i. 101 Organic Chemistry. Formation of Hydrocarbons from Carbon Monoxide. 1,120 VIGNON (Bul!. SOC. cJLZ'WZ. 1911 [iv] 9 lS-20).-Various observers have shown that when carbon monoxide is passed over heated sodium or potassium hydroxide soda-lime or calcium hydroxide a formate is produced and that on further heating hydrogen is evolved. I n the present investigation i t is shown that with lime and carbon monoxide bet ween 350" and 400" considerable quantities of methane ethylene and hydrogen are formed and that from 400" to 600" the quantity of hydrogen increases at the cost of the hydrocarbons. The reactions taking place are probably represented by the following equations 2CO + Ca(OH) = (H*CO*O),Ca = C,O,(O),Ca + H ; 2(H*COnO),Ca + CaO = 3CaC0 + CH ; 4(H*CO*O),Cit + 2Ca0 = 6CaC0 + C,H + 2H2 and experiments in heating calcium formate or oxalate alone and mixed with lime have confirmed this explanation of the origin of the hydrocarbons.Carbon monoxide may be converted into hydrogen and hydrocarbons to the extent of 99.5% by passage over hot lime several tirnep and it is suggested that in this way illuminating gas might be freed from this toxic constituent. T -4. H. A Secondary Heptane in Roumanian Petroleum. N. COSTACHESCU (dinit. sci. Univ. Jussp 19 10 6 294-301).-The fraction of petroleum from Colibasi having b. p. 87*5-93.5" con- tains P-methj lhexane with 1 3-dimethylcyclopentano and a small quantity of isomeric heptanes. When the fraction is heated with nitric acid (D 1.4) at 60' in sealed tubes the /3-methylhexane is converted mainly into a nitw-derivative C7HI5O2N b.p. 86-S6*5"/ 21.5 mrn 1); 0.9961 n 1.43855 ; the other hydrocarbons however w. 0. w. undergo oxidation to oxalic acid and carbon dioxide. Dimorphism of Iodoform. BRUNO BARDACH (Chem. Zeit. 1911 35 11-12).-The thin yellow needles obtained previously (Abstr. 1909 i 645) by the action of iodine and potassium iodide on acetone solutions of anhydrides and anhydride-forming compounds are now found to consist of iodoform. The crystals have m. p. 12l0 and on distilling in steam or crystallising from alcohol are transformed i r t o the ordinary hexagonal form. P. B. Estimation of Active Hydrogen in Organic Compounds by means of Magnesium Methyl Iodide. TH. ZEREWITINOFF Ber. 1910 43 3590-3595. Compare Abstr. 1907 ii 509 ; 1908 i 593).-The method previously described for the determination of replaceable hydrogen atoms is applicable also to the alkaloids.Those alkaloids which contain active hydrogen react with magnesium methyl iodide at the ordinary temperature and yield methane quantitatively. VOL c. i. ii. 102 ABS!CRACTS OF CHEMICAL PAPERS When heated no additional methane is formed showing the alkaloids t o contain no amino-group. The rapidity of the method and the fact that only small quantities of substance are required are important features. A number of the commoner alkaloids were tested. Pseudo-acids from nitromethane nitroethane etc. react as if they contained one bydroxyl although the amount of methane obtained is somewhat less than the calculated but it increases on warming.The experiments were made both in amyl ether and in pyridine solution; xylene mesitylene and anisole may equally well be used. E. F. A. [Pinacolin Derivatives] Corrections. MAURICE DELACRE (BUZZ. SOC. clhim. 1911 [iv] 9 41-43).-Polemical in reply to Richard (this vol. i 6) clainiiag priority as regards the synthesis of the alcohol CMe,*CHMe*OH (Abstr. 1906 i 477) and other matters. T. A. H. Preparation of Octan-yy-dione-a-ol and its Homologues. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 227177).-The condensation of unsaturated ketones by which 1 5-diketones are obtained is a reaction about which very little is known; the diketo- alcohols now described are of technical importance in pharmacological preparations. Octan-yy-dione-a-oZ CH,*CO*CH2*CH2*CH,*CO*CH,*CH,*OH b.p. 142-143'/22 mm. a colourless odourless oil miscible with water in all proport,ions is prepared as follows methyleneacetone (Abstr. 1910 i 652) is mixed with water (15 parts) either alone or in the presence of a small quantity of potassium carbonate and allowed to remain until the odour of methyleneacetone has disappeared ; the solution is acidified with tartaric acid saturated with ammonium sulphate aud the product extracted with ether dried and fractionated when a considerable amount of butan-y-on-a-01 CH,*CO*CH,*CH,*OH b. p. 84-85'/23 mm. is also obtained. Pc-DirnetAyloctccn- yq-dione-a-ol is prepared by boiling methyl methylone-ethyl ketone with aqueous formic acid during forty t o fifty hours unchanged mettiyl methylene-ethyl ketone is removed by steam and the solution rendered alkaline whereby any fornzyldimethyl- oclandionol is hydrolysed. The product a viscous odourless colourless oil b.p. 145.5'/16 mm. 148'/18 mm. and 264-268' under atmospheric pressure can also be obtained by either boiling dimethyl- octendione (this vol. j 114) with water or by shaking i t with cold dilute formic or with sulphuric acid; the semicarbctxone has m. p. 209-2 10'. F. M. G. M. Preparation of Narcotics [Glyceryl Ethers]. 0. F. BOERRINGER and S~~HNE (D.R.-P. 226454).-Glyceryl triethyl ether is not a narcotic but when mixed alkyl residues are introduced this property is developed ; these compounds are colourless mobile fluids. Glyceryl ay-dimet?hyl P-ethyl ether C7HI6O3 b. p. 65'/20 mm. DZo 0.917 was prepared by the ethylation of the ay-dimetbyl ether in benzene solution with the neeessary quantity of sodium ethoxide andORGANIC CHEMISTRY i.103 ethyl bromide. Glyceryl ay-dimethyl P-propyZ ether C,H,,O was similarly obtained with propyl chloride ; it has b. p. 76-77'/17 mm. atid D20 0.908. Glyceryl P-methpl ay-diethyl ether C,H,,O has b. p. 75'/17 mm. D20 0.902. Glyceryl ap-dimeth$ y-ethyl ether C7H160a b. p. 49'/7-S mm. D20 0,919 was prepared from glycerol ethyl ether methyl iodide and &odium methoxide in benzene solution. Glyceryl ay-dieth?yl P-propyl ether C,,H,,O has b. p. 77-78'1' 9-10 mm. and D'O 0.882. G'lyceiyl a/3-dirnethyl y-propyl ether C,H,,C) b. p. 66-67'/9-10 mm. D20 0,910 was obtained from glycerol propyl ether b. p. 122'112 mm. D2 1.034 which was prepared by the action of sodium propoxide on glycerol monochlorohydrin.Glyceryl a-methyl /3y-Jiethyl ether C,H,,O b. p. 57"/7-S mm. D20 0.901 was prepared from glycerol naethyl etJLer b. p. 108-109"/ 8-10 mm. D20 1.1 15. Glyceryl /I-beiaxyl ay-dimethyl ether C12H,s03f has b. p. 149-150°/17-1 S mm. and D2O 1.025. Glyce~ol a-ethyl y-propyl ether b. p. 86.5'/10 mm. D'O 0,935 was prepared from the sodium derivative of glycerol ethyl ether and propyl bromide and yielded on methylation g l y e r y l /3-methgl a-ethyl y-propyl ether C,H,oO b. p. 71.5-72"/7-8 mm. D20 0.893. F. nil. Q. M. A Very Basic Chromic Acetate. ERNST GUSSMANN (ZeitsCh anorg. Chem. 1911 69 217-220).-1n the preparation of hexa- acetatotrippridinetrichromi-diacetate (Abstr. 1910 i 503) it was found t h a t the mother liquors contained a violet basic acetate Cr2(OAc),(OH),,9H20.This is best obtained as follows To a solution of 10 grams of hexa-acetatotrichromium diacetate (Abstr. 1909 i 757) in 15 grams of water are added 10 grams of pyridine and the solution heated for half a day. After separating t h e crystals of the above-mentioned diacetate of the tripyridine base the mother liquor is allowed to evaporate at room temperatuke. After several weeks the crystals are collected and washed with cold water to remove the admixed diacetate of the tripyridine base. Rapid concentration of the solution is not favourable to the formation of crystals. The violet acetate forms violet four-sided double pyramids and loses 9H,O over sulphuric acid. It readily dissolves in dilute acids giving a violet solution which makes it probable that the hydroxyl groups possess on hydroxo- and not an ol-character. In phenol it gives a normal molecular weight.It is also formed when a solution of the diacetate of the trichromium base is repeatedly evaporated or when a solution of freshly cold-precipitat ed chromium hydroxide in acetic acid is allowed t o evaporate at room temperature. A green amorphous basic acetate has also been obtained by drying the diacetate of t h e hexa-acetatotrichromium base at 100-1 loo. 1b is less basic than the violet acetate. A formula cannot be given far it a t present. T. s. P. Behaviour of Acetic Anhydride at EL High Temperature. EUQEN BAMBERGER (Ber. 1910 43 3517-3580).-According t o the author the first stage in the formation of acetone by the distillation 'I 'ti. 104 ABSTRACTS OF CHEMICAL PAPERS.of calcium acetate is the dissociation of the salt into calcium oxide and acetic anhydride which at the high temperature necessary for its production decomposes into carbon dioxide and acetone. With a view t o confirming this supposition the behaviour of acetic anhydride at high temperatures has been studied. On heating the anhydride for several hours at 290-300° small quantities of acetone a111 acetyl- acetone were found amongst the products. Whether the formation of the last-named substance is due to the direct acetylation of acetone by means of acetic anhydride or to the intermediate formation of ket en has not been determined. These experiments also support the contention of Schmidlin and Bergmann (Abstr.1910 i 816) that the first stage in the synthesis of keten from acetic anhydride (Wilsmore Trans. 1907 91 1938) consists in the decomposition of the latter into carbon dioxide and acetone. The reaction O(COMe) = CO + COMe is probably reversible but the amounts of carbon dioxide and acetone are very small when equilibrium is attained. The fact that acetone is produced in large quantity by the distilla- tion of calcium acetate is not in opposition to this view for the dissociation products carbon dioxide and acetone are continuously removed during the reaction the latter by distillation the former by union with the calcium oxide produced by the decomposition of the acetate. Various by-products obtained in the manufacture of acetone were examined for acetylacetone but no indication of its presence was obtained.F. B. Salts of a Green and of a Violet Propionatochromium Base. RUDOLF F. WEINLAND and KARL HOEHN [with &I. FIEDERER] (Zeitsch. nnoi*g. Chern. 1910 69 158-178. Compare Abstr. 1908 i 847).-Salts of the green hexapopionatotrichromiurn base Y (OH) (o*coEt)61. To prepare the dichromute propionute where Y = [Cr Y(O*COEt)(Cr20Z),H,0 2 grams of chromium trioxide are warmed with 20 C.C. of propionic acid After filtering from the undissolved chromium trioxide the solution on keeping deposits four-sided brownish-green plates of the salt i n question. Molecular weight determinations in acetophenone gave 961-801 as against 937.6. The sesquichromate propionate Y(O*COEt)( HCr0,)($CrO4) is obtained by warming chromium trioxide and chromium hydroxide in the proportion of 2 mols.of the former to 1 mol. of the latter with propionic acid. On concentrating the solution dark olive crystals are obtained. Molecular weight in acetopheaone was 753-878 as against 877.5. When a mixture of chromium trioxide and chromium hydroxide in the molecular proportion of 1 3 is dissolved in propionic acid and the solution concentrated green six-sided plates of the chyomate propionate Y(O*COEt)(CrO4),1*5H,O are obtained. It may also be obhained by dissolving 1 gram of chromium trioxide in 50 C.C. of propionic acid and concentrating the solution. When less than ten parts of propionic acid to one part of chromium (OH,),ORGANJC CHEMISTRY. i. 105 trioxide are taken and the mixture heated chromates are obtained which contain less propionic acid in the anion than the above-mentioned salts.Whether a dichromate or a lower chromate of the base is obtained depends on the time of heating ; the longer the heating the poorer is the resulting chromate in chromic acid. Whenever the dichromate propionate is recrystallised from a little water propionic acid is lost from the anion and pure sesquichromate Y(Cr0,)($Cr0,),2H20 is obtained. Even when the chromate propionates are recrystallised from a solution of propionic acid some of the latter is split off from the anion. The chloride chromute Y(Cr0,)C1,H20 is obtained as yellowish-green six-sided plates by the addition of concentrated hydrochloric acid to strong solutions of any of the above salts.The nzonopropionate Y(O*COEt),ZH,O is prepared from the chromate propionates by removing the chromic acid with lead propionate or from the chloride (Abstr. 