701 Organic Chemistry. Direct Hydrogenation of Acetylene Hydrocarbons by Contact Action, By PAUL SABATIER and JEAN B. SENDERENS (Compt. Tend., 1902, 135, 87-89).-Heptylidene, in presence of excess of hydrogen and in contact with reduced nickel a t about 170°, is con- verted into normal heptane together with small quantities of higher hydrocarbons of the same series. Reduced copper above 200" produces a-heptylene, diheptylene, and triheptylene as well as normal heptane. Phenylacetylene, in presence of excess of hydrogen, is converted by nickel a t about 180' into ethylcyclohexane boiling a t 130" together with a small quantity of methylcyclohexane. Copper at 190" to 250' converts the phenylacetylene mainly into metastyrene, ethyl benzene, and diphenylbutane, the yield of the last reaching as much as 50 per cent.(compare this vol., i, 525). Reduction of Nitro-compounds by Direct Hydrogenation in Contact with Finely Divided Metals. By PAUL SABATIER and JEAN B. SENDERENS (Compt. rend., 1902, 135, 225-227. Compare Abstr., 1901, i, 459).-~-Nitronaphthalene with an excess of hydrogen, when in contact with finely divided copper a t 330-350°, is reduced to a-naphthylamine. The reduction can also be carried out with a mix- ture of carbon monoxide and hydrogen. With nickel at the same temperature, the reduction proceeds further, so that some tetrahydro- naphthalene is produced. I n presence of reduced nickel a t 150-180', nitromethane is com- pletely reduced to methylamine, but a t 320" reduction takes place to methane and ammonia. Nitromethane is not reduced by hydrogen in presence of copper below 300' ; above this temperature, reacbion takes place, part of the nitromethane suffers reduction, and a compoiind of nitromethane with methylamine results, the prodtlct being identical with a solution of nitromethane in aqueous methylamine.With nickel at 200°, nitroethane is easily reduced to ethylamine. The reaction with copper is analogous to that found for nitromethane. Action of Hydrazine Hydrate on the Aldol from isoButyr- aldehyde and Formaldehyde. By BERTHOLD KONIG (Monatsh., 1902, 23, 469-478. Compare Abstr., 1900, i, 212, 428).--y-Hyd~- oxy-PP-dimeth ylpr opionaldccxine, formed by the action of hydrazine hydrate on the aldol obtained from iso- butyraldehyde and formaldehyde, crystallises in colourless masses, melts at 151', boils and decomposes a t 190" under atmospheric pressure, a t 165" under 25 mm.pressure, is easily soluble in acetone, alcohol, ether, benzene, chloroform, or water, but only sparingly so in carbon disulphide or light petroleum, and gives the pyrazoline reactions with potassium permanganate or with wood-fibre in dilute hydrochloric acid (Abstr., 1895, i, 248). Cryoscopic and ebullioscopic molecular weight determinations indicate VOL. LXXXII. i. 3 d C. H. 3. J. McC. (OH CH, - C Me, CH : ), N,,702 ABSTRACTS OF CHEMICAL PAPERS, the formula C,,H,o02N2. When distilled or when exposed to moist air containing acid vapours, the aldazine is decomposed, giving an odour of amines and of ammonia. When heated with dilute sulphuric acid a t 90°, boiled with dilute aqueous or alcoholic hydrochloric acid, or when treated with hydrogen chloride in benzene solution, the aldazine is hydrolysed to hydrazine and the aldol.When heated with maleic acid a t 130°, the aldazine forms a yellow, crystalline derivative which melts at 121', decomposes at 150°, and is probably a pyrazoline compound. Sulphur and Nitrogen Derivatives of Carbon Disulphide. V. Dithiocarbamic Esters derived from Secondary Aromatic Amines. VI. Aromatic Xrninodithiocarbonic Esters. By MARCEL DELBPINE (Bull. Xoc. Chirn., 1902, [iii], 27, SO7-812. Com- pare Abstr., 1901, i, 518; this vol., i, 199, 353, 595, 597).-By the action of carbon disulphide on methylaniline in presence of an alcoholic solution of ammonia, the author obtained ammonium methylphenyl- dithiocccrbarnate, NMePh*CS*SNH,, in the form of -yellowish, lozenge- shaped plates, sparingly soluble in cold water or alcohol, and insoluble in ether ; it is only slightly stable in air.Ammoniumphenylethyldithio- car6ccmate, obtained in a similar manner, is closely analogous in its properties t o the preceding compound. Dithiocarbamic esters can be readily prepared by acting with an alkyl haloid on the preceding salts suspended in cold alcohol, By acting on a dithiocarbamic ester derived from aniline in cold ethereal solution with methyl iodide, the hydriodide of an iminodithio- carbonic ester is obtained which decomposes in aqueous solution into the ester and hydriodic acid. On employing an alcoholic solution and heating at 50-70°, the ester is also formed, but the reaction is more complicated.Quantitative yields are obtained by acting with an alkyl iodide on dithiocarbamates dissolved in alcoholic solutions of potassium hydroxide. Methyl phenyliminodithiocarbonate, NPh: C( SMe),, boils at 3Oo0, solidifies on cooling, and crystallises from alcohol in elongated prisms which melt at 36'. The hydriodide melts between 110' and 120' and froths a t aboixt 130'. The picrate is viscous and is decomposed by water. MethyZ p-tolyliminodithiocabonctte, C,H,Me*N:C(SMe),, boils a t 315'. Sulphur and Nitrogen Derivatives of Carbon Disulphide. VII. Dithiocarbamic Esters derived from Primary Amines. By MARCEL DEL&PINE (Bull. Xoc. Chim., 1902, [iii], 27, 812-818. Compare preceding abstract).-These are best prepared by acting on the sulphocarbonic derivatives of primary amines with 1 mol.of an alkyl haloid. I n this way, the author has prepared methyl methyldithio- carbamate, NHISlle*CS*SMe, a thick, heavy, refractive liquid which crystallises in methyl chloride ; ethyl methyldithiocarbamate, an oily liquid ; 6enxyZ methyldithiocarbamate, which crystallisee in small plates melting a t 49.5' ; and benzyl phenyldithiocarbamate, On being heated, these compounds all decompose into thiocarbimide and mercaptan. Wh'en heated with ammonia or with amines, they also undergo decomposition with formation of substituted thiocarbamides G. Y. A. F.ORGTANlC CHEMISTRY. 703 and mercaptan, a reaction which constitutes a new method of synthesis of mono-, di-, s-, and tri-substituted thiocarbamides.The dithiocarbamic esters derived from primary amines also combine with a second mol. of an alkyl haloid, yielding symmetrical or mixed iminodithiocarbonic esters. When subjected to the action of ferric chloride, those dithio- carbamates in which a fatty radicle is attached to nitrogen are un- attacked, whilst those in which an aromatic radicle is attached to nitrogen give rise to isothiuram disdphides ; the compound NPh:C(SMe)*S~S(SMe)*C:NPh forms colourless needles melting at 123O, and the compound forms colourless needles melting a t 158'. To explain the difference in the behaviour of the primary dithio- carbamates, the author, as also for other reasons, considers that the two classes of compounds differ in constitution, those derived from fatty amines having their hydrogen attached to nitrogen, whereas in the compounds derived from aromatic amines, the hydrogen is attached to sulphur.A. F. Action of Organic Acids on Metallic Antimony. I. By B. MORITZ and C. SCHNEIDER (Zed. physikcd. Chenz., 1902, 41, 129-138).- When powdered antimony is shaken with solutions of certain organic acids in the presence of air, the antimony is attacked. The presence of air is essential, and the diminution of the air volume accompanying the action corresponds with the quantity of oxygen it contains and with the quantity of antimony which has passed into solution. Only acids containing the hydroxyl as well as the carboxyl group have the power of attacking antimony under the above conditions; further, it appears that the hydroxyl and carboxyl groups must be attached to the same carbon atom ; thus, whilst a-hydroxybutyric acid acts readily on the metal, the /?-acid is almost without effect.I n all cases, the quantity of antimony passing into solution is greatest when the acid has been partly neutralised with soda, and the mixture therefore contains the acid salt. Of dibasic acids, oxalic, malic, tartatic, and citric acids readily attack antimony as above described. Malonic and succinic acids, on the other hand, are without effect, and the same holds for phenol and benzoic and salicylic acids. Solutions of gdlic and tannic acids produce in a few minutes precipitates containing antimony. I n the course of their work, the authors have isolated a crystalline compound of lactic acid with sodium and antimony, having the empirical formula S bONa,( C,H,O,),. By MARCEL GUERBET (BUZZ.Xoc. Chim., 1902, [iii], 27, 803-S07),-The author has prepared mercurous lactate by dissolving freshly precipitated mercurous oxide in dilute lactic acid, previously heated with water in order to destroy the anhydride, &c., which it contains. The solution thus obtained is allowed to evap- orate in a desiccator over sulphurio acid, when mercurous lactate separates out in short, white, prismatic needles having the composition (C,H,O,),Hg,,H,O. It does not dissolve entirely in water, hydrolysis occurring with formation of a basic lactate, which then decomposes into mercuric lactate and mercury. C,H,Me*N:C(SMe)*S*S(SMe)*C:N*C6H4Me [Me : N = 1 : 41 J. C. P. Mercury Lactates. 3 d 2704 ABSTRACTS OF CHEMICAL PAPERS.I n a similar manner, by dissolving yellow mercuric oxide in dilute lactic acid and allowing the solution to evaporate over sulphuric acid, mercuric lactate separates out in colourless prismatic needles having the composition (C,H,O,),Hg. It is very soluble in water ; on boiling this solution, the mercuric salt passes into mercurous, and there are formed at the same time carbon dioxide, aldehyde, and lactic acid. The substances described as lactates of mercury by Engelhard and Maddrel and by Briining are found by the author t o be mixtures. A. F. Action of Nitrous Acid on a-Substituted /!-Ketonic Esters. Synthesis of the Homologues of Pyruvic Acid. Ey LOUIS BOUVEAULT and RENE LOCQUIN (Compt. rend., 1902,135, 179-182).- By the action of nitrous acid on a-substituted acetoacetates, two pro- ducts are formed according to the equations : (I) COMe*CHR*CO,Et + HNO, = Me*CO,H + NOH:CR*CO,Et and (11) COMe*CHR*CO,Et + HNO, = EtOH + COMe*CR:NOH + CO,.In acid solution, the former reaction takes place exclusively. The same oximoglyoxylic ester is obtained in starting with ethyl ethylhexoylacetate or ethyl ethyl- acetoacetate, namely, NOH:CEt*CO,Et. This oxime of ethyl methyl- pyiwuate boils at 125-130' under 10 mm. pressure; it crystallises in white needles which are soluble in light petroleum and melt at 58'. From ethyl isoamylacetylacetate, the authors have prepared the oxime of ethyl iso6utylpyruwute, CHMe,*[CH,],*C(:NOH)*CO,Et, as a n oil which boils at 114' under 12 mm. pressure and has a sp.gr. 0,9114 at 4'/0'. The corresponding acid, obtained by saponification, melts at 160' with decomposition. Ethyl isobutylpyruvate boils at 105' under '18 mm. pressure. Starting with ethyl sec.octylacetoacetate, the oxime of ethyl ntethylhexylp yruvate, CH,Me [ CH,],* CHMe *C( : NOH) * CO,E t, has been obtained as an oil which boila at 177' under 16 mm. pressure and has a sp. gr. 0.9859 at 4'/0'. The corresponding acid melts at 88-89'. J. McC. Preparation of a-Derivatives of P-Ketonic Esters. By R E N ~ LOCQUIN (Compt. rend., 1902, 135, 108--llO).--When the C-esters of t h e acylacetoacetates (Abstr., 1901, i, 311) are treated with an alkyl iodide and a sodium alkyloxide in presence of a n excess of alcohol, a good yield is obtained in accordance with the equation CHAc(COR).CO,Et + NaOEt + R'I = Me*CO,Et + N a I + R*CO*CHR'*CO,Et, whilst if an alkyl bromide is used the reaction is more complicated and proceeds partly in accordance with the equation CHAc(COR)*CO,Et + NaOEt + R'Br = R*CO,Et + NaBr + UHAcR'*CO,Et.Ethyl ethylhexoyhcetate, boiling at 128-129' under 13 mm. pressure, and of sp. gr. 0.9325 at 4O/O", is obtained in this way from ethyl C-hexoylacetoacetate, which boils at 136' under 10 mm. pressure and has a sp. gr. 1.032 at 0'. The corresponding 4-ethyl-3-amyl pyraxolom melts at 136'. The action of ethyl bromide on ethyl C-butyrylaceto- acetate yields a mixture of ethyl ethylacetoacetate and ethyl ethyl-ORGANIC CHEMISTRY. 