the first sphere thereby transforming the tervalent into quinquevalent arsenic atom and that the diazoarsinic acid decomposes with evolution of nitrogen. p-Toluidine is diazotised in hydrochloric acid solution by means of sodium nitrite; the cooled solution is saturated with hydrogen chloride filtered to remove the precipitated sodium chloride and treated with arsenic chloride whereby a paste of colourless granular crystals is produced without evolution of nitrogen. The product can be coupled with phenols or apines thus showing the diazonium group to be intact. The addition of alkali hydroxide to the aqueous solution causes immediate evolution of nitrogen and the development of the colours and odours characteristic of Bart's reaction. In the presence of sodium hydrogen carbonate the arsenious acid can be titrated with iodine the end-point being shown by the formation of a dark coloured diazonium periodide. According to experimental conditions the campounds C6H,Me*N2C1,AsC1 C6H,Me*N,C1,2AsC1 C,H,Me*N2C1,AsCl,*OH and CGH4Me*N2C1,AsC1,,AsC12*OH can be obtained. The first two of these are extremely labile and particula,rly sensitive to moisture ; they can only be obtained from solutions which are completely saturated with hydrogen chloride. The fourth substance has m. p. 9 A 9 8 " (decomp.) ; it readily loses hydrogen chloride and passes into the pentuchloro-salt C,H,Me*N2(As2C1,0) pale pink octahedra m. p. 111-112" (decomp.) whereas when its solution in absolute alcohol is treated with anhydrous ether it gives the compound C6H4~~e*N2C1,AsC1200H colourless crystals m. p. about 90" (decomp.). The saEt C,H,Me-N,(AsBr,*OH) m. p. 105" is de- scribed. The hydroxy-chloro-salts can also be prepared from solid p-toluenediazonium chloride and arsenic trichloride in concentrated absolute alcoholic solution. The diazonium chloroarsenites decompose vigorously in aqueous or alcoholic solution or in suspension in organic media with evolu- tion of nitrogen in the presence of Gattermann's copper powder or cuprous chloride. In alcoholic solution the reaction is very com- plex giving di-p-tolyl p-tolyl ethyl ether arsenic acid p-tolylarsinic acid ethyl p-tolylarsinate and p-tolylchloroarsine. [ : J OH]i. 236 ABSTRAC!I% OF wEb6ICAL PAP'BRS. A study of the action of p-toluenediazodum sulphate on bmium araenife in the presence of water shows that diazonium arsenites am capable of existence in aqueous solution in the presence of an excess of arsenious acid but attempts to obtain them in the solid state were not successful. Attempts to prepare solutions of diazonium arsenites in the absence of excess of arsenious acid are rendered difficult by the impossibility of preparing undecomposed diazonium hydroxide solutions. When however solutions of p-toluenediazonium sulphate barium hydroxide and arsenious acid in the molecular proportion 1 1 1 are mixed a pale yellow turbid alkaline solution is obtained which is alkaline towards litmus but gradually becomes acidic ; decomposition of the diazonium arsenite is shown to occur in accordance with the two schemes 2C6H4Me*N2*O*As( OH),= C,H,Me*AsO( OH)*O*N2*C6H4Me +N +As( OH) and 2C6H4Me*N,*O*As (OH) = CGH4Me*N2*AsO( O13)*O*N,*C6H4Me +As( OH) the second being the more important. H. W.