1908 i 935) by treatment with silver propionate i t forms pale green rod-like crystals. Salts of a violet pentapropionutotrichromiurn base Y (OH) where The dipropionate Y(O*COEt) forms the starting point for the preparation of t h e other salts. It is best prepared by dissolving 1 mol. of freshly-prepared chromium hydroxide which has been washed with cold water in 3 mols. of propionic acid at the room temperature The solution is then heated in a sealed tube for five hours a t 140-160’ ; on cooling violet crystals of the dipropionate are found on the walls of the tube. After purification by a somewhat complicated method they are obtained as flat prisms which may be 1 cm.long. Molecular weight in acetophenone was 615 a s against 737.7. The nzono- pyopionate Y’(O*COEt),3H20 where Y’ = Cr,(OH) is obtained by saturating the aqueous solution of the dipropionate with sodium chloride or nitrate ; light violet crystals. The sesguipropionate Y(O*COEt)21Y’O*COEt,H,0 results on evaporating a solution of one part of the dipropionate with five parts of sodium propionate ; violet Bat prisms. The sulphatepropionate (Y O*COEt),S0,,4H20 crystallisc s i n violet plates on the addition of concentrated sulphuric acid to the saturated solution of the dipropionate. The bromide propionate Y(O*COEt)Br,4H20 forms violet prisms as also does the chloride Y’Cl,Y’O*COEt,lUH,O ; they are iorrned from the dipropionate by precipitation with concentrated hydrobromic and hydrochloric acid respectively. All t h e salts of the violet base are readily soluble in ether and chloroform; those of t h e green base are insoluble in ether.The salts of the violet base cannot be recrystallised from water. From the solution of chromium chloride hydrate CrC1,,6H20 in a solution of sodium propionate violet crystals are obtained having t h e composition Cr(O*COEt),*OH,H20. They are insoluble in ether in contradistinction t o the violet pentapropionatotrichromium salts. Y = 1 CI-,(OH)~ w 9 g [ Z 2 Y O 2 ) 7 T. S. P,i. 106 ABSTRACTS OF CHEMICAL PAPERS. Condensation of ap-Dibromopropaldehyde with Mslonic Acid. ROBERT LESPJEAU (Conapt. rend. 1910 151 1359-1361.Compare Spenzer Abstr. 1005 i 204).-a~-Dibromopropaldehyde Acts on malonic acid to form &WdmmwuaZeric acid m. p. P2S-l3O0; the ethyl ester has b. p. 160-161°/12-13 mm. Both t h e acid and the ester on treatment with zinc and alcohol furnish ethyl Ap-pentenoate CHMe:CH*CH,*CO,Et b. p. 145 -146'/760 mm. (On brominating the corresponding acid a su bslarice is obtained probably identical with ap-dibromovaleric acid. w. 0. w. The Oil and Wax of Coffee Beans. HAPI'S MEYER and ALFRED ECKEHT (Moizccfsh. 1910 31 1227-1251).-Uriroa,tsted coffee beans from which the greater part of the caffeine had boen extracted were dried powdered and digested with benzene. The oil thus obtained had a brownish-yellow colour WAS nearly odourless arid had the consistency of olive oil.On hydrolysis i t gave 21.2% of non-saponifi- able matter. For isolating the acids formed on hydrolysis it was found advisable t o saponify with lithium hydroxide solution (compare Yartheil and FeriB Abstr. 1904 i 4) but this method did not give a complete separation of saturated from unsaturated acids. The sparingly soluble lithium salts gave the following acids Carnaubic acid 10% (Sturcke Abstr. 1884 1280 ; Uarmstiidtcr and Liefschutz 1896 i 346; Dunham and Jacobson 1910 i 215); daturic acid 1-1*5% (Gerard Abstr. 1890 1396; Kreis and Hafner 1903 i 788 ; Holde Ubbelohde and Marcusson 1905 i 318) ; palmitic acid 25-28% and decoic acid 0.5%. I n order to obtain the carnaubic acid pure the least soluble fraction of the lithium salts was transformed into chloride by means of thioriyl chloride and then into ester ; the processes of conversion into lithium salt chloride and ester were repeated when the methyZ ester was obtained in the form of glistening plates m.y. 51-55' and this on hydrolysis gave the acid with m. p. 74' (not 70" or 72.5'). The lead salt has m. p. 109-110" and is soluble in toluene. The acid resembles stearic acid in many respects but its ethyl ester is not 80 soluble in alcohol. The detection of glyceryl esters of this acid in fats is readily accomplished by warming the fat with absolute alcohol and a little sulphuric acid when the sparingly soluble ethyl carnaubate mixcd with a little palmitate and stearate is deposited. JIetlqZ daturate CIGH,,*CO,Me has m. p. 30° and the magnesium Falt m. p. 137-142'.The more soluble lithium salts were converted into lead salts and the saturated and unsaturated acids separated by extraction with benzene. The acids isolated wero palmitic oleic 2% and linoleic SO% The unsaturated acids were identified by oxidation with 2% per- manganate solution in t h e cold when dihydroxystearic and sativio acids were obtained and by bromination when tetrabromostearic acid was isolated. The wax contained a small amount OF alkaloid which was removed by steam distillation and solution in glacial acetic acid. When finely divided and made into a n emulsion with potassiiim hydroxide solution the wax was oxidised by 4% permanganate to carnaubic acid and whenORGANIC CHEMISTRY i. 107 hgdrolysed with alcoholic potassium hydroxide solution a t 150-1 70° it gave carnaubic acid (50%) and a compound with the properties of a tannol.This latter has not been' obtained crystalline ; it has no definite m. p. but i s soluble in alkali solutioris and can be benzoylated. The wax is therefore a tannol resin. J. J. S. Preparation of Cfompounds of Unsaturated Acids with Aldehydes Ketones and Formic Acid. EARBWERKE YORRI. MEISTER LUCIUS Kz BRUN~NG (U.R.-P. 226222 and 226223).-It is found that unsaturated fatty acids of high molecular weight combine (in the presence of acid condensing agents) with kebones or aldehydes t o form a new series of oily compounds. The free acid may be replaced by the oil which under the experimental conditions becomes almost entirely hydrolysed. The substances employed were acetone formaldehyde acetaldehyde benzaldehyde dextrose lzevulose sucrose and maltose which were severally heated with castor oil ricinoleic acid oleic acid and cottonseed oil in the presence of either sulphuric acid zino chloride or phosphoryl chloride.The second patent states that formio acid may be employed in this reaction instead of formaldehyde and details are given of its condensation with ricinoleic acid. F. M. G . N. Preparation of Acyl Derivatives of Castor Oil [Ricinoleic Compare Abstr. 1909 i 696).-The aromatic acyl derivatives af ricinoleic acid have not previously been prepared ; it is now found that aromatic acid chlorides reacting with the hydroxyl group of the acid yield the corresponding acyl derivative ; these are usually tasteless odourless oils. The benzoyl ester vas prepared by boiling castor ail in benzene solution with bonzoyl chloride in the presence of pyridine during half an hour; the anisogl ester was obtained in a similar manner.The salicyl ester was prepared by heating castor oil and salql together a t a temperature of 200' during three hours and distilling off the separated phenol in a vacuum. Acid]. VEREINIGTE CHININFABRIKEN ZIhIMER & CO. (D.R.-P. 2261 11. F. M. G. &I. E&er Csndensations with Chloroacetic Ester. WILHELM WISLICENUS (Bey. 1910 43 2528-2533).-1n the Claisen con- densation ethyl chloroacetate can function as the ester component and also as the methylene compound. The interaction of ethyl chloroacetate ethyl oxalate and sodium ethoxide in ethereal solution yields ethyl chloro-oxalacetate CO,Et*CO*CHCl*CO,Et b.p. 150-152"/56 mm. (compare Peratoner Abstr. 1893 i 11 ; Roubleff Abstr. 1891 223) ; this forms a green copper salt and yields oxamide when treated with ammonia; at 240° it loses only half the theoretical amount of carbon monoxide ; in alcoholic solution it gives an intense red ferric chloride reaction. When equal molecular quantities of ethyl formate and ethyl chloro- acetate are introduced into a cold alcoholic ethereal solution of potaasium rpethoxide a potassium salt is formed from wbich byi. 108 ABSTRACTS OF CHEMICAL PAPERS. acidification ethyl a cicrZoroform?llacetats CHO*CHCl*Cd,Et is obtained a s a n oil giving a n intense violet ferric chloride reaction. On repeated distillation in a vacuum it is obtained i n colourless leaflets m. p.88-90°; the latter give only a faint violet coloration with ferric chloride and yield with copper acetate a green copper salt ; a f t e r fusion t8he crystalline ester gives the original intense violet ferric chloride reaction. The isomerism here exhibited has not been further investigated but there is little doubt that the liquid ester has the enolic structure 0 H*CH :CCl*CO,E t. The benxoyl derivative OBz*CH:CCl*CO,Et prepared from the above-mentioned potassium salt crystallises from alcohol in large colourless plates m. p. 90-91'. With phenylhydrazine both the ester and the potassium salt react to form the osazone of ethyl P-hydroxypyruvate CH( :N*NHPh) *C(:N*NHPh)*CO,Et (compare Will Abstr. 1892 356). The Condensation of two molecules of ethyl chloroacetate has also been effected (compare Erlenbach Abstr.1892 953) ; ethyl chloro- acetate (2 mols.) and sodium ethoxide (1 mol.) flee from alcohol are allowed t o react in ethereal solution at a low temperature; on acidifying the sodium salt thus produced ethJ a-y-dichlorouceto.ccetafe CH,Cl*CO*CHCl*CO,Et is obtained in a n impure condition. It is purified by converting it into the copper salt and decomposing this with hydrochloric acid; it forms a colourless oil with a penetrating odour b. p. 118-120"/15 mm. and solidifies on cooling m. p. lS-20° ; it gives an intense cherry-red coloration with ferric chloride and is hydrolysed by boiling with dilute sulyhuric acid to s-dichloro- acetone ; the copper salt (CH,CI*CO*CCI*CO,Et),Cu crystallises in microscopic green needles melting at 149' (decomp.) to a turbid yellow liquid.F. B. Ethyl y Chloroacetoacetate. ROBERT LESPIEAU (Bull. Soc. chim. 1911 [iv] 9 31-33. Compare Abstr. 1899 i 243; 1905 j 406 ; Picha Abstr. 1907 i 178).-Polemical with Schlotterbeck (Abstr. 1909 i 550) on the physical properties of this ester. T. A. H. Condensation of Ethyl Acetate with its Higher Homo- logues. ANDRB WAHL (Conzpt. rend. 1911 152 95-98).-1t has hitherto been found impossible to prepare P-ketonic esters by cond ms- ing ethyl acetate with its higher homologues. This condensation has now been effected by adding alternately t o the higher ester small carefully weighed portions of ethyl acetate and sodium. I n this way the formation of ethyl acetoacetate and of the compound R*CO*CHR*OK is prevented or diminished; the yield however is small 5-6% in the case of ethyl propionylacetste for the pure compound and lS-ZO% i n the case of ethyl butjyrylacetate.The latter forms a green copper derivative Cu(C8H1303) m. p. 125-1 26' ; on boiling with methyl alcohol it changes into a blue busic salt C,H,,O,*CuOMe. Ethyl butyrylacetate is converted by oxides of' nitrogen into ethyl butyiylglyoxylate CH,Et*C'O*CO*CO,Et an orange-yellow liquid b. p.ORGANIC CHEMISTRY. i. 109 87-8So/13 mm. becoming colourless on the addition of water or alcohol with which it combines ; the diketone condenses wit.h p-phenyl- en ed iam i n e for mi n g 8th y l 2 -prop yIguinoxali~ze-3- carboxylute N:yPIa C6H4<N :C*C*,Et' long needles m. p. 63-64'. w. 0. w. y-E thoxy-a-alkylacetoacetic Esters.MARCEL SOMMELET (Bull. SOC. chim. 1911 [ivl 9 33-38. Compare Abstr. 1907 i 21 10'7).- The considerable differences in the hoiling points ascribed by Isbert to the compounds he regarded as a-ethoxp butanone and a-ethoxypentanone (Abstr. 1886 1009) From those found by the author for his pre- parations of these substances has led him t o re-investigate esters having the constitution assigned by Isbert to the esters from which his ketones were prepared. The author finds that they do not correspond with Isbert's dewriptions and that on hydrolysis they furnish ketones identical with those he has described already (loc. cit.). Ethyl y - ethoxv - a - methylacetoacetate 0 Et.CH,*CO*CHMe*CO,Et Di 1.033 D;' 1.01'7 b. p. 112-114°/14 mm. 116.5-lIS*5°/19 mm.obtained by condensing ethoxyscetonitrile with ethyl a-bromopro- pionate in presence of zinc (compare Blake Abstr. 1901 i 252) is a faintly yellow liquid which reduces ammoniacnl silver nitrate in the cold and gives a violet coloration with ferric chloride. On hydrolysis with potassium hydroxide solution the ester yields a-ethoxy- butanone and with hydrazine hydrate gives a pyraxolone m. p. 1 35-13io which crystallises from boiling water. Ethyl y-ethoxy-a-ethylacetoacetate Di4 1 -0157 b. p. 125-128"/ 28 mm. similarly obtained resembles its lower homologue and on hydrolysis gives a-ethoxppentsnone and with hydrszine hydrate furnishes a pymxolone m. p. 99-99*5" which crystallises from boiling water in hard prisms. Eihyl y-ethoxy-aa-di?12ethy~(ic~toacetate D 1,065 D:' 1.047 b.p. 114-116°/17 nim. 11 1-1 1Y0/14 mm. obtained by condensing ethyl homoisobutyrate with ethoxyscetonitrile in presence of zinc is a pale yellow liquid reduces amrnoniacal silver nitrate and on alkaline hydrolysis furnishes ethozymethyl isopropyl ketone OEt*CH,*COPrp b. p. 160" (approx.) which gives a ssmicurbazone m. p. 12s-129.5'. Along with the cster there is formed i n this condensation a small quantity of a substance Cl2HI9O4N m. p. 90-9 1*5" which crystallises in needles or prisms is soluble in strong acids becomes yellow in contact with alkdi and gives no coloration with ferric chloride. Heated with alkali in a closed tube it evolves ammonia and Furnishes a trace of isobutyric acid and an unidentified oily product. T. A. H. Iso- and Hetero-poly-acids.11. Oxalato-tellurates. ARTHUR ROSENREIM and 33. W EINEIEBER (Zeitsch. anorg. Chem. 19 1 1 69 261-265. Compare this vol. ii 116) -Concentration of a solution containing molecular proportions of telluric acid and an alkali oxalate leads to the deposition of crystals of the oxtlato-tellurates. The potassium rubidium and caesium salts have the general formulai. 