705 butyrylacetnte which cannot be separated by fractionation, but S-rnethyl- 4-ethyl pyraxolone corresponding with the former melts a t 1 90°, whilst 4-ethyl-3-propylpyraxolone corresponding with the latter melts at 145' and is more soluble in alcohol or ether.Ethyl hexylbutyrylacetate, CH,Me*CH,-CO-CH(CHMe-[CH2],*Me)*C0,Et, obtained by the action of secondary octyl iodide on ethyl C-butyrylacetoacetate, boils a t 166' under 16 mm. pressure and has a sp. gr. 0,9347 at 4'/0'. I t s pyraz- olone is liquid and boils and partially decomposes at about 270' under 30 mm. pressure. Di-p-phenetidide of Agaric Acid. J. D. RIEDEL (D.R.-P. 130073).-The di-p-phenetidide of agaric acid, produced by heating this acid with 2.5 mols. of p-phene$idine a t 140--160' either under pres- sure or in a current of indifferent gas, crystallises from glacial acetic acid, alcohol, or a mixture of benzene and petroleum in small needles melting a t 150-152'; it is insoluble in water or dilute acid or alkaline solutions.The compound is very soluble in cold chloroform, but dis- solves less readily in other organic solvents of low boiling point. C. H. B. G. T. M. Action of Alkali Nitrites on a-Substituted p-Ketonic Esters. By LOUIS BOUVEAULT and R E N ~ LOCQUIN (Compt. rend., 1902, 135, 295-297).-When ethyl isoamylacetoacetate is treated successively with an alkali hydroxide, sodium nitrite, and an acid, it yields, in almost calculated quantity, nitrosoisoumylacetorte, C1HMe,*CH2*CH,*CAc:N OH, which melts at 32-33', boils at 128' under IS mm. pressure and with hydroxylamine yields a dioxime melting a t 181'. With the higher homologues of the ester, however, the reaction does not suc- ceed, because the action of the alkali hydroxide yields a very unstabre salt, which decomposes in accordance with the equation R*CO*CHR'*CO,Na + NaOH = R*CO*CH,R' + Na,CO,.If, however, the ester is mixed with the calculated quantity of sodium ethoxidc in presence of absolute alcohol and dry ethyl nitrite is passed into the solution, the reaction proceeds as in an acid solution (this vol., i, 704), CHAc(C,H,,)~CO,Et + EtNO, = Ne*CO,Et + NOH:C(C,H,,j=CO,Et. If amyl nitrite is used instead of ethyl nitrite, mixed esters are obtained by partial substitution of amyl for ethyl. The results indicate that if the reaction of nitrous acid with the a-substituted-P-ketonic esters takes place under such conditions that the alkyl group is not hydrolysed a t all or is hydrolysed in presence of an acid, the products are an acid and the oxime of a substituted glyaxylic ester, whilst if during the reaction the alkyl group is hydro- lysed so as to form a salt, R.CO*CHR*CO,M, the products are car- bon dioxide and the monoxime of an a-diketone.Dimethylene Tartrate. CHEMISCHE FABRIK AUF AETIEN (VORM. E. SCHERIN G ) (D. R. -P. 1 3 0 3 4 6 ) . - Dimethy lene tartrate, C. H. B. o*co co.0 produced by heating tartaric acid with paraformaldehyde or trioxy- CH2<0. &H. bH.*>CH29706 ABSTRACTS OF CHEMICAL PAPERS. methylene a t 140-150° and treating the clear solution thus obtained with concentrated sulphuric acid at 60°, crystallises .from alcohol, acetone, or chloroform in needles, melts at 120', and boils without decomposition at 296'.It is slowly hydrolysed by water and more readily attacked by solutions of the alkali hydroxides and carbonates. The substance may also be obtained by adding to an aqueous solution of tartaric acid and formaldehyde sufficient sulphuric acid or phosphoric acid to combine with the Who16 of the water. Hydrochloric acid does not induce this condensation. G. T. M. Action of Halogen Esters and Ketones on Sodioacetyl- acetone. By FR. MARCH (Ann, Chim. Ph,ys., 1902, [vii], 26, 295-366. Compare Abstr., 1900, i, 3'74; 1901, i, 312, 596, and this vol., i, 484).--1-PhenyZ-3 ; 5-dirnethyZpyraxole-4-acetic acid, produced by hydrolysing the correspondini ethil ester with concentrated sodium hydroxide solution, separates from ether in colourless crystals melting a t 140-141'; its copper salt, Cu(Cl,Hl,02N2),, is a violet compound, Methyl 1-phecnyZ-3 : 5-dimefhylp~raxole-4-acetate, resulting from the interaction of methyf bp-iiacetylpropionate, phenyl- hydrazine hydrochloride, and sodium- acetate in dilute methyl alcohol, crystallises from ether in prisms melting at 65'; i t is insoluble in water, but readily dissolves in methyl or ethyl alcohol, and yields the preceding acid on hydrolysis.Ethyl /3/3-diacetyl-a-met?Lylpropionccte, CHAc,*CHMe*CO,Et, prepared by heating a t 1 20-140° ethyl a-bromopropionate and sodioacetyl- acetone, is an almost colourless oil boiling a t 128-130' under 10 mm., and at 149-151" under 33 mm. pressure; it has a sp. gr. 1.067 at 15', and develops a coloration with ferric chloride ; its copper derivative, (C,oH?sO,)aCu, is unstable.The ester, when treated with sodium ethoxide, is hydrolysed into sodium acetate and ethyl a-methpl- Izvulate ; the action of sodium hydroxide on t'he ester gives rise to sodium a-me thyllawulat e. 1 -PhenyZ- 3 : 5-dimethy Zpyrazole-4-a-propionic acid, NPh<CMe :C*CHMe*CO,H ' Nr-YMe produced by hydrolysing the oily condensatio; product of the inter- action of the preceding ester and phenylhy drazine crystallises from alcohol and melts at 129-1309 The disernicarbccxone of ethyl a-methyl-&3-diacetylpropionate is a white, crystalline compound melting a t 207-208". The action of hydroxylamine on the ester gives rise to two products, the dioxime, (NOH:CMe),CH*CHMe*CO,Et, crystallising in needles and melting at 133', ,and ethyl 3 : 5-dimet?~yloxazole-4-a-propionute, N%DIe- ODCMe>C*CHMe*CO2Et, a liquid boiling a t 143-145' underORGANIC CHEMISTRY.707 21 mm. pressure; the corresponding acid, readily obtained by alkali hydrolysis, forms colourless crystals melting a t 106'; its copper salt, (C,H,o0,N2),Cu, is a light green, insoluble substance melting at 154-155'. When the condensation with hydroxylamine is effected by boiling the ester with excess of this reagent and potassium carbonate, another cornpound is formed which probably has the formula N O H : C M e - C H < ~ ~ ~ ~ ~ > O ; this product crystallises in needles and melts a t 202-204'. Methyl yy-diacetylbutyrate, CHAc,*CH,*CH,*CO,Me, a pale yellow liquid boiling at 160-161' under 24 mm.pressure, is produced by condensing methyl P-chloropropionate with sodioacetylacetone ; i t readily dissolves in dilute sodium carbonate solution and develops a red coloration with ferric chloride ; the silky, green, copper derivative is insoluble in water, alcohol, or ether, but readily dissolves in chloro- form; it melts at 220'. Ethyl yy-diacetylbutyrate boils a t 154-155" under 15 mm. pressure, develops a coloration with ferric chloride, and yields a silky, green, copper derivative dissolving in chloroform and melting a t 209'; when treated with alkali hydroxides, this ester gives rise to y-acetylbutyric acid. By the action of sodium ethoxide and methyl iodide, the ester loses an acetyl group and furnishes ethyl y-acetyl-ymethylbutyrate, CHMeAc*CH,*CH,-CO,Et, a pale yellow liquid boiling at 11 7-1 18' under 23 mm.pressure and having a sp. gr. 1.004 at O'/O'; the corre- sponding acid boils at 168-169' under 22 mm. pressure and has a sp. gr. 1 *114 at O'/Oo ; its semicarbazone, C,H,,O,N,, melts indefinitely at 152-158O. 1 -23eny2-3 : 5 -dimeth ylpyraxole-4-P-propionic acid, NPh<CMe:C*CH2*CH,*C0,H ' produced by condensing ethyl yy-diacetylbutyrate with phenylhydr- azine and hydrolysing the oily product with potassium hydroxide, crys- tallises from dilute alcohol, &c., in colourless :needles and melts at 134-1 35'. The dioxime, (NOH:CMe),*UH*CH,*CH,*CO,Et, and N'CMe*C* CH,*CH,*CO,Et' eth y I 3 : 5 -dime thy loxaxo Ze-4-P-propionat e, are produced by the action of hydroxylamine on ethyl diacetylbutyrate ; the former crystallises in colourless prisms melting at 108-110', the latter is an oil boiling at 157-15s' under 23 mm.pressure and yielding on hydrolysis the corresponding acid melting a t 109-1 10'. The ester, when condensed with semicarbazide, gives riae t o the N=$lMe O--EMe I I 114-1 15'. Ethyl bromoisobut,yrate, unlike its lower homologues, does not react with sodioacetylacetone. Acetonykccety Zacetone, CH Ac,*CH,* Ac, produced by condensing chloro- acetone and sodioacetylacetone, boils at 156' under 35 mm. pressure ; its copper derivative crystallises from chloroform in needles melting at 267-268O and is somewhat volatile. G. T. M.708 ABSTRACTS OF CHEMICAL PAPERS. Coloured Organic Ferric Compounds. By ARTHUR HANTZSCH and CECIL H. DESCH (AnnaEen, 1902, 323, 1 -31).-Determinations of the electrical conductivity of aqueous solutions of ferric acetyl- acetone indicate that the substance is practically a non-electrolyte, the values obtained being E~~~ = 0.72, and qo2? = 1-68.The compound is very slowly decomposed by hydrochloric acid, even when this reagent is in excess, and the change has been studied quantitatively by deter- mining the electrical conductivities of solutions of the substance with one, two, or three molecular proportions of the acid. The decomposition of the salt by hydrogen chloride in anhydrous solvents is instantaneous and complete, but when the reagent is gradu- ally added the change is seen to occur in three stages, the light red solution becoming deep red, then reddish-violet, and finally assuming the pale yellow colour of ferric chloride.The colour changes correspond with the gradual transformation of Fe(C,H?O,), into Fe(C,H70,),C1 and Fe(C,H70,)C11,. Aluminium acetylacetone is as poor a conductor of electricity as its ferric analogue, and is even less readily attacked by hydrochloric acid. Ethyl ferrihenzo ylacetate, Fe( C,,H,,Cl,),, obtained as an oily residue by extracting with ether a concentrated solution of ferric chloride, sodium acetate, and ethyl benzoylacetate in dilute alcohol, slowly becomes solid and separates from its alcoholic solution in deep red crystals melting a t 12s'. Ethyl ferrioxaloacetate, Fe(C,H,,O,),, prepared in a similar manner, separates as a lustrous, dark red, hygroscopic powder on diluting its alcoholic solution with water.Although ferric chloride and ethyl acetoacetate develop an intense coloration, the amount of ethyl ferriacetoacetate actually produced in aqueous solutions is but very small ; the reaction takes place, however, t o a greater extent when the reagents are dissolved in alcohol. Ferrisalicylic acid, OH*Fe( O*C,H,*CO,H),, produced by shaking an ethereal solution of salicylic acid with a concentrated aqueous solution of ferric chloride and sodium acetate, crystallises from the ethereal extract in red prisms which contain 1 mol. of ether. The compound, when freed from ether, has a purple colour and dissolves in water to a reddish-violet solution ; it behaves as an acid salt, dissolving in solu- tions of the alkali hydroxides without decomposition.o-Methoxybenzoic acid does not react with ferric chloride ; methyl salicylate and salicylaldehyde develop colorations with ferric chloride, but the products could not be isolated. Electrolytic determinations show that the amount of coloured salt formed from phenol and ferric chloride is very small ; this is also true of resorcinol, but its isomerides show more tendency to enter into reaction, the amount of double decom- position being greatest in the case of catechol. Pyrogallol and p-aminophenol, when treated with ferric acetate, yield violet-black substances which are insoluble in water or the organic solvents, but dissolve in hydrochloric acid to a yellow solution. Ethyl dicarboxyglutaconate and excess of ferric chloride in dilute alcoholic solution develop a blue coloration, but the actual amount of double decomposition is very small.Ferric cccetylhydroxamate, Fe(C,H,0,N)3, separates in deep red prismsORGANIC CHEMISTRY. 709 from an alcoholic solution of acetylhydroxamic acid and ferric ethox- ide ; it readily dissolves in water t o a bluish-red solution ; its equivalent conductivities at 25’ are P ~ ~ ~ . ~ = ‘7.5, and E ~ ~ ~ . ~ = 8.4 respectively. The salt is accordingly a ‘‘ half-electrolyte ” ; i t s degree of ionisation, although far less than that of a normal salt, is greatly in excess of that of ferric acetylacetone. The aqueous solution of the salt givesno precipitate with potassium ferrocyanide, but ferric hydroxide is slowly deposited on adding strong ammonia solution ; hydrochloric acid develops an intense violet coloration, which disappears on adding excess of the reagent.- o*?:NoH produced O-CNOH ’ Ferric oxalodihyhoxarnate, OH*Fe< the interaction of oxalodihydroxamic acid and ferric acetate, separates as a deep violet precipitate, dissolving in excess of ferric chloride solution t o a violet solution. The ferric salt is insoluble in water, alcohol, or ether, explodes on heating, and dissolves in solutions of the alkali hydroxides without decomposition. Ferric salicylh ydroxamccte, C 6 H 4 < c E > F e OH, resembles the preceding salt and dissolves without decomposition in solutions of the alkali hydroxides. Lanthanum acetylacetone, La(C5K70J3, is prepared by dissolving freshly precipitated lanthanum oxide in a dilute alcoholic solution of acetylacetone ; the reaction is accompanied by development of heat, and the salt crystallises, on cooling, in white needles.In solution, the sparingly soluble lanthanum salt is more highly ionised than its ferric and aluminium analogues; it is more rapidly attacked by hydrochloric acid than these substances. Acetylacetone and cntechol show a slight tendency to interact with boric acid. Solutions of colloidal ferric hydroxychloride, which have a marked acid reaction and a noteworthy electrical conductivity, contain their chlorine in a non-ionised condition, so that it is not precipitated as silver chloride until after acidifying. It must therefore be supposed that this chlorine exists in these solutions in the form of a complex chloroferric acid. Chlorine exists in a similar condition in the coagula obtained by carefully adding ammonia to aqueous solutions of alumin- ium chloride until the turbidity produced remains undissolved.G. T. M. &(1 :5)-Diketones. By PAUL RABE and FRITZ ELZE (Anncclen, 1902, 323, 83--112).-The 6- or 1 : 5-diketones containing a methyl group attached to one of their carbonyl radicles readily undergo rearrangement into cyclohexanolones. For example, diethyl benzylidene- bisacetoacetate, a condensation product from benzaldehyde and ethyl acetoacetate, gives the reactions of diethyl 3-methyl-5-phenyl- cyclohexan-3-01-1-one-4 : 6-dicarboxylate, the transformation being due t o an intramolecular aldol condensation, CHPh(CHAc*C02Et), - CHPh<~~[~$~))”(oH)>CH co 2’ In some cases, this change is complete, in others, the two isomerides710 ABSTBACTS OF CHEMICAL PAPERS, exist together in a condition of equilibrium.Evidence of the inverse transformation is furcished by Knoevenagel’s researches (Abstr., 1899, i, 214). The formation of the cyclic isomeride is brought about by the action of piperidine, sodium ethoxide, or other compounds of a similar nature. The 8-diketones, which have undergone complete rearrangement, are tabulated and their appropriate designations as cyclic compounds are indicated. The nature of the change involved in this rearrangement is indicated by the following diagram, C H , - C O * ~ ~ ~ ~ C O ~ ~ ~ . . . . .+ ~ H ~ ~ c o ~ ~ ~ ~ ~ . . . Diet hyl met h ylenebisace t oacet ate, when treated with hydrazine hydrate in alcoholic solution, yields 41nethylenebia-3-methyl-5-pyrazolonne, CH,( CHcb%:>N) , a substance separating in rhombic crystals and decomposing at 3 2 6 O .When left in contact with pyridine, the diketone slowly becomes transformed into diethyl 3-methylcyclohexan- 3-01-1-one-4 : 6-dicarboxylate, and the rate at which this change pro- ceeds is indicated by treating separate portions of the product at successive intervals of time with hydrazine hydrate. The yield of bispyrazolone steadily diminishes. Diethyl ethylidenebisacetoacetate is obtained as a viscid oil by mixing together ethyl acetoacetate, acetaldehyde, and a small amount of piperidine a t - 1 5 O to + 5 O ; the aliphatic nature of the product is demonstrated by theif ormation of 4-ethylidenebis-3-methyl-5-pyrazolone, which crystallises in prismatic needles and decomposes at 250’ (com- pare Rosengarten, Abstr., 1894, i, 547).The transformation product, diethyl 3 ; 5-dimethylcyclohexan-3-ol-1-one4 : 6-dica~boxyZate, melting a t 79-80”, and described by Knoevenagel as the unaltered diethyl ethylidenebisacetoacetate (Abstr., 1895, i, 50), when treated with 2 by Jrazine hydrate, yields a monopyrazolone .deri;ative, N= C--CH2*QMe*OH NH<co*bH*CHMe*CR*Co~Et’ which crystallises in needles, decomposes at 2 5 6 O , and dissolves either in acid or alkaline solutions. The cyclic ketone reacts in its enolic form when treated in ethereal solution with sodium, benzoyl chloride, and pyridine, giving rise to the OBx*f*CH,-?Me*OBz a pale yellow oil boil- CO,Et*C*CHMe *CH*CO,Et’ dibenxoyl derivative, ing at 175-185° under the atmospheric pressure and partly solidifying at the ordinary temperature.C,,H,,O,*O*CO*NHPh, of the cyclic ketone, produced by allowing its generators t o interact for 5 months a t the ordinary temperature, is a crystalline substance melt- ing a t 210’. The three isomeric PI-, &, and &-esters, obtained by condensing ethyl acetoacetate with benzaldehyde in the presence of pyridine, are now regarded as stereoisomeric diethyl 3-methyl-5-phenylcyclohexan- 3-01-1-one-4 : 6-dicarboxylates. The phenylhydrazone of the &-modifi- cation crystallises from alcohol in needles decomposing at 168-171O. The &- and &-esters both yield the same pyrazolone, C17H,,0,N,, melt- The phenylcadamide,ORBANIC CHEMISTRY. 711 ing a t 257O, which is identical with that obtained from the isomeric al-ester (compare Rabe, Abstr., 1901, i, 34).The &-ester gives rise to an isomeric pgrazolm crystallising in white needles and melting at 140". Diethyl 3-methyl-5-m-nitrophenylcyclohexan-3-01-1-one-4 : 6-dicarb- oxylate, described by Knoevenagel and Schurenberg as diethyl m-nitro- benzylidenebisacetoacetate (Abstr., 1899, i, 214), when heated with an alcoholic solution of hydrazine hydrate, yields apyrazolone, C17HI9O6N3, crystallising in prisms melting a t 260O; this forms an insoluble sul- phate and a sodium derivative. p-Nitrobenzaldehyde and ethyl acetoacetate give rise to two stereo- isomeric cyclohexanone derivatives ; the &-ester, first isolated by Knoevenagel (loc. cit.), melts a t 164O and yields a pyraxolone separating from alcohol in rhombic crystals and melting at 280'; the fl,-ester, melting at 152O, furnishes a pyraxolone crystallising in lustrous leaflets decomposing a t 260'.The ethereal alkylidenebisbenzoylacetates, unlike the corresponding condensation products from ethyl acetoacetate, are not affected by piperidine. Diethyl methylenebisbenzoylaetate (m. p. 86O), when treated with hydrazine . hydrate, furnishes a theoretical yield of 4-methylernebis-3~henyl-5-pyrazolm, which crystallises from alcohol in leaflets, decomposes a t 280°, and dissolves in dilute acid or solutions of the alkali hydroxides. 4-BenxyZidenebis-3-phnyl-B-pyraxolone, C,,H2002N4, is a very solubIe pyrazolone obtained by condensing diethyl benzylidenebisbenzoyl- acetate with hydrazine hydrate ; 4-benxytidenebis- 1-p-bromophyl- 3-phmyG5-pyrazolone, C37H260,N4Br2, is produced from the same &diketone by the action of p-bromophenylhydrazine ; it melts and decomposes at 2 9 0 O .The authors have obtained methylenebisacetylacetone only in the form of a viscid oil from which, after some months, a small quantity of a crystalline substance separates melting at 1 8 1 O (compare Scholtz, Abstr., 1898, i, 43, and Knoevenagel, i6id.) i, 449). 4-Methglenebis-3 : 5-dimethyZpyraxole, CH, ( C< zEz:$H); prepared by the action of hydrazine hydrate on the preceding &diketone, crys- tallises in rhombohedra and melts at 280O; it readily dissolves in alcohol, but is only sparingly soluble in water, The 8-diketone under- goes transformation under the influence of piperidine, but neither the cyclohexanone nor its pyrazole could be obtained in a state of purity.4 : 6-Diacetyl-5~~nyl-3-metiLylcyclohe~n-3-0l-1 -ma, ,,,,<cHAc*cMe( OH)> CHAc- 00 CH2, obtained by Knoevenagel, and also by Schiff (Abstr., 1895, i, 50, and 1900, i, 39), by condensing acetylacetone with benzaldehyde, is shown to be a cyclic compound by yielding a pyraxole, C17H2802N2, with hydrazine hydrate ; thia compound crystallised in prisms and decom- posed at 220'; the product of this reaction is a t first contaminated with an azine, which is destroyed by boiling with dilute hydrochloric acid, G, T. M.712 ABSTRACTS OF CHEMICAL PAPERS. [a-Glucoheptose.] By JULIUS WOHLGEMUTH (Zed. physiol. Chem., 1902, 35, 568-579).-The following compounds of a-glucoheptoae are described : the phen ylmethylhydraxone forms white crystals melting at 150' and the diphenylhydraxone white crystals melting a t 140' ; the osazone in pyridine alcohol mixture has the rotation +Oo30'.a-Glucoheptose does not give the resorcinol reaction, but with orcinol and phloroglucinol its reactions are very like those of the pentoses ; these two reactions are believed to be characteristic of sugars with an uneven number of carbon atoms. W. D, H, The Influence of Pressure on the Inversion of Cane Sugar by Sucrase. By VICTOR HENRI (Compt. rend. Soc. Biol., 1902, 54, 352-35 3).-Increase of pressure up to 400-800 atmospheres very slightly accelerates the inversion of cane sugar by sucrase. According to Rontgen, increase of pressure has the opposite effect on inversion by acids.W. D. H. Influence of the Concentration of Cane Sugar on the Rapidity of Inversion by Sucrase. By VICTOR HENBI (Compt. rend. Xoc. Biol., 1902, 54, 610-61 I).-No proportionality was observed between the concentration of solution of cane sugar and the rapidity of its inversion by sucrase, as described by Brown (Trans., 1902, 81, 373). W. D. a. Action of Sodium Chloride on Inversion by Sucrase. By VICTOR HENRI (Compt. rend. Xoc. Biol., 1902, 54, 611-612).-Sodium chloride is taken as an example of a neutral salt ; a constant quantity of salt inhibits inversion to a greater extent when a strong solution of cane sugar is employed than when a weak one is used. Its inhibiting action is greater when the amount of sucrase present is small.W. D. H. Action of Neutral Salts on the Inversion of Cane Sugar by Sucrase. By VICTOR HENRI (Compt. rend. Xoc. Biol., 1902, 54, 353-354).--The results show that various neutral salts exercise an inhibiting power on the rate of inversion of cane sugar by sucrase, and that t,here is a parallelism between this action and their capacity of precipitating colloids. W. D. H. Velocity of Hydrolysis of Acetylated Monoses and Bioses. By ROBERT KREYANN (Mor~atsh., 1902, 23, 479-488. Compare this vol., i, 134).-The rate of hydrolysis, k, is determined for the penta- acetyldextrose and -galactose, tetra-acetylgalactose, tetra-acetylchloro- dextrose, and -cblorogalactose, and octo-acetyl-lactose, -maltose, and -sucrose with sodium hydroxide in 96 per cent.alcohol. The value of k for tetra-acetylgalactose remains almost constant throughout the hydrolysis, but for the other acetyl compounds k diminishes gradually, in some cases to half of its original value. This is due to a difference in the rate of hydrolysis of the different acetyl groups, the most reactive acetyl group of penta-acetylgalactose being absent in the tetra-acetyl derivative, As the value of k is smaller for the acetyl-ORGANIC CHEMISTRY. 713 dextroses than for the acetylgalactoses, the acetyl groups in the former are less reactive, this observation is made use of to explain the forma- tion of tetra-acetylnitrodextrose, and the non-formation of tetra-acetyl- nitrogalactose, from the corresponding chloro-compounds. The value of r% for octo-acetyl-lactose, which contains a dextrose and a galactose grouping, is greater than that for octo-acetylmaltose, which contains two dextrose groupings. The rate of hydrolysis of octo-acetylsucrose lies between that of octo-acetyl-lactose and that of octo-acetylmaltose, approximating more nearly to the former.Tetra-acetylchlorogalactose is obtained in large, rhombic crystals. Attempts to prepare tetra-acetyl- dextrose by the action of silver carbonate and metallic sodium on tetra- ncetylchlorodextross resulted apparently in the complete decomposition of the acetyl derivative, G. Y. Preparation and Properties of Crystallised Gentiobione. By EMILE BOURQUELOT and HENRI H~RISSEY (Compt. rend., 1902, 135, 290-292. Compare Abstr., 1901, i, 25S).