110 ABS'rRAC'fS O F CHEMICAL PAPERS M2C,0,,HGTe0 where M = K Rb or Cs and crystallise in stellar aggregates of needles. The effect of beat on these salts shows t h a t the water is firmly combined so that telluric acid hydrate H,TeO and not the auhydride TeO is probably contained in the complex anion. Their solubilities increase from the potassium through the rubidium to the cmiurn salt this being the opposite order to what generally obtains with salts of these metals Comparison of the solubility of the potassium salt with the solubilities of potassium tellurate and oxaliu acid shows that a great diminution in solubility has taken place pointing to complex formation.This could not be verified by conductivity measurements however owing to the hydrolysis which takes place. Homogeneous ammonium or sodium oxalato- tellurates could not be obtained T. S. P. These compounds should therefore be formulated as M2[ HGTeo,C,o,]* Molecular Rearrangenients in the Camphor Series. VI isoCampholactone WILLIAM A. NOYES and A. W. HOMBERGER (J. Amer. Chem. Soc. 1910 32 1665-1669).-1n an earlier paper (Abstr. 1909 i 133) the authors described a compound obtained by the action of nitric acid on isocampholactone which they regarded as a dilactone of the composition C,HI30,.It has now been found that this substance is in reality a nitrolactone. isoCampholautone prepared by Noyes and Taveau's method (Abstr 1904 i SO?) gave [a]? - 63.1" in an 8.8% solution in alcohol ; Noyes and Taveau found [.ID - 60.7" in a 5% solution. On heating isocampholactone with ammonium hydroxide in a sealed tube a t loo" it yields the ammonium salt of the corresponding acid m. p. 13T0 which is re-converted into the lactone when left in the air When the lactone is heated with nitric acid (D 1-27} a mixture of products is obtained the chief of which is nit.r*oisocamphoEactone NOp-C,H,,<Xo m. p. 122O b. p. 27Z0 which crystallises in needles and has -85-4O in a 5.5% solution in alcohol.A monobasic lactonic acid C,H,,O m. p. 1 3 8 O was isolated from the mother liquor which has [.ID - 4 2 ~ 0 5 ~ in a 6% solution in alcohol ; its barium salt was prepared ; the amide has m. p. 164". Aminoisocamnpholactone NH,-C,H,,<b m. p. 84" obtained by reducing nitroisocampho1;tctone with tin and hydrochloric acid forms small crystals and is decomposed by sodium hydroxide with formation of a compound m. p. 152O. CO Hydl.ozylamninoisoca~~?~oZacton~ co 0 ' OHqNH*C,HI,< I m. p. 144O prepared by treating nitroisocampholactone with zinc dust and acetic acid forms small stellate crystals is slightly basic and readily reduces Fehling's solution. When nitroisocampholactone is shaken with OBN-sodium hydroxide until completely dissolved and afterwards acidified with hydrochloricORGANIC CHEMIS'I'RY.1. 111 acid an acid C,H,O,N*CO,H m. p. 73-74' is produced ; its barium salt crystallises in needles containing 2&H20 By the action of ammonium hydroside on nitroisocampholactone the corresponding amide m. p. 96-97' is obtained. E G. Molecular Rearrangement8 in the Camphor Series. VII. Derivatives of isoCamphoric Acid ; I-Hydroxydihydro- campholytic Acid. WILLIAN A. NOYES and LUTHER KNIGHT (J. A n w . Chem. Soc. 1910 32 1669-1674).-d- and l-isoCamphoric acids are usually regarded as cis- and trans-isomerides As however the evidence of this structure does not seem altogether conclusive in the case of the latter compound the present work was undertaken in order to throw some light on the question.Assuming that iso- camphoric acid is stereoisomeric with camphoric acid a is used in this paper to denote the secondary carboxyl and /3 the tertiary carboxyl group. By boiling isocarnphoric acid with methyl alcohol and sulphuric acid the a-methyl and dimethyl esters are obt:tined. The dimethyll ester C,H14(C0,Me)2 b. p. 146"/27 mm. has D2" 1.073 D@ 1.069 and [a]g - 65.3" ; a 10% solution in alcohol has [a]" - 63%'. The a-methpl ester m. p. 88' crystallises in needles and gives [.ID - 57.9'in a lo?; alcoholic solution ; its avaide m. p. 157" crystallises in plates arid has [a] - 60.05' in a 10% alcoholic solution /3-isoCan~pi~orarnic acid C0,H*C8Hl,*CO*NH in. p. 165-166' obtained by hydrolysing the a-methyl ester amide with sodium hjdroxide crystallises in needles.When i:s sodium szlt is treated with sodium hypobromite solution ccnz~.izoisod~hydrocccnapho~~t~c acid CO,H-C,H,,*NH,,. m. p. 225-22'i0 is produced ; its hydrochloride and lead salt are described. When this acid is heated a t 250-300° it is converted into an unhgdride which furnishes R mitroso-compound m. p. 194". Jf aniinoisodihy drocampholytic acid hydrochloride is treated with a solution of sodium nitrite there are produced a hydrocarbon a lactone d-campholytic acid and l - l ~ ~ d ~ o x ~ d i i ~ y d r o c ~ ~ ~ ~ p ~ ~ o acid CO,H*C,H,,-OH m. p. 132' which forms granular crystals and gives [ u ] ~ - 70.04' in an aqueous solution containing 1.45%. The formation of this compound instead of hydroxydihydroisocnmpholytic acid which was expected renders it probable that the former is the more stable and that part of the hydroxydihydroisocampholytic acid is converted into i t by the action of the nitrous acid or else that d-campholytic acid is formed as an intermediate product and unites with water to produce I-hydroxydihydrocampholytic acid.E. G. Saccharinic Acids. HEINRICH KILIANI (Ber. 19 1 1 44 109-113).-A reply t o Nef (Abstr. 1910 i 714). The phenyl- hydrazide of a-metasaccharin has m. p. 145" as previously found and not 113-115' as stated by Nef. The trihydroxyadipic acid described by Kiliani and Eisenlohr (Abstr. 1909 i 553) is not identical with the old trihydroxy-acid; it has m. p. 159-160° whereas a mixture of the two melts a h 142-145°. The silver salt also does not crystallise in the small plates characteristic of the silver salt of the old acid The presence ofi.112 ABSTRACTS OF CHEMICAL PAPERS. a compound with a branched chain in parasaccharin has been con- firmed by reduction to a-ethylbutyrolactone and the isolation of this in the form of Chanlaroff's calcium salt 3Ca(C,Hl10,),,2H20 (Abstr. 1885 374). The yield of calcium salt however is small and large quantities of syrupy salts are formed. By oxidising parasaccharin with nitric acid t o parasaccharone (Abstr. 1904 i 975) and reducing this with hydriodic acid a small amount of n-adipic acid has been obtained. These results indicate that parasaccharin must be a mixture. Nef's parasaccharin (a-d-galactometasaccharin) does not appear to be hygroscopic whereas the author's preparations are excessively hygroscopic.The acid obtained by the oxidation of barium parasaccharinic acid is not hydroxycitric acid as stated previously (Abstr. 1904 i 976) but &tartaric acid. J. J. S. Glucodeconic Acids. L. H. PHILTPPE (Conzpt. rend. 1910 151 1366-1367. Compare this vol. i 12).-On evaporating an aqueous solution of p-glucodeconic acid a mixture of two compounds is obtained (1) the hydrated p-lactone C,,H,,O, H20 crystaltising in hemihedral needles rn. p. 135' (anhydrous m. p. 193') [a]:7-41.2'; (2) a n anhydride C20H3s021 separating in microscopic granules resern bling those of starch m. p. 216-.218' [a] about - 10'. The lactone is the chief constituent in dilute solutions whilst the anhydride pre- dominates in concentrated solutions. The p-lactone is also formed when the a-lactone is heated a t 140' in pyridine. Sodium P-glucodeconate is gummy but the barium cadmium and strychnine salts are crystalline.The P-phenplhydrazide crystalliees in needles m. p. 246' and is ten times more soluble in water than the a-compound. w. 0. w. Derivatives of Aldol and Crotonaldehyde. RUDOLF W EGSCHEIDER and ERNST SPATH (iionatsh. 1910 31 997-1029).- The authors have examined the behaviour of aldol towards acetylating agents under various conditions and find that acetylation is accom- panied by the formation of condensation products; loss of water and rupture of the aldol molecule also occur. When aldol is boiled with acetic anhydride in the presence of a little sulphuric acid ethylidene acetate and mZdoZ triacefate OAc-CHMe*CH2*CH(OAc) are produced.The latter substance is a colourless oil b. p. 138-140'/ 1 2 mm. which yields crotonaldehyde when boiled with water or alkalis; when treated with bromine in chloroform solution it is converted into bromocrotonaldehyde. Gentle acetylation of aidol with acetic anhydride and sulphuric acid in benzene or chloroform solution yields amont. st other products aldol nzonoacstute OAc*CHMe*CH,*CHO; i t is a colourless oil b. p. 87-89"/18 mm. and is also obtained by the action of acetic acid and a little sulphuric acid on xldol a t the ordinary tempeiaature. By heating aldol with acetic anhydride alone Wurtz (this Journ. 1872 808) obtained two substances which he considered to be croton-OROAKIC CHEMISTRY. i. 133 aldehyde diacetate and acetylaldol. The authors have repeated Wurtz's experiments and find that his crotonaldehyde diacetate consists of a mixture of aldol triacetate and a compound Cl2HI8O5 whilst the substance described as acetylaldol is identical with crotonaldehyde diacetate.The compound C12H1805 is probably the diacetyl deriv- ative of dialdan C,H,,O a substance obtained by Wurtz by the action of acids on aldol; i t is produced by gently acetyIating aldol with acetic anhydride and sulphuric acid either alone or in chloroform and benzene solution and also by the action of acetic and sulphuric acids on aldol at the ordinary temperature; the b. p. varies from 144-147'/13 mm. to 152-154"/12 min. according to the method of preparation but whether this variation is due to impurity or the presence of two dialdan diacetates has not been decided.The constitution of the compound is discussed and arguments advanced in favour of the formula OAc*CHMe-C H (CHO) *C H( OAc)-CH CEI Me. The following condensation products were also isolated and examined a diacetate of C12H2,,02 colourless oil b. p. 201-203°/ 10 mm. produced by acetylating aldol with acetic anhydride in the presence of a little sulphuric acid and probably having the structure a substccnce C18H,,07 $!HRle.O* CHMe CHO CH,-CH(OAC)>~<CH(O~C)*CH CHMe ' b. p. 228-233"/13 mm. obtained by the action of a mixture of acetic and sulphuric acids on aldol and represented as a monoacetyl derivative of ? OH*CHMe*CH(CHO)*CH(OH) CHBIe-- CHMe:CH*CH(OIs)>c<CH(O H)*C'H,*C HMe ' a mixture of the monoacetyl derivatives of C8H1403 and C8H160+ produced by acetylating aldol with acetic anhydride and sulphuric acid in chloroform solution Acetyl chloride reacts with aldol in benzene solution forming a-chlorocrotyl acetate CHMe:CH-CHCl-OAc b.p. 76-77'1 18 mm. ; the same substance is also produced by the addition of acetyl chloride to crotonaldehyde. When aldol is acetylated by means of acetic anhydride in the presence of sodium acetate the main product is crotonaldehyde diacetate. AZdo/phenythydraxone is obtained in an impure condition by the action of phenylhydrazine on aldol in ethereal solution ; it is a viscid oil b. p. 196"/10 mm ; the p-nitrop7~enyZhydraxone crystallises in reddish-yellow needles m. p. 109-1 1 lo with previous sintering a t 107' ; aldoloxime has b.p. 117-1 1S0/1 1 mm. Crotonalclehydep~en~Z~~ydrazone prepared by the action of phenyl- hydrazine on crotonaldehyde in alcoholic solution a t 35-42O is a yellow oil b. p. 156-158O/11 mm. (compare Trener Abstr. 1901 i 232) ; the p-nitrophenylhydrazone crystallises in brown needles m. p. 1 S4-185". The authors also describe two new condensation products of acetaldehyde. A specimen of crotonaldehyde which had been kept for three and a-half months in a closed glass vessel filled with carbon dioxide,. yielded on distillation an oil ClOHl8O4 b. p. 88-95"/16 mm. and a viscid liquid C,,H2s0 b. p. 156-161°/16 mm. It is suggestedi. 114 ABSTRACTS OF CHEMICAL PAPERS that these two substances are produced by the condensation of acetaldehyde derived from the para-aldehyde (with which the original crotonaldehyde was probably contaminated) according t o the equations Cl,Hl,Op = 5C,H,O - H,O and CI,H,,O = 8C2H,0 - 2H,O.F. B. FARBEN- FABRIKEN VORM.FRIEDR. BAYER & Co. (D.R.-P. 227176).-The methylene ketones employed in the following reactions were recently described (Abstr. 