-Gentiobiose has now been obtained in a crystalline form by extracting the crude mixture of sugars produced by the pnrtial hydrolysis of gentianose first with ethyl alcohol to remove laevulose and then with methyl alcohol to dissolve out the uew hexobiose. The product crystallising from the latter solvent is white, hygroscopic, and has a bitter taste; it consists of gentiobiose combined with 2 mols.of methyl alcohol and has the formula C?,H2C,,0,,,2MeOH. These crystals melt a t 85-5-86' (corr.), become solid on further heating, and fuse again a t *189--195Oto a yellow liquid ; the alcohol of crystallisation is removed only by heating at 100-1 15'. When in solution, the substance exhibits the phenomenon of multirotation, the optical activity of the dextrorotatory solution diminishing to a minimum after 19 hours, the specific rotation at this stage being + 8 * 3 3 O . Gentiobiose separates from ethyl alcohol in crystals having the composition C12H22011. I n this form it also exhibits multirotation, but the optical activity of its solution increases until a maximum is reached after 6 hours, giving [aID 9*61*.This value of the specific rotation corresponds with that obtained for the crystals separating from methyl alcohol, providing that allow- ance is made for the solvent contained in this preparation. G. T. M. Action of Enzymes on Hemicelluloses. By J. GRUSS (Chem. Cennty., 1902, i, 1277 ; from WQch. Brauerei, 19, 243-245).-Galac- tose is formed by the action of diastase powder prepared by Lintner's method on tragacanth, and under similar conditions mannan, the herni- cellulose obtained from the endosperm of date seeds, yields man- nose.By the action of the enzyme contained in the date itself, mannan is converted into mannose about twice as quickly as by a 6 per cent. solution of Lintner's diastase. Hence the hemicelluloses contained in barley are attacked by diastase, and by its prolonged action the same sugars are formed as those obtained by the action of acids.'714 ABSTRACTS OF CHEMICAL PAPERS. The original paper also contains a description of experiments in which similar results were obtained by using two diastases prepared from barley malt and oat malt by Heinzelmann's methods. E. w. w. Organic Vapour in the Air. By H. HENRIET (Compt. rend., 1902, 135, 101--103).-Air contains an organic vapour which seems to be a substituted formamide, NHRoCHO.It is slowly converted into carbon dioxide by the action of the oxygen of the air, and if the air is moist and the moisture is condensed, the resulting water reduces silver nitrate solution on boiling, converts mercuric chloride into mercurous chloride, and reduces gold chloride and alkaline potassium permangaatite. With Nessler's reagent, it gives a yellowish-green opalescence, especially if the liquid is previously heated with a small quantity of potassium hydroxide or of hydrochloric acid. The reducing power disappears if the condensed moisture is evaporated with sulphuric acid ; if it is evaporated with hydrochloric acid, the residue gives the isonitrile reaction for primary amines. Dialkylamides of isovaleric and a-Bromoisovaleric Acids.ARTHUR LIEBRECHT (D.R.-P. 129967).-isoV~ZerodimethyZamide, prepared by the action of isovaleryl chloride on dimet hylamine dissolved i n ether, boils a t 188-192O under the ordinary pressure; the corre- sponding diethylamide and the diisoccmylccinide boil a t 2 10-2 12" and 270-275O respectively under the ordinary pressure ; the latter deriv- ative is produced by heating diisoamylamine with isovaleric anhydride, isovaleroamide, or ethyl isovalerate under pressure. a-BromoisovalerodiethyZanaide results from the interaction of diethylamine and a-bromoisovaleryl bromide in ethereal solution ; it boils a t 130-135' under 20 mm. pressure. Hydroxyisopropylphosphinic Acid. By CH. MARIE (Compt. rend., 1902, 135, 106--108).-The methyl ester of hydroxyisopropyl- phosphinic acid (this vol., i, 431) melting a t 76" and t h e ethyl ester which is liquid a t the ordinary temperature are readily prepared by the action of the corresponding iodides on the silver salt.They decompose when distilled, yielding acetone and products which are still under investigation. When the esters are treated with an alkali hydroxide, decomposition takes place in two well marked stages, the first change being practically instantaneous, whilst the other necessitates the addition of a large excess of alkali and the prolonged boiling of the liquid. When treated with benzoyl chloride in presence of excess of pyridine, the acid yields 6enxoyZisopropylphosphinic acid, OBz*C,H6*P0,H,, a crystallisable compound which melts at 102' and forms a white, crystallisable silver salt, OBz*C,H6*P0,Ag,.The above facts show that the constitution of the acid is OH*UMe,*PO(OH)2. Separation of Cyclic Aromatic Oxides or Sulphides from Coal Tar Hydrocarbons. AKTIEN-GESELLBCHAFT FUR THEER- & ERDOL- INDUSTRIE (D .R.-P. 1306 79) .-Mixtures of hydrocarbons containing C. H. B. G. T. M. C. H. B.ORGANIC CHEMISTRY. 716 cyclic oxides or sulphides are fused with potassium hydroxide, the fused product being subsequently lixiviated with water. Under these conditions, the oxides become converted into the soluble potassium derivatives of the diphenols, O(C,H,), + 2EOH = C12HB(OK), + H,O, and are thus separated from the insoluble hydrocarbons. Derivatives of 1 : 3-Dichloro-4 : 6-dinitrobenzene.By JAN JOHANNES BLANHSMA and P. C. E. MEERUM TERWOGT (Rec. trav. chim., 1902, 21, 286-291).-The authors have studied the nitration products of m-dichlorobenzene, By the action of sodium ethoxide on 1 : 3-di- chloro.4 : 6-dinitrobenzene, 1 : 3-diethoxy-4 : 6-dinitrobenzene (diethyl- 4 : 6-dinitroresorcinol) is obtained melting a t 133'. 1 : 3-Dimethoxy- 4 : 6-dinitrobenzene is formed in a similar manner ; it melts at 1 5 7 O , even after repeated cry stallisation from methyl alcohol, the melting point given by Loring Jackson and Warren (Abstr., 1891, 1024) being 167'. On heating this compound with alcoholic ammonia, the corresponding 4 : 6-dinitro-m-phenylenediamine is obtained, and on heating i t with hydrochloric acid in a sealed tube, 4 : 6-dinitroresorcinol is formed, When 1 : 3-dichloro-4 : 6-dinitrobenzene is heated with methyl- amine in alcoholic solution, the chlorine atoms are replaced and there is produced 4 : 6-dinitro-1 : 3-dimethyl-m-phenyZenediamine, which forms small, yellow crystals, sparingly soluble in alcohol or acetic acid, and does not melt even at 280'.On dissolving the latter in nitric acid and heating the solution for a short time, 2 : 4 : 6-trinitro-m-phenylene- 1 : 3-dimethyldinitroamine, C,H(NMe*NO,),(NO,),, is formed. U.. T. M. A. F. Preparation of Aromatic Sulphinic Acids. BASLER CHEMISCHE FABRIK (D.R.-P. 130119).-The aromatic sulphinic acid is obtained by adding t o the cold diazo-solution a 40 per cent. solution of sodium hydrogen sulphite and excess of alcoholic sulphurous acid containing a small quantity of cupric sulphate or other compound of copper.The reaction occurs at 0-20' in the case of aniline, o-toluidine, or methyl anthranilate, but more stable diazo-salts require a higher temperature. The solution obtained from o-anisidine must be warmed to 30°. G. T. M. Nitrodihydrophenanthrene. JULIUS SCHMIDT (D,R.-P. 129-990. Compare Abstr., 1901, i, 76).-Finely divided phenanthrene, when mixed with the liquefied crude product of the action of nitric acid on rjtarch or arsenious oxide, takes up the elements of nitrous acid and yields nitrodihydrophenanthrene, C,,H,,O,N ; this substance is a yellow, crystalline powder, softening a t 70" and decomposing at 100' ; i t readily dissolves in the ordinary organic solvents. C. F. BOEHRINGER & SOHNE (D.R.-P. 130742).-Nitrobenzene, when gradually added to copper powder suspended in concentrated sodium chloride solution contained in the cathode compartment of an electro- lytic cell, is quantitatively reduced to aniline at 80-looo by a cur- rent of 1500 amperes per square metre and 5 volts, A copper cathode is employed, whilst the anode compartment contains a carbon anode surrounded by concentrated sodium chloride solution, G.T. M. Reduction of Aromatic Nitro-compounds to Amines.716 ABSTRACTS OF CHEMICAL PAPERS. Under similar conditions, o-nitrotoluene and a-nitronaphthalene readily yield o-toluidine and a-naphthylamine, whilst m-nitroaniline is reduced to m-phenylenediamine, the yield being 80 per cent. G. T. M. Action of Formaldehyde [on Ethylaniline]. By CARL GOLD- SCHMIDT (Chem.Zeit., 1902, 26, 606. Compare Abstr., 1900, i, 436). -A mixture of monoethylaniline, formaldehyde, and hydrochloric acid forms, after some days, the compound NEtPh*CH,CI. This melts at 250' and is soluble in hot water ; alkali hydroxides added to its dilute aqueous solution separate a base which is soluble in chloroform and may be obtained pure by precipitating the solution with ether. Similar compounds may be obtained in this manner from the esters of the three aminobenzoic acids, and mention is made of the produc- tion of compounds by the action of formaldehyde on benzoylthymo1,- phenylhydrazine, and acetylphenylhydsazine. By treating resacetophenone for 2 hours with formaldehyde and hydrochloric acid and boiling the product with xylene, a n insoluble compound is obtained which, however, dissolves in chloroform and is precipitated from the solution by addition of ether.The xylene .con- tains a second product which separates as a white, crystalline sub- stance melting at 245-250' and is soluble in the alkali hydroxides. L. D E K . Iodo-derivatives of Aromatic Aminosulphonic Acids. KALLE & Co. (D.R.-P. 129808).-The aromatic amines, when treated with iodine monochloride, give rise to tarry products ; their monosul- phonic acids, on the other hand, furnish well-defined iado-derivatives when treated with hydrochloric acid solutions of this reagent. lodosulphanilic acid crystallises from its concentrated aqueous solu- tions in small, white needles, Di-iodosulphanilic acid, resulting from the action of excess of iodine monochloride on sulphanilic acid, separates from dilute aqueous solutions on the addition of sodium chloride.Di-iodometanilic acid crystallises from water in colourless leaflets. The diazo-compounds of these iodoaminosulphonic acids are yellow. G. T. M. Trisubstituted Naphthalene Derivatives. By ARTURO JACCHIA (Anncclen, 1902, 323, 11 3--134).-6-Nitro-/3-naphthylamine-8-sul- phonic acid is most conveniently obtained by nitrating /3-naphthyl- amine- 8-sulphonic acid dissolved in concentrated sulphuric acid with potassium nitrate. The 2 : 6-diaminonaphthalene-8-sulphonic acid produced by reducing the nitro-compound yields 2 : 6-diamino- naphthalene on treatment with sodium amalgam and was formerly supposed to be identical with the compound prepared by heating 2 : 6-dihydroxynaphthalenesulphonic acid with ammonia under pres- sure (D.R.-P.72222). An examination of the latter diamino-acid showed t h a t the commercial product consists of a mixture of free sul- phonic acids and their sodium salts, the principal constituent of which is a diaminonaphthalenedisulphonic acid. This substance, which is insoluble in alcohol, crystallises from water in leaflets having a silveryORGANIC CHEMISTRY. 717 lustre and the composition C,,H,(NH,),(S0,H),,4~H20 ; when the aqueous solution is treated with sodium amalgam, 2 : 6-diamino- naphthalene is produced. The ammonium salt of 6-nitro-~-naphthylamine-S-sulphonic acid crystallises in dark red, anhydrous prisms ; the barium salt separates in red crystals with 4$H,O.The adhydyide of 6-nitro-2-diazonaphthcc~ene-8-su~phonic acid, obtained by diazotising the preceding ammonium salt, is very sparingly soluble in cold water; i t combines with aniline, yieldipg a red colouring matter, and when boiled with water gives rise t o 6-nitvo-P-naphthol-8- sdphonic acid, N0,*Cl,H,(OH)*S0,H,4B,0, which crystallises from water in light yellow prisms and retains 2H20 even at 150"; the potci,ssium salt, NO,*Cl,H (OH)*SO,K, separates in anhydrous, orange prisms ; the bavium salt, ~N02*C,,H,(OH)~S0,],Ba,69H,0, crystallises in dark yellow prisms ; the sodium salt is less definite and crystallises either with 5 or 6H20. 6-Amino-fl-naphthol-8-sulplionic acid,NH,*C,,H,( OH)*SO,H,H,O, pro- duced by reducing the nitro-compound with stannous chloride, crys- tallises from water in lustrous, grey needles ; it is somewhat unstable, and when boiled with an emulsion of barium carbonate yields the barium salt of a dark blue colouring matter, the composition of which approximates to that required by the formula (C,,H,,O,,N,S,)Ba, or 6-Amanno-P-naphthol results from the action of sodium amalgam on the preceding sulphonic acid dissolved in an aqueous solution of sul- phur dioxide; it crystallises from water in grey flakes which decom- pose a t 190-195' and rapidly assume a blue colour on exposure to the air.(c40H28016N4s*) 2-ChZoro-6-nitronaphthccZene-S-sulphonic m i d , NO,*C,,H,Cl*SO,H, 6H,O, obbained from 6-nitro-2-diazonaphthalene-8-sulphonic acid by the Sand- meyer reaction, crystallises from water in bright yellow, silky prisms; the bavium salt crystallises in deep yellow needles with 7H,O; the silver salt separates in anhydrous, yellowish-brown needles.6- Chloro-fl-nuphthy lamine-8-suZphonic acid, NH, CloK,C1*SO,H, pro- duced by reducing the preceding nitro-compound, is precipitated from the aqueous solution of its sodium salt by excess of hydrochloric acid and crgstnllises in brown, silky prisms with a violet reflex ; the barium salt forms very soluble, light brown leaflets. G. T. M. m-Chloro- and m-Bromo-trinitrophenols. By S. TIJMSTRA (Rec. truw. chim., 1902, 21, 292-293).- On nitrating m-chlorophenol with a mixture of nitric and sulphuric acids, 3-chloro-2 : 4 : 6-trinitro- phenol is obtained in yellow crystals melting a t 119". I n the same manner, m-bromophenol gives 3-bromo-2 : 4 : 6-trinitrophenol, which melts a t 144".On treating these compounds with sodium methoxide, the halogen is replaced by the methoxy-group. A. F. Ionic Phenomena Exhibited by Triphenylmethane Colouring Matters. By OTTO FISCHER (Chem. Centr., 1902, ii, 91 ; from Zeit. Furben-Textil-Chem., 1902, j, 281).-If an excess of concentrated hydro- VOL. LXXXII. i. 3 e71s ABSTRACTS OF CHEMICAL PAPERS. chloric acid is added t o a solution containing a trace of rosaniline, methyl-.violet, or malachite-green dissolved in dilute hydrochloric acid, until the liquid becomes yellow, a point may be reached a t which the solution no longer shows the slightest coloration when poured into water, but, on the other hand, when added to alcohol, the red, violet, or green ions of the respective dyes are a t once apparent. The same phenomena are shown by solutions of the colouring matters in concentrated sulphuric acid (compare also Kehrmann and Wentzel, this vol., i, 89).E. W. W. '7-Amino-P-naphtholsulphonic Acid. LEOPOLD CASSELLA dz Co. (D.R.-P. 131 526).-7-Arnino-P-naphthol readily yields a disulphonic acid, even on treatment with 90 per cent. sulphuric acid ; this product readily parts with one of the sulphonic groups on hydrolysis with dilute acids and yields ~ - a r n i n o - p - ~ a ~ ~ t h o l s u ~ ~ o n i c acid. The sodium salt, OH* C,,H,(NH,)*SO,Na,H,O, separates in sparingly soluble nodular aggregates ; the diazo-compound is yellow and sparingly soluble in water. G. T. M. Preparation of Anthranilic Acid from 4-Sulphoanthranilic Acid.KALLE & Co. (D.R.-P. 129165).-When treated in aqueous solution with sodium amalgam, 4-sulphoanthranilic acid, obtained by the action of sodium hydroxide solution on o-nitrotoluene-4-sulphonic acid, readily loses its sulphonic group and gives rise to anthranilic acid. G. T. M. Preparation of Anthranilic Acid. BABLER CHEMISCHE FABRIK (D.R.-P. l30301,130302).-Phthalylhydroxylamine (this vol., i, p. 720) or its alkali derivatives, when heated with sodium or potassium carbonate in aqueous or alcoholic solution, becomes converted into the correspond- ing alkali anthranilate. G. T. M. o-Cyanomethylanthranilic Esters. BADISCHE ANILIN- & SODA- .FABRIK (D.R. -P. 12 95 62).-wCyanomethylant hranilic acid, CO,H C,H,*NH* CH,*CN, readily yields.its ethyl ester when treated at 100' with ethyl bromide in the presence of sodium hydroxide solution or milk of lime; this derivative melts a t 89O, whilst the methyl ester, prepared by means of methyl sulphate or the methyl ester of an aromatic sulphonic acid, melts a t 108O. The methylation with methyl sulphate takes place a t 5 0'. G. T. M. Action of Sulphites on Aromatic o-Hydroxycarboxylic Acids. By HANS BUCRERER (Zed. Paden- T'extil-Chem., 1902, 1, 477-480. Compare Abstr., 1901, i, 695, and this vol., i, 91).- A1 though 2-hydroxy-3-naphthoic acid is converted into 2-amino-3- naphthoic acid by the action of ammonia solution at 260' (Mohlau, Abstr., 1894, i, 138), yet, when heated with a mixture of this reagent and ammonium sulphite a t 125O, it loses its carboxyl group and becomes converted into P-naphthylamine.The acid also loses its carboxyl group when heated with a solution containing both sodiumORGANIC CHEMISTRY. 719 hydrogen sulphite and sodium hydroxide; in this case, P-naphthol is produced. 1-Hydroxy-2-naphthoic acid and 2-hydroxy-1-naphthoic acid both very readily lose their carboxyl radicles under these conditions, yielding a naphthylamine in the presence of ammonia and a naphthol under the influence of an alkali hydroxide. Salicylic acid, on the other hand, is very stable towards hot solutions of the sulphites, and remains unaffected when treated in the manner indicated. G. T. M. Derivatives of the Nitrophthalic Acids. By HEINRICH SEIDEL and 5. C. BITTNER (Moructsh., 1902, 23, 415-436. Compare Miller, Annalen, 1881, 208, 394!.-3-Nitrop?~thc~limid~, formed when 3-nitrophthalic acid is heated at 220' in a stream of dry ammonia gas, crystallises in yellowish-white needles, melts at 2 16O, sublimes unchanged, and is easily soluble in alcohol, glacial acetic acid, acetone, or solutions of the alkali hydroxides ; it dissolves with difficulty in hot water but is insoluble in the cold solvent ; the imide is converted, by Hofmann's reaction, into 6-~zits*oanthraniZic acid, melting at 184O, a n isomeride of Hubner's 3-nitroanthranilic acid (Abstr., 1879, 380) ; it has a sweet taste, is easily soluble, and yields a deep orange-red, crystalline, sodium salt and a hydyochloride crystallising in long, almost colourless, needles.When heated with alcohol and hydrochloric acid, 6-nitroanthranilic acid yields a small amount of m-nitroaniline but no ester ; when heated with diluted sulphuric acid (1 : 1) at 120°, it is converted into m-nitroaniline, and when diazotised and boiled with dilute sulphuric acid it yields m-nitrophenol.Reduction by tin and hydrochloric acid lea& to the formation of 2 : 6-diaminobenxoic acid, the hydrochloride of which forms colourless, glistening needles ; these become greyish-violet on exposure to light and air, and are easily soluble in alcohol but not in ether. Reduction in presence of excess of hydrochloric acid and rapid evaporation of the liquid leads to the formation of m-phenylenediamine. 4-Nitrophthalimide, formed at 170" from 4-nitrophthalic acid, crystal- lises in yellow, glistening leaflets, melts at 202O, sublimes unchanged, has solubilities similar to those of the 6-isomeride, and yields the two possible isomeric nitroanthranilic acids.5 -Nitroanthranilic acid crystallises from dilute alcohol in lemon- yellow, silky needles, melts at 2SOo, and not at 263' as stated by Hubner (Zoc. cit.), is insoluble in xylene, yields an ethyl ester which melts a t 146" (Kaiser, Abstr., 1886, 149) and an acetyl derivative melting at 214-216' ; it is converbed by diazotisation into 5-nitro- salicylic acid melting a t 288" (Hubner, Abstr., 1882, 503 ; Rupe, Abstr., 1897, i, 416), and reduced by tin and hydrochloric acid to a colourless solution which gives the p-phenylenediamine reactions either with aniline hydrochloride and potassium dichromate or with ferric chloride.4-ATitroanthraniZic mid [NH, : CO,H : NO, = 2 : 1 : 41 separates from dilute alcohol as a yellow, crystalline powder having an intensely sweet taste; it is soluble in xylene and forms an orange-red, crystalline sodium salt, easily soluble in water, and a Lqdrochloride which crys- tallises in long, delicate, glistening leaflet,s and dissociates on drying. 3 e 2720 ABSTRACTS OF CHEMICAL PAPERS. The ethyl ester, formed by the action of alcohol and hydrogen chloride, separates from dilute alcohol in clusters of yellow needles melting at 91" and when crystallised from benzene melts at 89' ; it has a burning, sweet taste, is insoluble in aqueous sodium carbonate solution, and soluble in benzene. The ace@ derivative crystallises in long, slightly yellow needles and melts at 188'.Djazotisation of the 4-acid leads t o the formation of 4-nit~oscdic?/lic acid, which crystallises in broad, short, orange-yellow needles, melts a t 235O, has a bitter taste, is easily soluble in alcohol, chloroform, or benzene, but insoluble in light petroleum, snd gives a blood red coloration with ferric chloride. This nitro-compound is reduced by tin and hydrochloric acid to 4-amino- salicylic cccicl, which forms a reddish-brown, crystalline powder, melts at 220°, is easily soluble in water or alcohol, but more sparingly so in ether, forms a hydrochloride which is easily oxidised to a dark brown mass on exposure to air, gives a n intense dark violet coloration with ferric chloride, and on diazotisation and boiling yields a solution which gives the reactions of 2 : 4-dihydroxybenzoic acid.Reduction of 4-nitroanthranilic acid by tin and hydrochloric acid leads to the formation of 2 : 4-diaminobenxoic acid, which is easily decomposed into carbon dioxide and m-phenylenediamine. G. Y. Phthalylhydroxylamine. BASLER CHEMISCHE FABRIK (2). R.-p. 130680, 1306Sl).-Phthalylhydroxylamine is produced by the interaction of h ydroxy lamine hydrochloride and sodium car- bonate in aqueous solution on phthalic anhydride, the reagents being present i n molecular proportion. When excess of sodium car- bonate is added, the intermediate product, phthalhydi*oxylamic acid, OH*NH*CO-C~H,-CO,H, may be isolated, being precipitated from the alkaline solution by hydrochloric acid; this substance melts a t 204-206" and is readily soluble in alcohol or water ; its aqueous solu- tion, when warmed at 50°, yields phthalylhydroxylamine.Monoacyl Derivatives of Indoxyl and Indoxylic Acid. DANIEL TORLANDER & BRUNO DRSSCHER (I).R.-P. 131400).-In addition to the results already published (compare Abstr., 1901, i, 563), the follow- ing compounds are described for the first time. 3-P~opionylindoxyl, obtainel by treating the decomposition product of phenylglycinecarboxylic acid with propionic acid and propionic anhydride, is insoluble in solutions of the alkali hydroxides and melts at 87". An isomeride, 1-;13ropionyZindoxyZ, produced by treating indoxy1 with propionic anhydride suspended in water, melts a t 1880 and is soluble in alkalis. 1-BenxoylindoxyZ, prepared from indoxyl by the Schotten-Baumann reaction, crystallises from dilute acetic acid and melts at 1 0 1 O ; its nitroso-derivative crystallises in pale yellow needles and melts at 104'.3-Benxoylindoxy1, resulting from the action of benzoic anhydride on indoxy1 a t 40°, crystallises from alcohol, melts at 123", and is soluble in a solution of a n alkali hydroxide; its isomeride does not dissolve in this medium. sodium ucetylindoxylcbte, formed by the action of acetic anhydride on a slightly alkaline solution of sodium indoxylat e, crystallises in lustrous G. T. M.ORGANIC CHEMISTRY. 