1910 i 653) ; it is now found that they polymerise readily yielding octendiones (and higher polymerides) of considerable thera- peu tic importance. A,-Octen-yr]-dio?te 11. p. 75-76'/21 mm. a colourless oil sparingly soluble in water and with a penetrating odour is prepared by the long boiling of methyleneacetone under reflux and subsequent fractional distillation of the products its semicarbuxone has m. p. 199". Pfj-DivtetlL yZ-Aa-octen-yr]-dione COMe- CHMw CH CH,*CO CMe CH is prepared in a similar manner from methyl methylene-ethyl ketone but owing to the higher temperature employed more of the higher poly- merides are simultaneously produced ; it is a colourless highly refractive oil b.p. 187-194" or 83-85"/17 mm. with pine-like odour immiscible with water and slowly decomposed by boiling at atmospheric pressure into its progenitors ; its seniioadaxone has m. p. 183". Dimethyl- octendione can also be obtained by tho slow distillation in a vacuum of P[-dimethyloctan-yq-dione-a-ol (see this vol. i 102) with a n equal weight of hydrogen potassium sulphate or by boiling it with acetic anhydride. Preparation of Octendione and its Homologues. F. M. G. M. The Influence of'. I n a c t i v e Substances on the Rotation of La3vulose.NEUMANN WENDJCR (Biochem. Zeitsch. 191 1,30 357-373). -The addition of inorganic acids to a solution of I~vulose was found in most cases to increase the specific rotation the increase varying with the degree of acidity of t h e solution. Inorganic salts as well as organic acids varied in their behaviour causing in some cases a rise in others a decrease in the rotation. Alcohols and acetone produced a marked diminution in the rotation which was proportional t o t h e amount added. W. J. Y. Mercerised Cellulose. CHARLES F. CROSS (Ber. 1911 44 153-154).-1n connexion with Miller's results (this vol. i 17) it is pointed out that bleached cotton is not a homogeneous cellulose and that by t h e action of sodium hydroxide solution the P-celluloses are dissolved.Previous heating at 90-100' renders the P-celluloses still more reactive towards alkalis. The increase in weight of tho cellulose on hydration is compensated by the loss in weight due to the removal of the P-celluloses (compare Cross and Bevan '' Cellulose," pp. 4 and 28). The author upholds the view t h a t a definite series of hydrated c?lluloses exists and t h a t these are stable within the limits 0' t o 50'. J. 3 . S. Mercsrised Cellulose. CARL G. SCRWALBE (Be?.. 1911 44 Compare preceding abstract).-Attention is drawn t o the 161-1 52.ORGANlC CHEMISTRY. i. 115 fact that during treatment with sodium hydroxide solution a portion of the cellulose is dissolved. Previous experiments (Abstr. 1908 ii 627) have shown that mercerised cellulose does not contain water (compare also Ost and Westhoff Abstr.1909 i 210). According to Liebermann (Dingler's polyt. J. 1886 1 8 1 133) an aqueous solution of rosaniline base does not dye cotton-cellulose. For behaviour of mercerised cotton towards sitbstantive dyes compare Knecht (J. SOC. Dyers 1908 24 6S) and Hiibner and Pope (.I. doc. Chem. Ind. 1904 23 401). Cellulose. 11. Hydrocellulose. H. JENTGEN (Zeitsch. angew. Chem. 1911 24 11-12 Compare Abstr. 1910 i 654).-1n support of the view that acid in the molecular condition brings about the conversion of cellulose t o hydrocellulose (compare Schwalbe Abstr. 1910 i 817) the following facts are given (1) A 1% aqueous acid solution has practically no hydrolysing effect ; (2) Methyl or ethyl alcoholic solutions act slowly and the action depends on the amount of dissociation ; (3) 1% solutions of acids in non-ionising media.hydrolyse readily. The compounds of cellulose with the molecular acids are regarded as catalysts. The hydrolysis observed by Schwalbe during acetylation is regarded as a secondary or tertiary process. J. J. S. J. J. S . Hydrocellulose. CARL G. SCHWALBE (Zeitsch. angew. Chem. 191 1 24 12-13. Compare Abstr. 1910 i S17).-Mainly polemical in reply to Jentgen (preceding abstract). Acyl Derivatives of Guanidine. WILHELM TRAUBE (Be?*. 19 10 43 3586-3590).-Guanidine interacts with the esters of monobasic acids forming simple acyl guanidines. Formylguanidine NH,*C(NH)*NH*CHO separates in crystalline granules m. p. 1'75" (decomp.). On shaking with bromine formylbromo- guanidine results ; it crystallises in almost colourless needles which decompose violently at 125'.Acetylguaniclirbe separates in colourless rhombic crystals m. p. 185' to a clear liquid; on further heating i t solidifies and the new compound after crystallisation from water has m. p. 261O. Acetyl- guanidine hydrochloride has m. p. 145" (Korndorfer found 142q Arch. Pharm. 1903 241 449). Chloroacet~lguanidir~e crystallises in slender colourless needles m. p. 125O. Tricrl~lo~oacet~lguanidine forms small colourless crystals In. p. 183' ; the hydrochlos.ide crystallises in platelets. Uenxoylguanidiue forms short colourless crystals m. p. 160' ; the bydrochloride separates i n lustrous needles m. p. 207" (Korndorfer found 210° loc. cit.). m-Nitrobenxoylguanidine crystallises in stellate needles m.p. 195-197". E. F. A. J. J. S. Complex Salts of Certain Amino-acids. LEO TSCHUaAEFF and E. SERBIN (Compt. rend. 1910 151 1361-1363).-a-Amino-acids form stable complex internal salts with certain heavy metals ini. 116 ABSTRACTS OF CHEMICAL PAPERS. this respect differing from the p- 7- and &acids which appear unable to do so. The following salts are sparingly soluble and were pre- pared in each case by boiling a n aqueous solution of the amino-acid with somewhat less than the calculated amount of purpureochromium chloride. The glycine salt Or ( \ **:zg:2)3 crystallises i n small bright red prisms; it is stable at 300° and is not decomposed by boiling with alkalis or dilute acids. ( .-NH,*ClfMe )5 has a similar c o n s t h i o n The ulunine salt Cr x0-- and shows the same properties; it crystallises in rosy needles.The aspctragine derivative Cr( C,H70,N,) is less soluble and separates in microscopic rose-violet needles. a- Aminoisobutyric acid a-arninoiso- valeric acid and leucine form similar compounds. The salts can a l e 0 be prepared but in a less pure state by boiling the amino-acids with a n aqueous ammoniacal solution oE chromic chloride. When glycine is treated in this way a basic salt is obt.rined for which the OH 00NH2*(?H2)2 is suggested. constitution ( Xz2”HG>)2Cr<OH>Cr (KO --co w 0. w. Action of Carbon Disulphide on Amino-acids. MAX SIEGFRIED and 0. WEIDENHAUPT (Zeitsch. physiol. Chem. 1910 70 152-160).-Carbon disulphide combines with amino-acids in the presence of barium hydroxide or other alkalis in much the same manner t h a t carbon dioxide does (compare Abstr.1905 ii 332 ; 1906 i 324 ; 1908 i 379) yielding dithiocarboxylic derivatives of the amino-acids; for example glycol yields a salt of CO,H-CH,*NH-CY*S H. Nost of the salts are readily soluble but when treated with benzgl chloride yield spaiingly soluble acid benzyl esters of the type C0,H*CH2*NH*CS*S*UH2Pb by means of which the dithiocarboxylic acids can be isolated with great ease. Benxyl hydrogen glycinedithiocarboxylate C,,H,,02NS2 crystallises from water in long broad colourless needles with a silvery lustre and has m. p. 165’; 100 C.C. of an aqueous solution saturated at t h e ordinary temperature contains 0.0096 gram of ester. The bavium salt ( C,,Hlo02NS2),Ba cry stalli5es from hot water in broad needles.The yield ot ester is 50% when the theoretical amount (2 mols.) of potassium hydroxide (78.6% solution) is used but falls t o nil when 1.5 times the theoretical amount is used. Benayl hydrogen dl-alunincditl~iocur~oxylnte CO,H* CHMe-N H*CS,*CH,Ph crystallises from water in Short colourless glistening needles m. p. 136’. I t s solubility a t 20’ is 0-0102. Benzyl hydrogen pheny Iglycineditl~rocarboxylute CO,H*CH,*NPh* CS,*CH,Ph crystallises from water i n slender needles m. p. 171’. Its solubilityORGANIC CHEMISTRY. i. 117 in water at 20" is 0.0038 and it is only sparingly soluble in hot water. The acid beizxyl ester of difhioca~boxyphenylarninoacetic acid CO,H* CHPh*N H*C'S,,*CH,Ph crystallises from aqueous alcohol in needles m.p. 88" ; the butiurn salt (C,,H,,O,NS,),Ba crystallises in slender needles. Banxyl hydrogen samosinedithiocarboxylute CO,H*UH,*NRle* CS,*CH,Ph crystallises from hot water in colourless needles m. p. 1 2 5 O and has solubility 0.0153 a t 20". The barium salt forms rhombs. Benxyl hydrogen as~arccgi.i.zedit~iocc~rbozyZate CO K*C,N,( CO*NH,)-NH*CS,*CH,Ph has m. p. 180° and yields a barium salt which crystallises i n slender needles. Similar compounds have not been obtained from arginine lysine histidine aspartic acid and glutamic acid ; the leucine derivative is oily. The formation of the sparingly soluble benzyl ester affords a simple method for the separation of glycine from aspartic or glutamic acids. J. J. S. Syntheses of Bases of the Sugar Group.EMIL FISCHER and KARL ZACH (Ber. 19 1 1 44 132-1 35) .-AminomethyZglucoside hydro- bromide C7H1505N,HEr is formed when triacetylmethylglucoside bromohydrin (Fischer and Armstrong Abstr. 1902 i 263) reacts wit,h ammonia a t the ordinary temperature The acetyl derivative (10 grams) is sealed up with 12-15 C.C. of solid ammonia. The temperature is allowed to rise gradually t o the ordinary temperature at which it is kept for seven days and the tube then opened after the ammonia has been again solidified. After removal of the excess of ammonia the syrup is extracted with absolute alcohol the alcohol evaporated under reduced pressure and the residue extracted with warm dry ethyl acetate which removes acetamide and leaves a mixture of ammonium bromide and the hydrobromide of the amino- glucoside; the latter is obtained from t h e mixture in a crystalline form by dissolving in a little warm methyl alcohol and adding much ethyl acetate.To remove the last traces of ammonium bromide the compound is dissolved in absolute alcohol. The yield is 56% of the theoretical. The salt has not a well-defined m. p. but melts and decomposes at about 2 0 5 O (corr.). The hydro- chloride has m. p. 315" (decomp. corr.) and [.]? -25*l0 and both salts dissolve readily in water. The free base dissolves in methyl alcohol but is precipitated as a flocculent mass on the addition of ether. When heated with N-hydrochloric acid in a sealed tube at looo the hydrochloride yields the salt of an amino-sugar. This reduces Fehling's solution b u t is not identical with glucosamine hydrochloride since i t dissolves more readily in water and concentrated hydrochloric acid and is decomposed much more readily than glucosamine by con- centrated hydrochloric acid.The osazone which it yields with sodium acetate and phenylhydrazine hydrochloride is not identical with p hen y 1 g 1 ucosazone. It has [a] - 21.2". J. J. S . VOL. c. i Ei. 118 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Double Compounds of Carbamide with Alkaline-earth Bromides. GEHE & Co. (D.R.-P. 226224).-The action of carbamide on the alkaline-earth bromides yields compounds of therapeutic value in heart complaints. Culcium bvomocaybumide m. p. 186' is prepared by heating calcium bromide (250 parts) with carbsmide (225 parts) in the presence of a small quantity of alcohol or water during three hours under a reflux condenser ; it crystallises from alcohol or ether.F. M. G. M. Preparation of Substituted Carbamic Acid Esters. VEREINIGTE CHININFABRIKEN ZIMMER St Co. (D.R.-P. 22571 2)- a-Methyl-P-tciclhloroethyZ allop?hanate C,I&O,N,CI3 prisms m. p. 186O is prepared by heating trichloroisopropyl alcohol (1 mol.) with carbamic chloride (2 mole.) on the water-bath. Yetrachloroethyl ullophanute C,I3,O3N2CI is obtained by substitut- i n g chloral for the alcohol in the foregoing preparation and allowing the mixture to remain a t the ordinary temperature during two days; it forms colourless crystals which decompose at about 1 60'. When molecular proport ions of trichloroisopropy 1 alcohol and p - e thox y - phenylcarbimide are heated together at 1 S5O ts.ichloroisopropy1 p-etIiox~~T~en?/Zcarbamc~te C,,H,,O,NCl is obtained as a syrup which after crystallisation from petroleum has m.p. 86'. Preparation of Esters of Allophanic Acid. CHEMISCHE WERKE VOBM. DR. HEINRICH BYK (D.R.-P. 236228).-Tertiary alcoholic esters which are therapeutically important are not readily prepared by the ordinary methods and allophanic tertiary alcoholic esters have not previotisly been obtained. AnayZ atlophanate CMe,Et*O*CO-NH*CO*NH colourless needles m. p. 149-150° is prepared by treating a cooled solution of ainylene hydrate in an indifferent solvent with cyanic acid and evaporating in a vacuum ; i t is sparingly soluble in water ether or benzene readily so in alcohol and is decomposed by hot alkalis.Preparation of a-Bromo-a-ethylbutyrylcarbamide. FARBEN- a-et~~ylbutycylcarbamide CBrEt,*CO*NH*CO*NH colourless tasteless odourless crystals m. p. 1 14-1 1 f0 and of therapeutic value is prepared (1) by heating a-bromo-a-ethylbutyryl bromide (obtained by the action of bromine on a-ethylbutyric anhydride) with carbamide at 100' ; (2) by the action of sulphuric acid on a-bromoethylbutyrylcyanamide (prepared from cyanamide and a-bromoethylbutyryl chloride) ; (3) from the interaction of ammonium acetat,e with phenyl a-bromo-a-ethyl- 6utyrpZcarbnrnute which forms colourless crystals and is prepared from a-bromo-a-ethylbutyryl bromide and the sodium derivative of phenyl carbarnate ; (4) by the oxidation of a-bromo-a-ethylbutyrylthiocarb- amide with potassium permanganate or (5) the direct brornination of a-eth ylbutyrylcarbamide. Calcium Cyanamide.NIKODEM CARO (Zeeitsch. angew. Chem. 19 10 23 2405-241 7).-[ With B. Scauc~]-\Vlien solutions contain F. M. G. M. F. M. G. M. FABRIKEN VORM. FRIEDR. BAYER & C O . (u. R.-P. 225710).--a-Bromo- F. 31. G. Rl.ORGANIC CHEMISTRY. i. 119 ing dicyanodiamide and silver nitrate in the mol. proportions 1 I 2 1 and 3 1 are mixed the compounds AgNO,,C,H,N AgN0,,2CpH4N4 and AgN03,3C,H4N are produced. The first of these substances is converted by sodium hydroxide into the compound C,HpN,Ag whilst the second yields a mixture of the same compound and sllver oxide. Silver dicyanodiamide decomposes when boiled first into silver cyanamide ; when the boiling is more prolonged the latter is further decomposed with production of cyanamide.Cyanamide dicyanodiamide and carbamide are estimated as follows Calcium cyanamide (7 grams) is shaken for two and a-half hours with 400 C.C. of water and the solution made up to 600 C.C. A portion of the solution (250 c.c.) is treated with ammonia and silver acetate diluted to 400 c.c. filtered and the precipitate mashed. The nitrogen (cyanamide) is then estimated by the Kjeldahl method. A part of the filtrate (300 c.c.) is boiled with potassium hydroxide diluted to 400 c.c. and the nitrogen in the precipitate (dicyanodiamide) estimated as before. A part of the filtrate (300 c.c.) is evaporated down the silver precipitated with hydrogen sulphide and the excess of t h e latter expelled by carbon dioxide.It is then diluted to 400 c.c. and t h e nitrogen (carbamide) estimated in 100 C.C. [With RICHARD JACOBY and B. SCH6CK.]-When calcium carbide is heated in absence of air with 10% sodium cyanide for three hours a t 900° nearly the whole of the cyanide is converted into cyanamide. The same change occurs when barium cyanide is heated in a current of acetylene diluted with hydrogen. [With B. Sc~ucK.]-\vhen calcium 2yanamide is heated in a current of dry carbon dioxide the carbide present is completely decompoled and the calcium cyanamide is decomposed with production of carbon. [With R. .TACOBY and B. SCH~JCK.]-AS regards the alleged production of nitrides by the action of nitrogen on a mixture of alumina and carbide it was found that neither nitrides nor cyanamide are produced at 800-1 200° products being obtained containing not more than 0 8% per cent. N st the lower temperature and generally no nitrogen a t temperatures of 1000" or more.Calcium carbide when heated with alumina in an inert atmosphere yields a black substance concaining neither calcium nor aluminium carbide. [With B. Sc~ijc~.]-Piire cyanamide can be prepared by slowly adding sodium cyanamide to well cooled strong hydrochloric acid and distilling off the water in a vacuum. The cyanamide is then dissolved in ether. It can also be obtained by adding a concentrated solution of aluminium sulphate to a n aqueous extract of calcium cyanamide. The filtrate is distilled in a vacuum and extracted with ether. Cyanamide forms colourless crystals m. p. 41-42" readily soluble in water alcohol and ether.When heated it is at onceconverted into dicyano- diamide (in. p. 2 0 4 O ) ; the same change takes place when it is exposed t o air. [With I:. JACOBY.]-T~~ temperature n t whbh nitrogen acts OD mixtures of baryta aud carbon is reduced by adding fluorides; the I,. 2i. 120 ABSTRACTS OF CHEMICAL PAPERS. action takes place at a temperature below the m. p. of the fluoride. When a mixture of barium carbonate carbon and calcium (or barium) fluoride is heated without nitrogen a t the temperatures employed for nitrogen fixation there is a production of carbide. No carbide is formed at this temperature in absence of fluoride. N. H. J. M. Preparation of Phenylnitromethane [a-Nitrotoluene] by the Action of Mercurous Nitrite on Benzyl Chloride.PARCHANAN NEOGI and BIRENDRA BIIUSAN ADHIC~RY (Zeitsch. c6nol.g. Chem.. 191 1 69 270-272).-o-Nitrotoluene is readily obtained by the inter- action of mercurous nitrite and benzyl chloride the reaction mixture being fractionally distilled under diminished pressure. The yield is much better than when silver nitrite is used. T. S. P. Preparation of Diphenylmethane and its Homologues. ERNST VON MEYER (J. pr. Chem. 1910 [ii] 82 538-540).-The hydrocarbon obtained by the action of phosphoric oxide on benzyl ethyl ether in benzene solution and regarded by Schickler as an isomeride OF stilbene is shown to be diphenylmethsne not only by the fact that it is not formed wheu light petroleum is used as the solvent but also by its oxidation to benzophenone by chromic and acetic acids and by its nitration to 4 4'-dinitrodiphenylmethnne and tetranitro- diphenylmethane.Phenyl-p-tolylmethane and phenyl-a-naphthylmethane are obtained in a similar manner by replacing the benzene by toluene and naphthalene respectively ; p-chlorodiphenylmethane is obtaiiied by using p-chlorobenzyl ethyl ether instead of benzyl ethyl ether and triphenylmethane by employing diphenylmetbyl ethyl ebher. c. s. Triphenylmethyl Chloride Diphenylcarbamyl Chloride and Cyanuric Bromide Acting as Acid Halogenides. ERNST VON MEYER (J. pr. Chem. 1910 [iiJ 82 521-538).-A compnrative study of transformations in which trjphenylmethyl chloride diphenyl- carbamyl chloride and cyanuric bromide function as acid halogenides. [With P. FiscHE~.l-l'riphenylmethyl chloride reacts with carbamide methylcarbamide and phenylcarbamide in pyridine to form s-ditri- phe4lyzmethylcccrbarif~e CO(NH*CPh,) s-triphenyZmeth?lZ~,zeth?/Zcnrb- mnide NHMe*CO*NH-CPh m.p. 263O and s-phenyltriphenylmethyl- carbunzide NHPhG0.N HOCPh rn. p. 2 4 2 O respectively and with thiocarbamide to form tl.iphenylmelhyEthiocarbccmide NH,*CS*NH*CPh m. p. 217'. Triphenylmethyl chloride reacts with potassium phthal- co imide a t 200' to form triphenyZmethylphthalimide C,H,<CO>N*CPh m. p. 172y with pyrrole and with piperidine yielding triphan.yltueth?yI- pyrrole C,NH,*CPh m. p. 258O and trii0iLenylmethyl~ipel.idine C,NH,,*CPh m. p. 153O respectively and with pyridine or yuinoline in benzene solution readily forms the crystalline additive compounds C,NH,,CPh,CI m.p. 171° and C,NH,,CPh,Cl m. p. 163" which are decomposed by water or alcohol and form intensely yellow solutions in hot pyridine. When fused with phenol or with resorcinol triphenyl- methyl chloride yields p-hydroxytetraphenylmethane and dihydroxy-ORGANIC CHEMISTRY. i. 121 tetrup~&enylmet?&ane CPh,*C,H,(OH) m. p. 268' respectively ; with mercaptans in benzene or ethereal solution however the chloride acts as a n acid chloride yielding thio-ethers triphenylmethyl methyl sulphide m. p. 105' from methyl mercaptan triphanylmethyl ethyl sulphide m. p. 125' from ethyl mercaptan and phenyl triphenylmethyl sulphide m. p. 105O from phenyl mercaptan. Triphenylmethyl chloride reacts with alcoholic p toluene-sulphinic acid a t 1 30' to'form acetaldehyde and triphenylmethnne by the decompohition of the initially formed tri- phenylmethyl ethyl ether and yields with sodium p-toluenesulphinate in benzene p-tolyZIri~hsnylmethyZsulr)hone CPh,*SO,*C,H,Me m.p. 173' which is decomposed by water into triphenykarbinol and p-toluenesul phinic acid. Triphenylmet hyl chloride reacts in ether with magnesium benzyl chloride to form triz~hennylbenzylmethane m. p. 140° with magnesium p-chlorobenzyl chloride to form triphenyl- p-c~~Zorobsnx~,lmethane m. p. 172' and with magnesium phenyl bromide to form diphenyl and triphenylmethyl the latter being obtained in the form of its peroxide. [With A. NIcoLAos.]-DiphenylcArbamyl chloride and pyridine yield an additive compound C,NH,,NPh,*COCl m. p. 107'. which forms a platinic?&wicle decomp.170' picrate m. p. 161' and iodide m. p. 182'. The formation of esters from diphenylcmbamyl chloride and alcohols only occurs very slowly ; easily however in the presence of a little alkali or potassium cyanide ; ethyl diphenylcarbamate has m. p. 72' the corresponding methyl arid isop-opyl esters 86' and 117' respectively. lbipheny lsemicai*baxide ( R-D iphe n y barbam ylphen y lh ydrazide) NHPh*N H COON Ph (ncetyl derivative m. p. 165' ; nitroso-compound m. p. 131') is obtained readily from phenylhydr azine (2 mols.) and diphenylcarbamyl chloride in benzene and is oxidised by alcoholic ferric chloride to diphenpl- ca~,bam~luxo~l~enyl NPh N*CO*KPh In. p. 1 3S0 red needles which develops a deep red coloration with conwntrated sulphuric acid. The interaction of diphenylcarbamyl chloride and aliphatic amino-acids is accomplished best by employing the latter in the form of their esters or sodium salts acetone being used AS solvents ; thus a-diphsnyl- carba~niflo)7ropio?zic acid CO H *CHMe*NK*CO*NPh m.p. 1 4 9 O is obtained from alauin e a n d u-diphen y lcar bamidohexoic mid CH,Me*[CH,];CH (CO,H)*NH*CO*NPh in. p. 52' from leiicine. E'th!/Z o-dii)henyZcarban2idobenzoc~t~ C0,Et*C,H,*NH*CO*NPh2 m. p. 1OSo obtained by heating eqiial molecular quantities of ethyl anthrxni1:tte and dipheriylcarbamyl chloride with a n excess of zinc dust R t about loo' yields the free acid m. p. 178' by hydrolysis. The halogen in diphenylcarbarnyl chloride is readily replaced by an aikyl or aryl group by the Grignaril reaction ; thus with magnesium ethyl iodide i t yieltls diphen?/lpl.ot'ionccmide m.p. 58' with magnesium propy1 bromide diphsn?l?butyrarriide m. p. 47' and with magnesium phenyl bromide diiul~s?z?/lbenzamide m. p. 176'. Diphenylcarbumyl cyanide NPh,*CO.CN m. p. 126' obtained from the chloride and an excess of potassium cyanide at 1 80-200° yields diphenylamine hydrogen cyanide and carbon dioxide by hydrolysis with alcoholici. 122 ABSTRACTS OF CHEMICAL PAPERS. potassium hydroxide; it forms an amido-oxime NPh,*CO*C(NH,):NOH m. p. 2225" with alcoholic hydroxylamine at 60-80° and is converted in alcoholic eolution into the tlhioamide NPh,*CO-CS-NH m. p. 220' by hydrogen sulphide in the presence of aqueous ammonia. {With FRAULEIN NA~~.]-Cyanuric bromide is obtained in 70-80% yield by the action of nascent hydrogen bromide on a benzene solution of cyanogen bromide. Cyanuric bromide forms cyanuric trihydrazide with 10% hydrazine cyanuric triphenylhydrazide with ethereal phenyl- hydrazine and in boiling benzene reacts ( a ) with o-chloroaniline t o form cyanuric tri-o-chloroanilide (trichlorophenylmelaarraine) m.p. 161'; (b) with 2 4-dichloroaniline to form cyanuric tri-2 4-di- chloroanilide m. p. 261"; (c) with nz-nitroaniline to form trinitrophnyl- melamine (CN),(NH*C,H,*NO,) ; (d) with a-naphthylamine to form iri-a-napl~t~~ylmelumiiae (CN)3(NH*C,oH7)2 m. p. 225"; (e) with methyl- aniline to form tripheiayltrimellyl~el~rna~e (CN),(NMePh) m. p. 1 15" ; (f) with benzylaniline to form triphen~ZtribenzyZm~elamine m. p. 1 20' ; (9) with $7-aminophenol to form cyanuric di-p-hydroxyanilide bromide (CN),(NH*C,H,*OH),Br m.p. 275' (decomp.) ; ( I t ) w i t h p-anisidine to form a correspoading anisidide (CN),(NH*C,H,mOMe),Br rn. p. 250' (decomp.) and (i) with anthranilic acid to form the substance (CN),(NH*C,K,-CO,H),Br m. p. 197'. Cyanuric bromide and carb- amide (3 mols.) at 130-140' yield ti*icarbamylmelamine m. p. above 300". Cyanuric bromide reacts in the normal way with aluminium chloride and an aromatic hydrocarbon in the presence of carbon disulphide forming substances of the type (CN),Ar,; -4r=Ph m. p. 231"; Ar-p-C,H,Me m. p. 275-276"; A r = 3 4-C6H,Me m. p. 210" ; Ar = 2 4-C,H,Me2 m. p. 155"; Ar =p-C,H,*OMe m. p. 115" ; A r = a-CIoH1 m. p. 190-200" ; the constitutions of these compounds (excluding the first) are determined by the fact that hydrolysis by hydrochloric acid at 200-220' yields p-toluic 3 4-dimethylbenzoic 2 4-dimethylbenzoic anisic and a-naphthoic acids respectively.The analogous triethyl compound (CN),Et obtained by Otto and Voigt from dicliloropropionitrile is also produced by the interaction of (CN),(NH.C6H,Cl) (CW),(NH*CO*NH,) cyanuric bromide and ethereal magnesium ethyl iodide. c. s. Triarylmethyls. v. WILHELM SCHLENK and ANNA HEGZENSTEIN (Bey. 1910 43 3541-3546. Compare Abstr. 1909 i 791; 1910 i 236 237 469).-According to the authors the sole objection t,o the hexaphenylothane formula for the colourless form of triphenylmethyl lies in the comparative stability of the closely related pentapbenylethane. Investigation of the behaviour of the latter compound in high boiling solvents shows however that the remarkable power of dissociation characteristic of " colourless " triphenylmethyl is also shared by pentaphenylethane a1 though in a less marked degree.Solutions of pentaphenylethane in anisole or ethyl benzoate on being heated rapidly t o boiling acquire the deep yellowish-brow11 colour of n hot solution of triphenylmethyl ; on quickly cooling the colourORGANIC CHEMISTRY. i. 123 diminishes to a light yellow. The solution decolorises iodine and at once becomes colourless when shaken with air ; the colour however rapidly reappears and finally vanishes only by repeated shaking with air. This behaviour SO closely resembles that of tripheriylrnethyl solutions that there can be no doubt that triphenylmethyl is one of the products of dissociation of pentaphenylethane Ph,C-I-CHPh,.The second dissociation product diphenylmethyl polymerises to tetra- phenylethane which can be readily isolated by boiling pentaphenyl- ethane in ethyl benzoate solution in an atmosphere of nitrogen. On passing oxygen through a boiling solution of pentaphenylethsne in e thy1 benzoate the diphenglmethyl is oxidisecl to tetraphenylethylene. A new method of formation of hexa-arylethanes is also described. When n concentrated benzene 'solution of molecular quantities of 4-pbenyl-triphenylmethaiie and 4-phenyl-triphenylmethyl chloride is exposed to sunlight i t acquires a reddish colour due to the formation of 4-phenyl-triphenylmethyl C,H4Yh.CPh2H + C1CPh;C6H4Ph Z C,H4Ph* CPh,* * a CPh2-C,H4Ph + HCl.The reaction is however reversible the amount of 4-phenyl- t riphenylmethyl being w r y small when equilibrium is attained. In n similar manner phenylbisdiphenylmethpl CPh(C,H,Ph) is obtained from phenylbisdiphenylmetliane and pheriylbisdipheriylruethyl chloride. Q .H Diphenylbisdiphenylene-ethane ?6R4>CPh*CPh< ' 4 on account C,HA G H A of its stability towards hydrochloric acid is produced 'In buantitative yield by exposing a concentrated benzene solution of phenyldiphenylene- methyl chloride and phengldiphenylenemothane (phenylfluorene) to Applications to Phenanthrene. PIERRE BRETEAU (Compt. !rend. 19 10 151 1368-1 369).