721 white leaflets containing water of crystallisation. The corresponding salts of calcium and the heavy metals are sparingly soluble in water ; the magnesium salt separates in glistening leaflets.By P. N. RAIKOW and J. RASCHTANOW (Chem. Cent?*., 1902, i, 1212-1213; from Oesterr. Chem. Zeit., 5, 169-173).-By the acbion of solid alkali hydr- oxide on benzaldehyde, p-tolylaldehyde, cuminaldehyde, and o-chloro- bsnzaldehyde, theoretical quantities of alcohols and acids are formed. The reaction with benzaldehyde takes place without the formation of any resinous bye-products (compare Meyer, Abstr., 1882, 195). When the chlorobenzaldehydes are similarly treated, the chlorine is divided equally between the two products. o-ChZoi*ohenzyZ alcohol crystallises in white, lustrous leaflets, melts at 69-5', and is only very slightly soluble in water, but readily so in alcohol or ether. p-Chlorobenz- aldehyde is only slowly attacked by alkali ; p-chlorobenzyl alcohol melts at 7 lo.Salicylaldehyde, 23-hydroxybenzaldehyde, and vanillin do not undergo Cannizzaro's reaction with the alkali hydroxides. Anisaldehyde forms anisic acid, which melts a t 178.5'. The presence of a hydroxyl group in the ortho- or para-position renders the aldehyde incapable of reacting with alkalis. o-Nitrobenzaldehyde yields an acid which de- composes completely a t 190-ZOOo, and contains 7.5 per cent. of nitrogen. p-Nitrobenzaldehyde and its m-isorneride do not form alcohols, but by saturating the products with hydrogen chloride, amorphous substances containing 6 and 8.1 per cent. of nitrogen re- spectively are obtained. Thus the nitrobenzaldehydes do not yield the normal products, but either form acids with loss of a portion of the nitrogen o r compounds in which hydroxyl groups are present in the benzene ring.E. W. W. a-Substituted Anthraquinone Derivatives containing Chlorine or Bromine. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 131538).-~-Diazoanthraquinone, when treated with hydro- chloric or hydrobromic acid, yields the corresponding halogen deriv- ative. I n this reaction, the presence of cuprous salts is not essential. G. T. M. Action of Solid Alkalis on Aromatic Aldehydes. G. T. M. Blue Colouring Matter of the Anthracene Series. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 129845, 129846, 129847, 129848). -2-Aminoanthraquinone, when melted with potassium hydroxide a t 200-300°, yields a leuco-compound which, by aerial oxidation, changes into a pigment closely resembling indigotill ; it is insoluble in solutions of the mineral acids or the alkali hydroxides, and crystallises from nitrobenzene in blue needles with a copper-bronze lustre.This substance, C,,H70,N, which may also be obtained from 2-aminohydroxyanthranol, yields a yellow product, and, on oxidation by alkaline reducing agents, is converted into the soluble leuco-derivative. 2-Aminoanthraquinonesulphonic acid, when submitted to fusion with potash a t 170-175°, yields the sulphonic acid of the pigment C,,H70,N, a soluble, blue colouring matter, which may also be obtained by sulphonating the insoluble compound with fuming sulphuric acid, either with or without boric acid.722 ABSTRACTS OF CHEMICAL PAPERS. The sodizcnz derivative of the leuco-compound can be isolated in the form of copper-coloured needles by reducing the insoluble colouring matter with a solution of sodium hyposulphite and sodium hydroxide; it dissolves in warm, alkaline solutions, but is readily dissociated by water, regenerating the pigment.Anthracene Colouring Matters containing Nitrogen. FAR- BENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 127439).-2-Bromo- 4-nitro-1-hydroxyanthraquinone is obtained by heating 4-nitro-1 - hydroxyanthraquinone-2-sulphonic acid with bromine a t 120' ; it crys- tallises from glacial acetic acid in lustrous, yellow needles, dissolving in concentrated sulphuric acid t o a light yellow solution which becomes reddish-yellow on the addition of boric acid. When heated with primary aromatic amines, it yields blue colouring matters. By the action of p-toluidine, for example, the nitro-group is replaced by the tolylamino-radicle and a substance is obtained identical with that pro- duced by condensing this amine with 2 : 4-dibromo-1-hydroxyanthra- quinone.When boric acid is added during the fusion, the colouring matters are green. HAARMANN & REIMER (D.R.-P. 129027). -$-Ionone, when treated with warm dilute mineral acids, always yields a-ionone mixed with varying quantities of its /?-isomeride. The latter compound is formed almost exclusively when the transformation is induced by 70 to 100 per cent. sulphuric acid in the cold, whereas a-ionone containing only traces of the isomeric compound is produced when the reaction is carried out with concentrated Dhosphoric acid G. T. M. 0. T. M. Preparation of Ionone. at 30' (compare Abstr., 1901, i, 157 j this vol., i, 342,h71j.G. T. M. New Syntheses in the Terpene Series. By OTTO WALLACH (Chein. Centr., 1902, i, 1293-1296 ; from Nachr, k. G'es. Wim. Gottingen, 1902, 92-107). [With NICOLAI SPERANSKI.] (Compare Abstr., 1901, 7H2* CH 2>C(OH)*CH,*C0,Et, CH,* CH2 i, 155).--Ethyl cyclopentanolacetate, produced by the influence of zinc on cyclopentanone and ethyl bromo- acetate, boils at 105-107' under 11 mm. pressure. By the elimination of water, it forms an unsaturated ester, CQH1,O,, which boils a t 82-84' under 11 mm. pressure. The corresponding mid, C7H,002, melts a t 49-50' and boils at 122' under 11 mm. pressure ; the dibrornide, C7H10Br202, melts at SS', and the amide, C,H,*CO*NH,, at 144'. The unsaturated ester, CloHl,O,, derived from ethyl /?-methyl- cyclopentanolacetate, boils at 90-92' under 11 mm.pressure ; its acid, C,H1,O,, boils at 128' under 10 mm. pressure or about 240' under the ordinary pressure with liberation of carbon dioxide. The nitrile, C7Hll*CN, boils at 208--210'. The amide, C,H,,*CO*NH,, melting a t 128', together with a hydrocarbon, C7H1,, is prepared by heating the ammonium salt of the Unsaturated acid at 230'. The hydrocarbon boils a t 96-97' and has a sp. gr. 0-7750 and rz, 1.4336 at 16'. Similarly, by means of the ethyl bromoacetate synthesis, from dihydrocnrvone a d carvenone on the one hand and menthone and tetrahydrocarvone on the other, unsaturated acids can be obtainedORGANIC CHEMISTRY, 723 which decompose with liberation of carbon dioxide and formation of homoterpenes, C11H18, and homomenthenes, Cl1H2,.[With FRITZ T H ~ L K E . ] - T ~ ~ teipsne, C,,H, 8, prepared from dihydro- carvone, boils at 191-192' and has a sp. gr. 0.8465 and TZ, 1.4771. The unsaturated ester, C,,H,,*CH,~C02Et, from which it is derived, boils at 145-148" under 18 mm. pressure. The terpene, CllHI8, obtained from carvenone, boils a t 194-197" and has a sp. gr. 0.8510 and nD 1.4821. The unsaturated ester, C,,HlS*CH2*C02Et, boils at 135-137" under 16 mm. pressure. Xe.nthene, C11H20, prepared from menthone, boils a t 196-197' and has a sp. gr. 0.13215 and r / ~ , 1.4579. The isomeric menthene, C,lH20, from tetrahydrocarvone, boils at 194-195" and has a sp. gr. 0.8300 and n, 1.4619. [With NICOLAI SPERANsKI.]-In order to distinguish between a- and P-adipic acids, the methylpentanones obtained by distilling the calcium salts are condeased with benzaldehyde.a-MeLhylpentanone yields a monobemy Zidene derivative, C,H,O:C:CHPh, which cry stallises in colourless needles and melts at 123-1 24", whilst P-methylpentanone forms dibenzylidene-P-methylpentanone melting a t 149-15 1'. By means of this condensation, the acid obtained by oxidation of pulegone and methylhexanone has been proved to be P-methyladipic acid (com- pare Markownikoff, Abstr., 1900, i, 475). When P-methyladipic acid is distilled in a vacuum, it is partially converted into the anhydride; only a portion of the distillate is sol6ble in dry benzene and melts at 84O, whilst the insoluble residue melts at 91". [With 0. RAHN.]-when the terpineol (m.p. 32') discovered by Helle and Stephan in liquid terpineol (compare Schimmel & Co., Abstr., 1901, i, 394) is treated with bromine and a solution of hydrogen bromide in glacial acetic acid, a terpineol tribromide, OMeBr<CH2*CH2 CH2*aH2>CH*CMeBr*CH2Br, is formed which melts a t 65'. By the oxidation of this compound with potassium permanganate, a trihydroxy-derivative, C,,H2,0,, is obtained. This compound crystal- lises from ethyl acetate, melts a t 116-117°, and when boiled with dilute sulphuric acid loses water and forms the compound C,,H,,O, which boils at 217-225' under atmospheric pressure, has a sp. gr. 0,977, n, 1.4930 at 20°, and is analogous to the isomeric compound prepared from the oxidation product, C10H2003, of dihydrocarveol. By warming the oxyketone, C,H,,O,, prepared by Helle and Stephan (loc. cit,), with dilute sulphuric acid or by oxidising the trihydroxy- terpineol with chromic acid, tctralqdro-p-tolyl methyl ketone, CMe<:~~:~>CH*COMle, is formed; i t boils a t 205-206', has a sp.gr. 0,940, and m,, 1.4719 at 19", and when heated with sulphuric acid (4 vols.) yields p-tolyl methyl ketone. The semicadhone of tetra- hydro-p-tolyl methyl ketone melts a t 164-1 65'. The oxime crystal- lises from dilute alcohol, melts at 51-52', and is readily soluble in light petroleum. The dibromo-oxime, C,H1,Br2:NOH, melts at 130'. The secondary alcohol, C,H,,O, prepared by the action of sodium on an alcoholic or ethereal solution of the ketone, is a lower homologue of the terpineol melting a t 35'; it boils a t 212-213", has a sp.gr. 0.942, and TZ, 1.4836 a t 1 9 O . 11. 111.724 ABSTRACTS OF CHEMICAL PAPERS. When the oxylactone, Cl0HI6O3, prepared by oxidising pulegenic acid with potassium permanganate, is treated with a small quantity of concentrated sulphuric acid, the ketone pulenone, C,H,,O, is formed which boils a t 183' and has a sp. gr. 0.8925 and n, 1.44506 a t 21'. Pulenol, C,H,,O, obtained by reducing pulenone, boils a t 187-189', has a sp. gr. 0.8953, and n, 1.4569 at 20" ; by the elimination of water it forms pulenene, CgH16. Pulenene nityosochloride, CgH16*NOC1, is a blue substance melting at 88 -89'. Pulenoneoxime, CgH,,: NOH, melts at 94-95' ; pulenoneisooxime melts a t 96-97' and by the action of acids forms nonylenic acid. Both oximes are easily converted into the nitrile of nonylenic acid, which boils at 216-217'.[With cOLMANN.]-PUlegerte, C9H16, prepared by eliminating carbon dioxide from pulegenic acid, boils a t 138-139') has a sp. gr. 0,791, m, 1.44, and on oxidation yields a ketonic acid, CgHlB03, which boils at 265' or a t 164' nnder 15 mm. pressure. The semzcarbazone melts at 164' and pulegene nitrosochloride, CgH16*NOCI, is a readily soluble, white substance. [With THEDE.] -f'degene nitvolepi'ridide, CgH1GON*C,NH,o, melts at 106-107". By elimination OF hydrogen chloride from the nitroso- chloride, pulegenoneoxime, C,H,,:NOH, a liquid boiling at 120-125' under 11 mm. pressure, is formed, and by the action of acids on this compound puleyenone, CgHI40, is obtained. The latter boils a t 189-190' and has a sp.gr. 0.914 and nD 1.4645. The alcohol, CQH180, prepared by reducing pulegenone, boils a t 77-78' under 15 mm. pressure and on oxidation yields dihydropulegenone, CgHiGO, which boils at 188-189', has a sp. gr. 0,889, and n, 1.4439 at 20' and is not attacked by cold potassium permanganate. The semicarbazone melts a t 176-178' and is very slightly soluble in alcohol, The oxirne does not readily solidify. [With A. S c ~ ~ u ~ ~ ~ ~ . ] - c y c l o - ~ e r a n i o l e n e resembles pulegene, boils at 138-139', and has a sp. gr. 0.8030 and n, 1,44406. The nitroso- cldovide, CgH,,*N OCI, and nitrosate, CgHi,N,O,, have been prepared, The nitrolepzperidide, C,H,,ON*C,NHlo, melts at 136-1 38' and the nityolebenzylamine, CgH,,ON*NH*C,H7, a t 106'.By boiling with alcoholic potassium hydroxide, the nitrosochloride and nitrosate form trimethylcyclohexenoneoxime, CgH1,:NOH, which crystallises from ether or light petroleum, melts at 128--129', boils a t 131-132' under 15 mm. pressure, and by the action of acids forms trirnethylcyclohexea- one, C,H,,O. The latter compound boils a t 195-196', has a sp. gr. 0.9245, and n, 1.4749 at 25') and appears to exist only in the enolic form. The semicadaxone melts a t 158-159' and is rather soluble in cold ether, By the action of sodium and alcohol on hexenone, a pina- cone melting at 128-1 30' and tl.imethylcyclo~exanol, C9H180, are formed. The latter is an oil, has the odour of camphor, boils at 192-1 93', and on oxidation yields trimeth&yclohexanone, C9Hl6O, which boils a t 191' and has a sp.gr. 0.9 and n, 1.4548; the oxime melts at 108-109'. [With Kosc~.]