-By passing a mixture of pherianthrene vapour and hydrogen over spongy palladium a t 160° a mixture of the tetra- and octa-hydride is obtained; when hydrogenation is carried out a t the oiatiinarg temperature in presence of palladium black suspended in cyclohexane only the tetrahydride is formed.Precipitated palladium prepared by treating a solution of the chloride in hydrochloric acid with zinc also yields the tetrahydride when brought into contact with Action of Concentrated Sulphuric Acid on Some Aromatic Nit roamin es. 11. Derivatives of Met hylanili ne Methyl- p-anisidine and Methyltoluidines. FREDSRIC EEVEBDIN (Bull. ASoc. chirn. 1911 [iv] 9 43-49. Compare Abstr. 1910 i 255).- Fiirther instances are given of tbe reduction of the nitro- to the 1,itroso-group by sulphuric acid in certain aromatic nitro-derivatives and i t is shown that this reaction explains why such nitro-derivatives respond to Liebermann's test. 3 4 6-Trinitrophenylmethylnitroamine on treatment with sulphuric acid a t atmospheric temperature furnishes picramide and some nitroso- methylpicramide (Bamherger and Miiller Abstr.1900 j 217). The latter is also produced if alcohol is used along with sulphuric acid the action of sunlight. F. 3:. Hydrogenations in Presence of Palladium. phenanthrene in alcoholic solution. w. 0. w.i. 124 ABSTRACTS OF CHEMICAL PAPERS. but in this case the principal product of the reaction is trinitromethyl- aniline. Dimethyl-p-anisidine on nitration in the cold furnishes the N-nitroso-derivative of dinitromethyl-p-anisidine m. p. 11 1-1 1 3' but with hot nitric acid gives the N-nitro-derivative m. p. 1 2 5 O which may also be obtained by the further action of nitric acid on the nitrosoarnine and conversely the latter is reproduced by the action of sulphuric acid on the nitroamine.Further when the nitroamine is heated with phenol or the nitrosoarnine is heated with hydrochloric acid dinitromethyl-p-anisidine m. p. 129O is formed. By bailing the nitroamine with sodium hydroxide solution a small yield of Weselsky and Benedikt's dinitroquinol methyl ether (Abstr. 18SL 1139) is obtained. The fact that this nitroarnine like that obtained from dimethyl-o-anisidine (Abscr. 1910 i 255) gave the Liebermann reaction led the author to examine nitroamines obtained from alkyl- toluidines and for this purpose 3 5-dinitro-o-tolylmethylnitroamine and its p-isomeride were prepared by the method described by van Romburgh (Rec.trav. chim. 1884,3 392). As secondary products in these preparat,ions some 3 5-dinitro-2-nitromethylanlinobenzoic acid and its 4-isomeride were obtained (Ahstr. 1908 i 167). These melted at 187' and 204' respectively. Both nitroamines gave Liebermann's reactiou. The first on treatment with sulphuric acid at atmospheric temperature gives Stoermer's 3 5-dinitro-o-tolylmethyl- nitrosoarnine (Abstr. 1899 i 44) but is recovered unchanged from sulphuric acid a t - 10". 3 5 -Dinitro-o-tolylmethylnitroamine with sulphuric acid at atmospheric temperature furnishes 3 5-dinitro- 2-nitromethylaminobenzoic acid (see above) and a substance cry stallis- ing in colourIess needles and decompo;ling above 300° but with sulphuric acid a t - 10' it gives the same acid with as chief product 3 5-dinitro-p-tolylmethylnitrosoamine m.p. 127-1 28' (compare van Romburgh Abstr. 1896 i 478). The Reaction of Cellulose Nitrate with Dimetbylaniline. JORANN WALTER (Zeiiech. angew. Chem. 191 1 24 62-64).-Gun- cotton and celluloid absorb dimethylaniline the colour gradually deepening through green and blue to violet. The coloration becomes darker on exposure t o light and is not removed by solvents. Strongly- coloured specimens have a n odour of phenylmethylni trosoamine. Other aromatic amines produce similar colorations but less rapidly and of less intensity. Velocities of Addition of Bromine to the I m i d e s of Some Substituted Maleinamic Acids. 11. ARNALDO PIUTTI and G. CAJXAGNI (Rend. Accad. Xci. Pis Mat. Napoli 1910 [iii] 16 255-261.Compare Abstr. 1909 i 36O).-Continuing their investi- gations on this subject the authors have measured the velocibies of addition of bromine t o the following imides (compare Abstr. 1910 i 672) hydroxyphenylmaleinimide (white form) methoxyphenyl- maleinimide (white and yellow forms) ethoxyphenylmaleinimide (white and yellow forms). The velocity is very slow in a11 these cases ; for the white imides the reaction is complete in about fifty days for the yellow forms in about seventy-five days. Since Bnuer has shown that I?. A. H. C. H. D.ORGANIC CHEMISTRY. i. 125 substance of t h i s type the power of adding on bromine diminishes with increase in the number of negative groups this forms an additional argument for assigning t o the yellow form the symmetrical formula I 1 >N*C,H,*OR.The white isomerides behave as weak bases and that is consonant with their having the constitution CH*CO CH-CO R. V. S. Preparation of Alkali and Ammonium Salts of Nitrosoaryl- hydroxylamines. OSKAR BAUDISCH (D.K.-P. 227659).-Nitroso- arylhydroxylamines a r e known but their salts have not previously been obtained; they a r e now prepared by either the oxidation of an amine or the reduction of a nitro-compound i n alkaline solution in the presence of sodium nitrite or an alkyl nitrite. Ammonium nitrosophsnyli,ydroxy?ccmin~ prepared from nitrobenzene concentrated ammonium hydroxide zinc dust and amyl nitrite crystnllises in silvery leaflets m. p. 163-1 64" and sublimes readily. The sodium salt C,H,*N(NO)*ONa and the potassium salt form snow-white needles ; the iron palt crystallises in garnet-red needles or rosettes with a blue metallic lustre; it is insoluble in water but soluble in the ordinary organic solvents; the copper salt forms dark grey crystals and has similar properties.Ammonium a-nitrosonaphthyl- hgdroxylamine colourless leaflets is rather unstable turning pink in the light; i t dissolves i n water and is converted on boiling into a-nitrosonnphthalene ; the sodium and potussium salts are colourless ; the copper salt (C10H702N2)2C~~ forms glistening bluish-grey needles insoluble in water. The formation of complex double salts of ammonium with copper nickel cobalt or iron is also discussed. F. M. G. M. Separation of p- and m-Nitro-o-anisidine. CHEMISCHE FABRIK GRIESHEIM-ELEKTRON (D.R.-P. 228357).-The nitration of aceto-o- anisidide yields a mixture of two isomeric nitroaceto-0-anisidides ; these have previously been separated by the more ready hydrolytic disso- ciation of p-nitro-o-anisidine which is precipitated by the addition of water t o a n acid solution of the mixed sulphates whilst m-nitro-o- anisidine sulphate remains in solution.It i s now found that a separation can be effected by fractional crystallisation of the mixed sulphates ; t h e mixture of m- and p-nitro- aceto-0-anisidides is hydrolysed by heating with 70% sulphuric acid and the mixture then diluted with hot water until the concentration of the sulphuric acid is reduced to 40% ; on cooling pure p-nitro-o-anisidine sulp?mte separates i n colourless crystals and the m-nitro-o-anisidine i s precipitated from the filtrate by the addition of alkali.F. M. G. M. Preparation of Phenyl Ortho-oxalatee. SCHULKE and MAYR (D.R.-P. 22623 l).-When dehydrated oxalic acid is mixed wit.h fusedi. 126 ABSTRACTS OF CHEMICAL PAPERS. phenol (2 mols.) at a temperature of about 40° and then heated to 90-100" with continual stirring pure diphmyl ortho-oxalate OPh*C(OH),*C( OH),*OPh is obtained in quantitative yield; it crystallises from acetic acid and has m. p. 126". F. M. G. M. Synthesis of Alcohols in the cycZoHexane Series. ALPHONSE MAILHE and MARCEL IXURAT (Bull. ~Soc chirn. 19 10 [iv] 7,1083-1089). -The co n d ensation of 1 -meth y lcyclob exan-3-one with various magnesium alkyl haloids has been studied and t h e alcohols obtained and some of their derivatives are described (compare Sabatier and Mail he Abstr.1906 i 254 ; Murat Abstr. 1909 i 146). l-~lethyl-3-ethylcycZohexan-3-ol Do 0.9201 D20 0.9013 n 1,459 b. p. SS"/ZO mm. obtained by condensing 1-methylcyclohexan-3-one (Abstr. 1905 i 275) with ethyl magnesium bromide is a colourless liquid with a feebly camphoraceous odour (compare Zelinsky Abstr. 1901 i 661) ; the phenylurethane m. p. 98" crystallises i n colourless prisms ; tho acetute DO 0.9493 DZo 0.9303 n 1.441 b. p. 9S-100°/ 30 mm. has a fruity odour. The alcohol is readily dehydrated yielding 1 -meth?yl-3 -ethylcycloh,exene Do 0.8366 DZ0 0.8296 n 1.454 b. p. 149-151"/760 mm. a mobile colourless liquid of pleasant odour; i t gives a greenish coloration with sulphuric acid and alcohol furnishes a nit?-osochloride m.p. 124-1 26" and on reduction yields I-met?qZ-3- eth7~lcyclohexane DO 0.8320 D20 0.S313 n 1.460 b. p. 145-146O. l-niIethy1-3-propylc~cZohexan-3-ol Do 0.9063 D15 0.896 I n 1.461 b. p. 96-98"/20 mm. is a colourless viscous liquid (Zelinsky Eoc. cit.); it yields a phenylus*ethane m. p. 112O and a n acetate DO 0-9367 1)20 0.9248 n 1.454 and h.p. 108-110"/20 mu. which is colourless and has a fruity odour. The alcohol is readily dehydrated yielding l-methyl-3-propylcyclohexene Do 0.83'75 D15 0.8302 n 1 m4.56 and b. p. 16S-171"/760 mm. which absorbs bromine and gives a yellowisb-green colour with alcohol and sulphuric acid furnishes a nits*osochloride m. p. 128-131' (decornp.) and on reduction gives 1 -methyl-3 propylcyclohexane b.p. 164-1 65O. 1 -Meth~l-3-isobutyZcycloJ~exc~n-3-ol Do 0.901 1 D19 0.8972 n 1.465 b. p. 107-109°/20 mm. is best obtained by condensing magnesium isobutyl chloride with methylcyclohexanone although the secondary reaction already described (Abstr. 1905 i 706) occurs and occasions some loss. The alcohol is viscous and dehydrates easily giving an ethyleiaic hydq-ocarbon b. p. 192-1 95" having a somewhat alliaceous od our . l-Meth~Z-3-isoarnyZcyclohexnn-3-oZ Do 0.8982 lY2 0.8856 n 1.464 b. p. 12d-I 2s0/2O mm. is a viscous colourless pleasant-smelling liqrrid; the phen,yZumthane m. p. 128O is crystalline and the acetate DZo 0.9146 n 1-457 b. p. 140°/20 mm. is a thick liquid with a pleasant odour. The alcohol on dehydration gives l-metA,p?- 3-isoarnylcyclohexesze DO 0.8301 D2O 0.8190 n 1.459 b.p. 209-21 1'1 760 mm. which gives a greenish coloration with sulphuric acid and alcohol yields a nitrosochloride m. p. 136O and on reduction furnishes l-mathyl-3-isoamylcyclohexane b. p. 205" a colourless liquid with a n odour recalling that of petrol.ORGANIC CHEMISTRY. i. 127 3-cyclo~€exyZ-l-metJ~ylcyclohexun-3-oZ Do 0.981 5 UlS 0.9685 nD 1,495 b. p. 153-155O/20 mm. is a viscous liquid of agreeable aroma yields a phen?/luyethane m. p. 141" gives an intense blue coloration with bromine in chloroform and on dehydration furnishes 3-cvclohexyZ- l-metl~yZcyclohexe?za Do 0.9634 DlS 0.9 138 n 1.492 b. p. 240'/760 mm. a mobile liquid which is scarcely coloured by sulphuric acid and alcohol but gives a nitrosochloride m. p. 142-146' which is possibly a mixture of isomericles.3-Phenyl-l-meth~Zcyclo~exan-3-ob m. p. 61° b. p. 153"/20 mm. (decomp.) crystallises i n monoclinic prisms yields a phenytuwtl~ar~a m. p. 143" and on dehydration furnishes 3-phen~l-1-methylcyclo- Iiexene DO 0.9859 1120 0,9702 n$' 1.555 and b. p. 145"/20 mm. as a colourless mobile liquid which absorbs bromine and with sulphuric acid and alcohol gives a rose-red coloration. 3-Benx~Z-l-~~et7~ylcyclohe.z.a~~-3-oZ DO 1.0032 D17 0.9873 n Z -532 b. p. 165O/18 mm. (decomp.) is a colourless liquid having a lemon-like odour and is obtained in small yields by condensing methylcycZo- hexanoue with benzyl mngnesiuni chloride the chief product being dibenzyl. 3-BenzyZ-l-~nethyZcyclohexene DO 0-9693 D20 0-9591 n 1.547 b. p. 156"/20 mm.or 271°/760 mm. is colourless and has a disagreeable odour. T. A. H. A Solid Molecular Compound of Hexamethylenetetramine and Guaiacol. E. HOFFMANN-LA KOCHE & Co. (D.R.-P. 225924).- The preparation of a hexamethylenetetraminetriguaiacol has been previously described (hbstr. 1910 i 378). A compound obtained in a similar manner and with identical properties is now found t o have tho composition of a hexamethylenetetraminediguaiacol and it is suggested that the former compound was possibly not an individual sumtance. F. M. G. Di31. Fermentation of Tyrosine to p-Hydroxyphenylethanol (Tyrosol). FELIX EHRLICH (Ber. 191 1 44 139-146. Compare A bstr. 1907 ii 384).-A 60-80% yield of p-hydroxyphenylethanol OH*C,H,*CH,-CH,*OH can be obtained by the fermentation of tyrosine with large amounts of yeast in the presence of much sugar and of nutritive salts.Small amounts of acids are also formed; these are soluble in ether and give Millon's reaction. The hydroxy-alcohol is termed iyrosol. It crystallises in long glistening needles and rods of rhombic habit; it has m. p. 93' and b. p. 310'. It has .zi bitter taste does not reduce Fehling'a solution and gives a Bordeaux-red coloration when warmed with concentrated sulphuric acid. With ferric chloride solution it gives an indigo-blue coloration and with Rlillon's reagent and also with diazobenzenesulphonic acid dark red colorations. It does not give the Piria reaction but develops an iutense yellowish- green coloration with formaldehyde and sulphuric acid. It is oxidised by alkaline permanganate solutions reacts with phosphorus penta- chloride yielding a yellow oil and also forms an oily acetj 1 derivative.The dibenzoyl derivative C22H1s04 prepared by the Schotten-Baumann method crystallises from alcohol in felted needles m. p. 11 1". The formation of tyrosol is brought about by either top or bottomi. 128 ABSTRACTS OF CHEMICAL PAPERS. yeads. It is also formed in appreciable amounts when a sterilised solution of tyrosine and sugar is inoculated with pure cultures of yeast and in small amounts during t h e fermentation of pure sugar solutions by pure yeasts. I t s formation in the latter case is due t o the autolysis of the dead yeast cells and the Formation of tyrosine which is used as nitrogenous nutritive material by the living cells and transformed into tyrosol.It is not formed in the absence of sugars. Tyrosol thus appears t o be a by-product in most processes of fermentation by yeast and is present in all fermented liquors especially in beer and wine the flavours of which are due in part to the presence of the hydroxy-alcohol. J. J. S. Preparation of Nitrobenzoic Acids from the Corresponding Nitrotoluenes. GUSTAV L~TTGEN (D.R.-P. 226225)-The oxidation of nitrotoluenes to the corresponding nitrobenzoic acids with nitric and sulphuric acids is not satisfactory; it is now found that the reaction proceeds smoothly in nitric acid solution with potassium chlorate as the oxidising agent. 2 4 6-Trinitrotoluene was dissolved in concentrated nitric acid (48 Be) and warmed to 90-95'; potassium chlorate (2 parts) was gradually stirred in the temperature being maintained meanwhile at 100-120° i pure trinitrobenzoic acid separated from the reaction mixture on cooling. P.A$. G. M. Synthesis of Compounds of the Normal Amy1 Series from Piperidine. JULIUS YON BRAUN and W. SOBECKI (Bey. 1910 43 3596-3599).-Although benzo-c-chloroamylamide derived from piperidine is very stable the corresponding benzoiodoamylamide is relatively easily reduced. It is prepared from the chloro-compound by boiling this with sodium iodide in alcohol and is dissolved in much concentrated hydrochloric and acetic acid cooled and stirred with zinc dust for a number of hours. Banzo-n-amyZc6mide separates RS an oil and is purified by dis- tillation; b. p. 208-210°/15 mm. It is readily hydrolysed to n-amylamine or when distilled with phosphorus pentachloride or pentabromide is converted into cn-amyl chloride or bromide respec- tively.To prove that the normal carbon-chain structure had remained intact the bromide was boiled with potassium cyanide and converted into the nitrile of n-hexoic acid. E. F. A. Secondary Anthranilic Acids and the Transformation of their Nitroso-derivatives into a Peculiar Class of Intensely Red Substances Soluble in Water. JOSEF HOUBEN and TH. ARENDT (Ber. 1910 43 3533-3541. Compare Abstr. 1908 i 27; 1909 i 645 794).-Previous attempts t o nitrosylate methyl dimethylanthranilate failed. The authors now find that the action of sodium nitrite and fuming hydrochloric acid on the ester yields 5-nitroso- N-methylanthranilic acid one of the methyl groups being split off from the nitrogen atom.When 5-nitroso-N-methylanthranilic acid is dissolved in sodium carbonate and shaken with acetic anhydride a red substance is formed,ORGANIC CHEMISTRY. i. 129 which is very soluble in water. Similar red products have been obtained by the action of various acid chlorides and anhydrides either in aqueous or pyridine solution on a large number of nitroso- derivatives of secondary anthranilic acids and their esters and also on quinoneoximecarboxylic acid but oiilg in one instance has the product been isolated. When 5-nitroso-N-rnethylanthranilic acid is shaken with pgridine and acetic anhydride a red solution is formed from mhicb by the addition of ether a brownish-red pyridine salt C,,H,,O,N is pre- cipitated ; the salt is very soluble in water forming blood-red solutions and melts with decomposition t o a dark red liquid.CO,H-C,H,=NH-CH;COMe prepared by dissolving anthranilic acid in the equivalent quantity of potassium carbonate and boiling the solution with chloroacetone has m. p. 169-170'; the nitrosuntine which forms white crystals m. p. 115-1 16' (decomp.) could not be transformed into 5-nitroso- N-acetonylanthrariilic acid by t h e action of hydrochloric acid ; the semicarbuxone obtained from the sodium bisulphite compound of ace tonylanthranilic acid has m. p. 240-241' (decomp.). MethylucetonyZxntiLruniZic acid CO,H*C,H,*NMe*CH,.COMe pre- pared from metl ylanthranilic acid and chloroacetone crystallises in small light grey needles m. p. 123-126'.[With L. ET~1~0E~.]-N-8cetonylanthl.anilic acid CO2H-C,H,*NH* CH ,- CNe N N €3 CO N H 2 4 - D i r ~ i t r o d i p ~ e n y l ~ t ~ ylarnine-2'-cardoxylic acid CO,H*C H4*NMe-C,H,(N0,) is obtained by boiling 4-chloro- 1 3-dinitrobenzene with methyl- anthrnnilic acid in aqueous potassium carbonate ; it forms clusters OF yellow needles m. p. 178". Action of Ethereal S a l t s on the Monosodium Derivative of Phenylacetonitrile. P. Bouiioux (Conhpt. rend. 19 10 151 1357-1359. Compare Abstr. 1910 i 623).-Ethyl benzoate con- denses with the sodium derivative of phenylacetonitrile to give a 75% yield of cyanophenylacetophenone CN-CHPh*COPIi lamellae m. p. 93-94' (compare Walther and Schickler Abstr. 1897 j 522). Ethyl carbonate in the same way forms ethyl cyanophenylacetate CN*CHPh*CO,Et b.p. 163-165"/19 mm. D17 1.085 the yield being 55?& Ethyl oxalate yields a small quantity of ethyl cyanophenyl- pyruvate. The foregoing cyano-derivatives are sufficiently acidic to be capable of titration using phenolphthalein as indicator. F. B. w. 0. w. Crystallographic Examination of Some Nitrophenylmethyl- acrylic Derivatives. FHAKCESCO RANFALDI (Bend. Accud. Xci. Fzs. Mut. Napoli 19 10. [iii] 16 225-234).-P-o-Nitrophenyl-a-methyl- acrylic acid N0,.C,H',*CH:CR~e.CO,H forms monoclinic prismatic crystals [a b c = 1.3446 1 1.4562 ; = 92"24'51"]. P-m-Nitrophenyl- a-methylacrylic acid forms colourless acicular crystals which could not be obtained in a measurable form. P-p-Nitrophenyl-a-mettiylacrylic acid forms triclinic pinacoidal crybtals [a b c = 1.2567 1 1.4602 ; a = 84'42'8'' ; /3 = 83'31'31" y = 87'35'18"].Sodium P-o-nitrophenpl-i. 130 ABSTRACTS OF CHEMICAL PAPERS. a-methylacrylate forms rhombic disphenoidal crystals [a 3 c = 1,3940 1 2.05441. K. v. s. Preparation of Glycol Monosalicylate. C. F. BOEHRINGER & SOHNE (D.R.-P. 225984. Compare Abstr. 1908 i 176).-The esterification of salicylic acid with ethylene chlorohydrin yields P-chloroethyl salicyhte OH*C,H;CO2.CH,.CB,cl which on careful hydrolysis with mild reagents gives the therapeutically valuable glycol salicylute OH*C6H;C0,*CH,*CH2*OH. The hydrolytic agents described a s suitable are (1) sodium acetate axid dilute acetic acid; (2) disodium phosphate and water or (3) sodium salicylate and water a sealed tube being employed and a temperature of 130" maintained in each case.F. &I. G . M. Pyrogenetic Decomposition of cycZoGallipharic Acid. HERMANN KUNZ-KRAUSE and PAUL MANICKE (Arch. Phuwn. 19 10 248 695-709. Compare Abstr. 1904 i 587; 1910 i 458 677),- The decomposition of cyclogallipharic acid when heated alone or with various dehydrating agents has been studied and the results correlated with those recorded in previous papers (Zoc. cit.). When heated with potassium hydrogen sulphate the acid furnishes unsaturated gaseous hydrocarbons acraldehyde cyclogallipharol and 4-hydrox y-m-xylene. Sulphuric acid is without action on cyclogallipharic acid in the cold but on heating with this reagent it is converted into the keto- anhydride of cp!ogallipharic acid at 125-130° ; a t 150-160" some cyclogallipharol is formed and a t 180' this substance is the sole product of the reaction.When heated alone the temperature being gradually raised from 130" to 250" the amounts of carbon dioxide evolved indicate that the acid undergoes the same progressive decomposition as with sulphuric acid the same stages however being reached at somewhat higher temperatures. Above 250' complete decomposition into carbon dioxide and volatile hydrocarbons takes place. I n conclusion a summary of the results recorded in this and the two preceding papers of the series is given. T. A. H. Preparation of Carvacrolphthalein. CURT EHRLICH (D.R.-P. 235983).-Cucl.~ucrolpht7~aZe~~ colourless transparent needles m. p. 246-2247" is prepared by heating phthalic anhydride ('1 part) with carvacrol (2 parts) and stannic chloride ( 2 parts) a t 100' during two hours.It is insoluble in water soluble in sodium hydroxide with a deep blue colour and compares very favourably with phenol- phthalein as a n indicator. F. M. G. I\I. Esterifhation of Unsymmetrical Di- and Poly-basic Acids. XXIII. Trimellitic Acid. RUDOLF WEGSCHEIDER HEINRICH FELIX PEKNDANNER and OTTO AUSPITZER (Uoncctsl~ 1910 31 1253-1301). -The formation of acid esters of trimellitic acid (benzene-] 2 4-tri- carboxylic acid) by diEerent methods has been studied in order t o determine whether the rules previously laid down for dibasic acidsORGANIC CHEMISTRY. i. 131 hold good. The investigation was complicated by the fact that the three carboxgl groups differ but little from one another arid therefore mixtures of acid esters are obtained by each method; these mixtures cannot be separated readily into their constituents.They do not crystallise well and several of them tend t o form mixed cryhtals. The 1 4- and 2 4-dimethyl esters crystallise extremely slowly and are usually obtained as syrups although from their con- stitutions their m. p.’s should be relatively high. The constitution of the 4-methyl ester C0,R5e*C,H,*(C02H) [(CO,H),:CO,Me = 1 2 41 follows from the fact t h a t it is formed by the addition of water to the methyl ester of the anhydro-acid CO,~f.e*C,H,:(CO),O and the constitutions of the two isomeric monomethyl esters were deterininecl by conversion in to the corresponding nmidedicarboxylic acid and then by means of bromine and potassium hydroxide transforming the amides into aminoiso- and aminotere-phthalic acids.The constitution of the dimethyl esters was determined by the elimination of carbon dioxide from their potassium salts in the presence of lime. The products formed by the esteritication of the acid both by the direct and by the catalytic method could not be obtained pure with the exception of small amounts of the 1- and 2-monometbyl esters but the fact that the syrups obtained yield appreciable amouxits of the methyl ester of anhydrotrimellitic acid points t o the conclusion that by these methods the carboxyl groups in position 4 that is the carboxyl group least affected by “steric hindrance,” is first esterified. The 1- and 2-monomethyl esters uiider similar conditions yield the 1 4- and 2 4-dimethyl esters and but little 1 %dimethyl ester.By partial hydrolysis of the normal ester with potassium hydroxide t h e 1 2-dimethyl ester is first formed and by further hydrolysis the %monomethyl ester with smaller amounts of t h e isomeric 1 -ester. By the addition of methyl alcohol to the acid anhydride both the 1- and 2-monomethyl esters are formed but at the same time the csrboxylic group in position 4 is esteri6ed to a slight extent. The mono-silver salt with methyl iodide yields mainly 1-methyl together with the 2-methyl ester and the disilver salt yields mainly 1 2-di- rnetbyl ester. These results agree on the whole with the generalisation that in the formation of acid esters from the acid by esterification or t rom neutral esters by hydrolysis steric hindrance is the determining factor whereas in the formation from the anhydride or from the acid metallic salts the relative strengths of the carboxyl groups are of first importance.Full details of the methods used for separating the mixtures obtained in each experiment are given. Methyl hydrogen isophthalate has m. p. 167-1669’ and not 126” as stated by Meyer (Monatsh. 