-By the action of methyl iodide on the ethyl esterof aminodecoic acid obtained from menthoneisooxime (Abstr., 1900, i, 589), a quaternary iodide, CgHlqNMe,I*CO,Et, melting at 117', is formed, and by treating the chloride prepared from this compound IV.ORGANIC CHEMISTRY. 725 CHMe2*~H.CH,*CH2*QHMe , is ob- with silver oxide, an c-betake, NMe,*O*CO---CH, tained. The hvdrochloride melts at 191-162'. I " C HMe*CH2*CH,*SHPr NMe,*O*CO-CH, ' [With L, FRESENIUS.]-A~ isomeric betaine, I a .G may also be prepared from the aminodecoic acid obtained by the decomposition of te t rah y drocar voneisooxime. [With BoCBER.]-By the reduction of phellandrene nitrite, pre- pared from water-fennel oil by Pesci's method with zinc and glacial acetic acid (Gaxxetta, 1886, 16, 229), a lzevorotatory diamine is obtained which boils at 250-253', but resembles Pesci's diamine (b.p. 209-2 14') in every other property. When phellandrene nitrite from Eucalyptus amygdalina is simply reduced, a lsvorotatory diainine which is not identical with Pesci's is formed. It boils at 250-253O or a t 132-134' under 17 mm. pressure, and is not readily volatile in steam. The hydrochloride, CloH,,(NH,)2,HCl, or CloH,,( NH,),,HCl, melts a t 209-210', is not affected by exposure to air, is slightly soliible in cold alcohol, and on dry distillation yields cymene, ammonia, and ammonium chloride. The platinichloride is readily soluble i n water. The phellandrenes obtained from different sources cannot, therefore, be identical, and the earlier formula for the nitrite containing the group NO*bH*6HO*KO requires modification.Double Glucoside of Frangula Bark. By E. AWENU (Chew,. Centr., 1902, ii, 147; from Apoth. Zeit., 1'7, 372-373. Compare Abstr., 1901, i, 39).-The original paper contains a detailed descrip- tion of the preparation of the double glucoside of frangula bark in a state of purity, together with an account of its decomposition products and its relationship to $-frangulin and frangulic acid. V. E. W. W. E. W. W. Theory of the Dyeing Process. By P. D. ZACHARIAS (Chem. Zed., 1902, 26, 680-681. Compare this vol., i, 635)-The dyeing process is governed by t w o phases: absorption and fixation. The colloidal nature of the fibre and the catalytic influence of the fibre on the formation of a colloidal precipitate must be taken into account.The equation given by Wegscheider (this vol., i, 635) should be dc/dx = d(c;)/dx = 0, in the integration of the formula developed from Fick's law, The value of Y may be greater than, equal to, or less than unity, J. McC. aZloCinchonine. By ARP~D VON PECSICS (Monatsh., 1902, 23, 443-454. Compare Hlavnizka, Abstr., 1901, i, 404)-When boiled with acetic anhydride, allocinchonine forms an acetyl derivative, which crystallises from light petroleum in white plates, sinters a t 88", melts at 92-94', is easily soluble in alcohol, ether, benzene, or chloroform, and yields aZZocinchonine when hydrolysed by alcoholic potassium hydroxide. Benxoylslloci72chonie hydrochloride, formed from allo- cinchonine and benzoyl chloride, is an amorphous powder; it melts at 230°, crystallises either from water in plates or from dilute alcohol in prisms which lose 2H20 at 105" and melt a t 223".The726 ABSTRACTS OF CJ3EMiCAL PAPERS. benzoyl derivative crystallises from ether in short, white needles, melts at 118-119O and is hydrolysed by alcoholic potassium hydroxide to allocinchonine and benzoic acid. When acted on by phosphorus pentachloride in chloroform solution, allocinchonine yields allo- cinchonine chloyide, C,,H,,~,Cl. These reactions distinguish allo- cinchonine from a- and P-zsocinchonine, these bases giving negative results in the preceding experiments. These differences may be ex- plained by assuming that allocinchonine contains a reactive hydroxyl group which is either absent in the molecules of its isomerides or marked by a different spacial configuration. With methyl iodide, allocinchonine forms a methiodide, C,,H,,ON,,MeI,~H,O, which crystallises in clusters of white needles, melts and decomposes a t 245O, is easily soluble in hot water or ethyl alcohol, and sparingly so in methyl alcohol, and a dimethiodide, C,,H,,0N2,2MeI,2H20, which crystallises in red needles or large, garnet-red monoclinic crystals, loses 2H,O a t 1 0 5 O , and melts a t 235O.The methiodide forms a hydriodide, C,9H220N2,MeI,HI, which crystallises in clusters of yellow plates, contains no water of crystallisation, and melts a t about 232O, is easily soluble in hot water or alcohol, sparingly so in cold water or methyl alcohol, and gives a white, crystalline product on treatment with warm sodium carbonate solution.alloCinchonine hydriodide, C,,H,,0N,,HI,H20, crystallises in white prisms, is easily soluble in ethyl alcohol, sparingly so in methyl alcohol, and forms with methyl iodide a second methiodide hydriodide, C19H,,0N,,MeI,HI,~H20, which crys tallises in glistening, lemon- yellow needles, loses +H,O a t 105O, melts at 250-253', is easily soluble in ethyl alcohol, sparingly so in methyl alcohol, insoluble in ether, and on treatment with warm sodium carbonate solution yields a red, amorphous substance insoluble in ether. alZoCinchonine must there- fore be a di-tertiary base. G. Y. alZoCinchonine. By ZDENKO HANNS SKRAUP and RUD. ZWERGER (Monatsh., 1902, 23, 455-468.Compare preceding abstract).- nlZoCinchonine sulphate is oxidised by chromic acid to carbon dioxide, formic acid, acetic acid, cinchonic acid, kynurine, and allomeropuinenine; the last of these forms a platinichloride, (C,H,,0,N)2,H,PtCl,,3H20, crystallising from water in microscopic prisms which lose 3H20 at l l O o and melt at 210-211° ; a hydrochloride, which crystallises in clusters of needles, has a sp. gr. 1.0175, and ra], - 114O, and an auri- chloride, C,HI,0,N,HAuC14, which crystall'lses in delicate needles, melts a t 165-166', is soluble in warm water, and is partly decom- posed by boiling water. alloMeroquinenine is isomeric with meroquinenine and with /I-;so- meroquinenine obtained by oxidation from cinchonine and also from P-isocinchonine. When heated with lime, it gives the same odour as is observed on similar treatment of cincholeuponic acid, cincholeupon, and /3-isomeroquinenine, and when heated with zinc dust an oil having an odour resembling that of pyridine.The molecule of allocinchonine contains a quinoline nucleus and the remainder must be constituted similarly to that of cinchonine. Cincholeuponic acid is not formed in the oxidation of aZZocinchonine,ORGANIC CHEMISTRY. 727 8s the part of the product insoluble in alcohol does not form an opti- cally active hydrochloride. On oxidation by potassium permanganate, allocinchonine sulphate yields formic acid and an amorphous substance resembling cincho- tenine. Cinchonine and allocinchonine in sulphuric acid solution decolorise potassium permanganate, at first rapidly, the rate of oxidation gradually decreasing; with a- and P-isocinchonine, the action is at first slow, increases in rapidity, and is accompanied by much frothing.a- and P-isoCinchonine are probably stereoisomerides of cinchonine and a Uocinchonine. G. Y. Correlation of the Constitution and Physiological Action of Morphine. By ERNST VAHLEN (Chem. Cerztr., 1902, i, 1302-1303 ; from Arch. exp. Path. Pharm., 47, 368-410).-Si1ice epiosine, Y6H4*fl *NMe N>CH, has been found to possess physiological properties C,H;C- sikirar to those of morphine, the pharmacological action of the latter must be dependent on the presence of the phenanthrenoid group, Y6H4'g- c,H,*c*N= ' Y6'H4* :* OH Mwphig e nine h y dr ochlovide, , prepared by reducing phenanthraquinone hydrazone with stannous chloride, crystallises in coloured needles, becomes reddish at lSOo, but does not melt a t 290°, is decomposed by water, especially on heating, and is readily soluble in boiling glacial acetic acid or in hot concentrated hydrochloric acid, but only slightly so in the cold solvents. By the action of alkali hydroxides or carbonates on the hydrochloride, phenanthraquinone is regenerated.By the action of zinc chloride on morphigenine hydro- chloride, products were obtained which were not isolated, but their aqueous solutions had a distinct narcotic effect on dogs and frogs, Epiosine, prepared by the action of methylamine on morphigenine hydrochloride, was found to be identical with Japp and Davison's N-methylphenyleneimidazole (Trans., 1895, 67, 32) ; it melts a t 195'.The physiological actions of morphigenine hydrochloride and epiosine C6H4*C*NH,,HCl are described in detail in the original paper. E. w. w. ZCyanopyridine. By HANS MEYER (Monatslh., 1902,23,437-442. Compare Abstr., 1901, i, 407).-Picolinamide is best prepared by the action of aqueous ammonia on picolinyl chloride and extraction with chloroform. In the preparation of the amide from the ester, the solu- tion of the hydrochloride from the latter, obtained by passing hydrogen chloride into an absolute alcoholic solution of picolinic acid, is con- centrated and shaken with aqueous ammonia (compare Abstr., 1894, i, 425, 4'72). 2-Cymopyridine, prepared by the action of thionyl chloride on picolinamide at 90-1 OOO, crystallises from ether in long, colourless needles, melts at 26O, is slightly volatile at the ordinary temperature, boils at 212--215O, has an intense odour resembling those of benz-728 ABSTRACTS OF CHEMICAL PAPERS aldehyde and of coumarin, and is easily soluble in water, alcohol, ether, or chloroform.It has slight basic properties and forms an orange-red, crystalline platinichloride, (C,H,N,)~,H,PtCl,, and an aurichlorids, C6H,N,,H AuCl,, which crystallises in lemon-yellow needles, losing about lH,O and becoming opaque a t 100’; it melts a t 190’ and is sparingly soluble in water, dissolving easily in dilute hydrochloric acid. Picolinic acid forms an aurichloride which crystallises in glistening, straw-yellow leaflets, melts at 200”, decomposes with evolutim of gas at 204’, and is easily soluble in water.Picolinamide aurichlol-ide is an insoluble, light yellow, crystalline powder which sinters a t about 2 1 5 O , but melts only a t a much higher temperature. The aurichloride of 2-aminopyridine crystallises from concentrated hydrochloric acid in long, glistening, garnet-red needles and melts at 231”. 2-Cyanopyridine is hydrolysed by concentrated hyflrochloric acid at 120°, giving a quantitative yield of ammonia and picolinic acid. G . Y. Tetra-aquodipyridinechromium Salts. By PAUL PFEIFFER (Zeit. anorg. Chew,., 1902, 31,401--436).-Werner’s theory connecting the metal-ammonia compounds and salt hydrates is supported by the facts now known about the intermediate products. The author has investigated some of these intermediate products containing pyridine in place of ammonia.The chloride, CrC11,,2Py,6H20, loses 2 mols. of water in a desiccator containing phosphoric oxide and gives CrC1,,2Py,4Y20 ; therefore, according to Werner’s theory, i t is to be regarded as and is consequently an intermediate product between [CrPy,]Cl, and [Clr(H20),]C1,. I n aqueous solution, all the chlorine is ionised and i t undergoes metathetical reactions. Like the pure hydrates, i t gives basic salts such as [CrPy2(H20),(0H),]C1 when hydroxides are added. The salts are all red, crystallise well from water, and the aqueous solutions have an acid reaction. When heated, they give off pyridine and become green. The basic salts dissolve in acids, giving red solutions. because the basic salts dissolve in alkalis or ammonia.The author has already introduced a slight modification (Nctturwiss. Rundsch., 1901, 366) into Werner’s theory, According to the pro- position suggested, a definite place in the molecule is assigned to the negative radicle. For the tetra-aquodipyridinechromium salts, the formula X { (H20)2>Cr<2E$ is given, indicating that the position of one X is uncertain. The properties of the hydroxylopyridine salts which have been obtained indicate that they are not the basic salts corresponding with they are rather to be regarded as salts of pseudo-bases formed from the true bases by splitting off of water : [In the formulz given Py = C,NH,.] [CrPy 2(H20)41C13,2H20, It has not been possible to prepare the free base, W Y ,(H,O) (OHM 9 PY, This shows that these are oxonium salts.[CrPY,(H,O),IX, ; + 2 ~ 4 0 .ORGANIC CHEMISTRY. 729 The idea of pseudo-salts can also be advantageously applied to metal-ammonia compounds. The starting point for the preparation of the tetra-aquodipyridine- chromium salts is diuquodihydroxylodipyridineclwomiun,t chloride, LCrPg,(OH),( H,O),]Cl, which is obtained from green chromic chloride hexshydrate, I Cr(H20),Cl2]Cl,2H2O, by the actionof pyridine ; it may be prepared in like manner from the double salt, [Cr( H20),C1,],2HClPy, which is most easily obtained by adding successively pyridine and a large excess of concentrated hydrochloric acid t o a solution of chromic chloride; a third method of preparation is by warming CrC13Py, with a 10 per cent. solution of ethylenediamine. The diaquo- salt is obtained in fine needles which decompose at looo; i t is quite insoluble in the ordinary solvents, but can be recrystallised from pyridine.When the dihydroxylochloride is treated with concentrated hydro- chloric acid, the greenish-grey compound is converted into a red, crys- talline mass of tetru-aquodipyridineclrornium chloi*ide, [CrPy2(H,0),]C1,,2H20 or 01 { (H20)2>Cr<H~OC1 H OC1 + 2H20. This is very easily soluble in water, ethyl alcohol, or methyl alcohol, but insoluble in ether, acetonitrile, acetic acetate, acetic acid, or chloroform. The aqueous solution remains unchanged at the ordinary temperature, but decomposition occurs when i t is heated on the water- bath. The red, alcoholic solution quickly decomposes and deposits the greenish, basic chloride.The reactions with various reagents have been studied. I n the air, the salt is converted into the greenish-violet ?Lydroxylotria~uod~~yridinechl.omizcm chioride, [CrPy,(H,O),OH]Cl,. Tetra-uquodipyridinechromium bromide, lCrPy2(H2O),]Br,,2HzO, obtained from the dihydroxylochloride, or the normal chloride, by solution in concentrated hydrobromic acid, separates i n red crystals from concentrated hydrobromic acid solution. It closely resembles the chloride but is rather more stable. Dih,ydroxylodiaqzcodipyridine- chronzium bromide, [CrPy2( H,O),(OH),]Br, is almost quantitatively precipitated by the addition of pyridine to a solution of the normal bromide; it has a greenish tinge and is decomposed on heating. When the dihydroxylochloride is rubbed with sulphuric acid, a red solution is produce? from which flat, red needles of tetra-aquodi- pyridinechromium Iydrogen sulphute, S04[CrPy2( H20),]S04H, 2H20, separate.The salt is very easily soluble in water and the solution has an acid reaction ; i t is insoluble in alcohol or ether. When alcohol is added to the concentrated aqueous solution of this salt, violet crystals of tetra-aqzcodipyridinechl.omium sulphate, are formed. This sulphate remains unchanged in the air, but is decomposed by water ; when placed beside phosphoric oxide, it does not lose in weight. When a solution of the tetra-aquo hydrogen sulphate is precipitated with pyridine, fine, greyish-blue crystals of hydroxylo- Iriuquodipyridinechromium subhate, [CrPy,(H,O),( OH)]SO, separate ; the latter salt is soluble in much water to a greenish solution having a neutral reaction. 3 3 2 [CrPY2(H,O)412(S~4),,3H,O,730 ABSTRACTS OF CHEMICAL PAPERS.Tetra-aquodipyridinechromiwm chromicyanide, [CrPy,(H,O),1Cr(CN),,2H,P, is precipitated when potassium chromicyanide is added to a solution of the tetra-aquochloride containing some hydrochloric acid. It is obtained in red plates which are insoluble in water. Hydroxypyrazolone Derivatives of the Naphthalene Series. FARBENFABRIKEN VORM. F. BAYER & Go. (D.R.-P. 131537).-The hydrazine derivative obtained from 7-amino-a-naphthol-3-sulphonic acid, when condensed with ethyl acetoacetate in the presence of dilute acetic acid, gives rise t o hydroxypyrazolonesulphonic acid, which separates in granular crystals when the mixture is treated with excess of hydrochloric acid.This product yields a yellow nitroso-derivative. Other hydrazines of the naphthalene series may be employed in this condensation and the reaction also occurs with ethyl oxaloacetate or di h yd roxy t a r t aric acid. Chloro-m-phenylenediaminecarboxylic Acid. By PAUL COH.N and MARKUSCHIFFERES (Chern. Centr., 1902, i, 1293; from Zeit. Far ben- Text il-Chem. ,,I 9 02,1,205 -2 06). -4- CT~loro-m-phenyZenedic~mir~- 6-carboxylic acid or 2-chloro-3 : 5-diainino-1-benxoic acid, prepared by reducing 2-chloro-3 : 5-dinitrobenzoic acid with stannous chloride and hydrochloric acid, is very readily soluble in water and was not isolated, The hydrochloride, C,H~0,N2C1,2HCl, crystallises from alcohol in small, pale yellow needles.was also prepared, The dzacetyl derivative, C6H,CI(NHAc),*C0,H, crystallises from water in needles and melts a t 288-289’. 2-Amino- 3 : 5-dinitrobenzoic acid, on reduction with stannous chloride and hydrochloric acid, forms 2 : 3 : 5-triaminobenzoic acid. The free acid prepared by treating the solution of the hydrochloride, C7H902N3, 3HC1, with sodium acetate quickly becomes red. The sulphate forms brownish-yellow needles and is almost insoluble in water. E. W. W. 3-Arnino-4methylpheno-fl-naphthacridine. FRITZ ULLMAN (D.R.-P. 1 30943) .-3-Amino-4-methyZp7eno-~-naphthacridine, formerly obtained by condensing 2 : 4 : 2’ : 4’-tetra-amino-3 : 3’-ditolylmethane with P-naphthol, is now prepared by heating the latter compound at 200° with the product, C8HloN2, formed by the interaction of form- aldehyde and tolylene-8 : 4-diamine in molecular proportion, the reaction being effected in neutral solutions.Proteids of Yeast. By R. SCHR~DER (Beitr. chem. Physiol. Rath., 1902, 2, 389--403).-Tbe proteid substance, which can be obtained from yeast by treatment with ether and water, and can be precipitated from this solution by heating, gives all the proteid reactions ; the lead reaction is feeble. By decomposition with acids, it yields leucine, tyrosine, phenylalanine, and bases. The bases contain about a quarter of its total nitrogen, and of them lysine is the most abundant. A J. MUG. G. T. M. C6H2C1( NH?)2*C02H, The suZphate, C7H7q,N,C1,H,SO,,H,O, G. T. M.ORGANIC CHEMISTRY. 731 part of the sulphur is present in a cystin-like combination.tion of a carbohydrate group is left for future consideration. The ques- W. D. H. Melanins which Originate from Proteid. By FRANZ SAMUELY (Beitr. chem. Physiol. Puth., 1902, 2, 355-388).-The ill-characterised and probably numerous substances, named melanins and melanoidins, can be artificially prepared from proteids. I n their formation, the tyrosine group, and especially the heterocyclic nucleus (pyrrole, pyr- idine, skatole) of the proteid appears to be important. The relationship of these substances to humin is discussed. W. D. H. The Albumose Precipitates produced by Papain and Rennin (Coaguloses and Plasteins). By D. KURA~EFF (Beit?.. chem. Physiol. Pccth., 1902,2,411-424).-The precipitates produced by adding rennin and papain to various albumoses and caseoses were examined and analysed.These substances are probably closely related to anti- albumid, and possibly to bacterial coagulins. These are characterised by a high percentage of carbon and a low percentage of nitrogen, so differing from the proteoses. Decomposition of Proteids. By H. STEUDEL (Zeit. physiol. Chem., 1902, 35, 540-544).-The usual method of obtaining hexon bases from proteids is by means of mineral acid. If boiling baryta water is used instead, the proportion of the bases is different, lysine being by far the most abundant. Whether this is due to the destruction of the other bases during the boiling is uncertain. The decomposition of proteids produced by ferments is very similar to that produced by bary ta, W. D. H. The Nucleo-proteid of the S u p r a r e n a l Gland. By WALTER JONES and G. H. WHIPPLE (Amer. J. Physiol., 1902, 7, 423--434).-- This substance is not a nucleo-histon, and its composition is identical whether prepared from the ox or sheep. It is closely similar t o t h a t obtained from the pancreas. On decomposition, i t yields guanine and adenine in the same relative proportion. Xanthine, hypoxanthine, and epiguaiiine are either absent or present in the merest traces. As these three bases were found by Okerblom (Abstr., 1899, ii, 778) in suprarenal extracts, there is an interesting and curious differ- ence between the bases preformed in the gland and those which result from the hydrolytic decomposition of its nucleo-proteid. The Constitution of Proteid Cystin. By ERNST FRIEDMANN (Beit?*. chem. Phylsiol. Path., 1902, 2, 433--434).-The older physiologists re- garded the sulphur-containing complex in a proteid as the source of taurine. Recent research has shown that the sulphur-group of proteid is cystin or cystein. The possibility of its transformation into taurine is excluded if Baumann is correct in considering that cystein is a-aminothiolactic acid, SH*CMe(NH,)-C0,H. The present research shows that the cystin from proteid is different from ordinary cystin. Proteid cystein is a compound of P-thiolactic acid, SH.CH;CH(NH2)*CO,H. By the usual treatment, this W. D. H. W. D. H.732 ABSTRACTS OF CHEMICAL PAPERS. can be changed into cy steic acid (aminosulphopropionic acid), S0,H*CH2*CH(NH2)*C02H, and from this, by the loss of carbon dioxide, taurine, S0,H*CH,*CH,*NH2, is obtained. Proteid cystein is thus a derivative of glyceric acid, not, as with mercapturic acid cystein, of pyruvic acid, and stands in close relation- ship to serin. W. D. H. Action of Iodine on Proteids. I. By C. H. L. SCHMIDT (Zed. physiol. Chem., 1902, 35, 386-395. Compare this vol., i, 251).-The amount of amic nitrogen eliminated from the proteid molecule dur- ing iodination is a function of the concentration of the iodine solution used; the more concentrated the solution, the greater is the amount of iodide and iodate formed and the less that of hydriodic acid. J. J. S. Experiments :on Malt Diastase. By ARTHUR R. LING and BERNARD F. DAVIS (J. Ted. Inst. Brewing, 1902, 8, 475-495).- When diastase from well-grown, low-dried malt is allowed to act on starch paste of 2-5 per cent. strength at 50-60°, the starch is hy- drolysed in about 18 hours to a point a t which [aJD .1.93 is 149*5-150° and the cupric reducing power R,.,, is 77-78, whilst after 42 hours these constants are substantially those of maltose, and in such a solution nothing but maltose can be detected. Diastase prepared from malt grown under abnormal conditions (such as small quantities prepared in the laboratory) and diastase which has been slowly heated to 115-120° do not hydrolyse the starch completely to maltose, even if allowed to act in large excess ; diastase which has been rapidly heated t o 115-120" produces a more pronounced effect. Keither the fhal temperature at which a sample of malt has been kilned (considered alone), nor the '' diastatic power " determined in accordance with Kjeldahl's '' lam of proportionality " by Lintner's method, is a criterion of its behaviour towards starch. When a dias- tase solution is heated above 65", its reaction with starch paste appears to be quite different to that of a solution which has not been heated above 60"; this is shown, not only by the specific rotatory and cupric reducing power of the dissolved matter, but also by the presence of dextrose among the final products of hydrolysis. E. G. Catalase. By OSCAR LOEW (Zeit. Biol,, 1902, 43, 256-257).- The ferment in milk which causes decomposition of hydrogen peroxide has been termed superoxydase by Raudnitz. It is identical with the ferment previously named catalase by the author (Abstr., 1901, i, 435). W. D. H.