1901 22 437). A 90% yield of triniellitic acid can be obtained by the action of nitric acid on French colophony (compare Scheder Anu. Chem. Piturm. 1874 1’72 94) provided the mother liquors are worked up. It has not been found possible t o prepare the acid from naphthol yellow-S by Ree’s method (Trans. 1886 49 510) but Schultz’ method (Abstr. 1909 i 897) gives fairly good yields if the chromic anhydride is addedi.132 ABSTRACTS OF CHEMICAL PAPERS. gradually. The m. p. depends on the method of heating; when dipped into a bath at 200° it has a. p. 215-217O in a n open tube or 239-234' in a closed tube. A 2% solution of the normal ammonium salt gives precipitates with solutions of mercuric cadmium lead ferric aluminium uranyl and silver salts. The following acid halts have been prepared C0,H~C6H3(C02Ag) slender needles from hot water ; C02Ag*C6H3(C0 H) ; C,H406Ba,H,0 insoluble in water. The l-??tonome~lzyZ ester CIOHSOB is most readily prepared from the mono-silver salt and is most conveniently separated from the free acid by precipitating the latter i n the form of its barium salt ; it may be purified by the addition of benzene to its ethereal solution and has m.p. 203*5-205*5O but frequently melts to a certain extent at 177O resolidifies at 179O and then melts at the higher temperature given. The two m. p.'s a r e probably due t o dimorphism. When mixed with the isomeric S-monomethyl ester its ni. p. is not appreciably affected. The latter ester is best prepared hy the partial hydrolysis of the 1 %dimethyl ester ; i t is sparingly soluble in water wheieas the 1-ester dissolves readily and crystallises from this medium as a colour- less powder m. p. 208'. The 4-methyl ester is most readily obtained by the addition of water t o the methyl ester of the anhydro-acid and crystallises from water in compact plates rn. p. 145-14i". The CO co anhydro-ester CO,Ne*C,H,< >0 has m.p. 94-99O is transfurmed into a syrup by the addition of a little alcohol and when kept for some time even in a desiccator yields the 4-monomethyl ester. 'l'tie 1 2-dimethyl ester CI1H,,O crybtallises from carbon tetrachloride or better from a mixture of ether and light petroleum in nodular masses of needles m. p. 115*5-117° after softening at 108'; when slowly heated above the m. p. the ester resolidifies and then has m. p. 121". It has b. p. 200°/12 mm. The 1 4- and the 2 4-dimethyl eaters are both syrups and the solution of the ammonium salt of the former gives a precipitate with concentrated solutions of copper sulpliate whilst that of the latter is precipitated even in dilute solution The trimethyl ester has b. p. 194'112 mm. (cow.) and solidifies in a freezing mixture at - 13' to a vitreous mass. The 1-amide NH2*CO*C,H3(C0,H) is obtained by heating the corre- sponding ester with a concentrated solution of ammonia in methyl alcohol at 100' for one and a-half hours then acidifying removing trimellic acid by extracting with ether and extracting several times with amyl alcohol.After removal of the amyl alcohol and iecrystal- lisiog the residue from a mixture of methyl alcohol and benzene the amide is obtained pure and has m. p. 185-186'. The isomeric 2-amide obtained by a similar method has m. p. 199-200'. The 1-amide reacts with bromine and alkali yielding 4-amino-isophthalic acid which was isolated in the form of i t s methyl ester (m. p. 130'). The 3-amide under similar couditions yields aminoterephthalic acid which was isolated as i t s methyl ester m.p. 123-126O (Cahn- Speyer Abstr. 1907 i 549 gives m. p. 133"). By the action of a methyl-alcoholic soliltion of ammonia on the a n h j dro-acid a mixture of the 1- and 3-amides is obtained. J. J. S.ORGANIC CHEMIS'L'RP. i. 133 Ring Syntheais of Pyrornellitic Acid. FRANZ FEIST (Ber. 1911 44 135-138).-Small amounts of pyromellitic acid (14% yield) are formed according to the eqiiation 2C0,Et*CH2*CH:Br*CHBr*C02Et + 8KOH = C,H2(C02K)4 + 4KBr + 4EtOH + 4H,O + H2 when ethyl up-dibromoglutarate is mixed with alcoholic potassium hydroxide solution. The acid is isolated by acidifying the potassium salt and extracting eighteen times with ether. It is accompanied by large quantities of oily impurities which can be removed by stirring with a small amount of ether i n which the impurities dissolve.The anhydrous acid has m. p. 275" and the tetramethyl ester m. p. 141.5'. T T C I Preparation of Diglycollyldisslicylic Acid. CHEMISCHE FABRIK VON FRIEDR. HEYDEN (D.R.-P. 227999).-DiylgcoZlyldi- saZicpZic [o-digZycoZZyEoxybenzoic] acid O(CH2*CO*0.C6H,*U02H)2 glistening leaflets m. p. 168-170° is readily prepared b y boiling salicylic acid (or a salicylate) in benzene solution with diglycollic anhydride in the presence of an indiffereni; base (such as pyridine); it is of therapeutic importance and compares favourably with acetyl- salicylic acid in this respect. F. M. G. M. An o-Hydroxyaldehyde of Triphenylcarbinol. AUGUST IBisTHzYcKI and MARTIN EELLMANN (Ber. 1910 43 3579-35%)- Salicylaldehyde can be condensed with benzylic acid forming 4-hydroxy-3-aldehydotriplienylacetic acid (Abstr.19 10 i 32 l) and this by the elimination of carbon dioxide is readily converted into 4- bydroxy-3-aldehydotriphenylcarbinol which is the third aldehyde of the triphenylmethane series to be described. 4- Hydroxy-3-aldehydotriphenylacetic acid prepared by the con- densation of the components in benzene in presence of tin tetra- chloride crystallises + &C7HSl in microscopic prisms or needIes m. p. 198-200' (from toluene) or in stellar aggregates of prisms +&C,H m. p. 197-198' (from benzene). The aaine N,[ :CH-CGH,(OH)*CPh2-C02HJ2 derived from the action of hgdrazine sulphate and sodium carbonate ia a yellow powder (decomp. 270-280') ; the sodium salt crystallises in slender yellow needles.The oxime crystallises in microscopic colourless needles which turn yellow at l l O o m. p. 2%' (decomp.). The semicar6~6xone forms bunches of microscopic slender prismatic needles m. p. 198-199" (decomp.). The aniline derivative is a granular yellow powder m. p. 85-86' (decomp.). Methyl 4-methoxy-3-aklehydotr~p~ennyZucetate prepared by the action of methyl sulphate iii cold sodium hydroxide solution crystallises in bunches of faintly yellow-coloured four-sided prisms m. p. 4-Benxoxy-3-aldehyclotriphenylacetic acid crystallises in concentric- ally-grouped colourless needles m. p. 195.5-1 96.5". 4-Hydroxy-3-aldehydotriphenylcarbinol (Zoc. cit.) prepared by the action of concentrated sulphuric acid on the aldehydo-acid crystallises in aggregates of light yellow prismatic plates m.p. 1213-124O decomp. at 170". The solution in concentrated sulphuric acid is 148-1 4 9'. VOL. C. i. Ii. 134 ARSTRACTS OF CHEMICAL PAPERS. orange-red; a second isomeric form could not be obtained. The acetyl derivative crystallises in reniform aggregates of colourless prisms m. p. 131-132' the fused mass being orange-yellow. The phenyl- hydruxone forms rounded aggregates of microscopic prisms decomp. 177". The ozime separates in bunches of colourless flat prisms; on heating it becomes yellow and softens at 95' becomes colourless and solid again at 102' m. p. 151' (decomp. 175'). The semicarbaxone crystallises in colourless microscopic needles which become yellow at 140' and decompose at 164' with an intense red coloration. On heating the hydroxyaldehydocarbinol in a stream of dry air in a sulphuric acid bath a t I 90-200° the anhydride 2-aldehydodiphenyl- qzcino,methnne CPh,:C,H,O*CHO is obtained as a brown powder.This darkens in colour at loo' and begins to melt indefinitely a t a somewhat higher temperature. E. F. A . Hexahydroacetophenone [cycZoHexyl Methyl Ketone] and Hexahydrobenzoylacetone. MARCEL GODCHOT (Compt. rend. 1 9 10 151 1131-1 134).-Adigic acid is the sole product of the oxidation of cyclohexyl methyl ketone by alkaline potassium perrnanganate. cyclo- Hexyl methyl ketone (Bouveault Abstr. 1904 i 61) forms an oxime b p. 145-150°/20 mm. m. p. 60'; no isomeric form wits detected. I t undergoes the Beokmann change forming acetylaminocgclohexune (hexahydrocccetnnizide) C,H,,*NHAc crystallising in needles m.p. 103' identical with the product obtained by acetylating cyclohexyl- amine. Irexaliydrohenzoylaceto~~ C,H,,*CO*CH,-COMe is obtained in the form of its sodium salt by the addition of sodium ethoxide to a mixture of cycEohexy1 methyl ketone and ethyl acetate. The diketone has b. p. 103--105'/25 rnm. D15 0.9933 and was prepared in the pure state from its copper derivative which crystallises in pale green needles m. p. 210' ; the phenylhydrazone and oxime appear to be oily. w. 0. w. Ketones Derived from 0- m- and p-Toluic Acids. JEAN B. SENDERENS (Compt. rend. 1911 152 90-92. Compare Abstr. 1909 i 286 627 ; 1910 i 11 179,489).-The under-mentioned ketones have been prepared by passing the vapour of an aromatic and an aliphatic acid over thorium oxide at 460-470'.A single distillation of the product usually suffices to yield the aromatic ketone in a state of purity. The new ketones are liquids ; their odour resembles that of citrons in the case of the ortho-compounds and of fennel in the case of the para- derivatives; the odour of the meta-compounds is not characteristic. The b. p.'s given are corrected o-Tolyl methyl ketone b. p. 211'/745 mm. D 1.0262; semicarhazone m. p. 192'. m-Tolyl methyl ketone b. p. 221'/745 mm. DS 1.0165; semicurbaxone m. p. 188' (decomp.). p-Tolyl methyl ketone b. p. 224.5'/745 mm. D! 1.0150 ; semicarbccxone m. p. 200'. o-Tolyl ethyl ket'one b. p. 224'/745 mm. D 1.0119; semicurbaxone m. p. 169'. m- Tolyl ethyl ketone b. p. 234'/745 mm. DS 1.0059; semicarbaxone m.p. 166'. p-Tolyl ethyl ketone b. p. 23S0/745 mm. D 1.0053; eeinic irbazone m. p. 180° 0-Tolyl proyyl ketone b. p. 238*5'/788 mm.,ORGANIC CHEMISTRY. i. 135 D! 0.9836 ; sm~ca~bazone m. p. 176'. m-Tolyt propyl ketm b. p. 247'1758 mm. DI 0.9882; samkarbazm m. p. 152O. p-Tolyl p o p y l ketone b. p. 261*5O/758 mm D9 0.9774; semiccrrhsona m. p. 190°. O-Tdylieopropyl ketoru b. p. 230°/758 mm. Di 0.9858; the sem&mrbazma is an oil. m-ToZyl isoFopyl ketone b. p. 238'/758 mm. D 0.9841 ; samicarbazone m. p . 120'. p-Tolyl ieopropyl ketone b. p. 243O/ 758 mm. DS 0.9778 ; serraicai*bazone m. p. 101'. o-Z'olyZ isobutyl kstolte b. p. 247*5'/758 mm. DS 0.9744 ; semicurbaxone m. p. 166'. m-TolyZ isobutyl ketone b. p. 254'/758 mm. DS 0.9712 ; semicarbazcma m.g. 172". pTolyl isobutyl ketone b. p. 259"/758 mm. DP 0.9707; semi- cwbazoite m. p. 212'. w. 0. w. Quinonee. EERMANN HAAKH (J. pr. Chem. 1910 [ii] 82 546-551).-A theoretical paper in which an attempt is made t o account for the recent numerous examples of the formation of highly. coloured additive corupounds of p-benzoquinone with inorganic acids and salts aromatic hydrocarbons and other substances. The author assumes that the comparatively feebly-coloured p-benzoquinone itself has Graebe's peroxide constitution in which the oxygen atoms have no residual affinity ; when it forms highly-coloured additive com- pounds the quinone acquires the Fittig constitution addition occurring by means of the residual affinity of the oxygen atoms. c. s. Oxonium Hydrosulphides of p-Benzoquinone.M. M. RICHTEB (Bar. 19 10 43 3599-3603).-On mixing hydropersulphide and p- benzoquinone in anhydrous solvents at the ordinary temperature a voluminous brilliantly blue compound is obtained which is labile in character and under certain conditions changes to a faintly yellow substance. The blue compound is obtained in presence of an excess of benzoquinone the yellow with an excess of hydropersulphide. The amorphous indigo-blue substance bis-p-benxopuinoneoxo!nium H H hydrotrisulphide 0 C6H, O<s.s.s>O C,H,:O decomposes at 1 1 5 O or when exposed to moisture. It dissolves in anhydrous solvents with an orange coloration but- is more or less decomposed. By the action of p-benzoquinone dissolved in carbon disulphide and potassium hydrosulphide in absolute alcohol in a stream of hydrogen pbernxoquinoneoxonium hydrosulphide 0 C6H4:O<EK is obtained as EL dark greenish-black powder extremely sensitive to traces of moisture.~risquinhy~roneoxonium hydrosulphide C,,H,,O,,S is obtained by passing dry hydrogen sulphide through a solution of quinone in formic acid It is a microcrystalline almost black powder decomp. 140'. The same compound is obtained on passing dry hydrogen sulphide over fused p-benzoquinone. Hydropersulphide does not combine with substituted quinones ; the entry of substituents particularly of strongly negative groups into t h e quinone molecule weakens the basic properties of oxygen and prevents salt formation E. F. A 1 2i. 136 ABSTRACTS OF CHEMICAL PAPERS. Constitution of Quinhydrone-like Subatances.M. M. RICHTER (Ber. 1910 43 3603-361 l).-The characteristics of oxonium salts namely simple addition of the components in their formation ready decomposition in solution or when sublimed and marked increase in the intensity of the colour are also those of the quinhydrones. It is suggested that quinhydrones phenoquinones alloxantin etc. are all to be regarded as oxonium compounds and their dissociative and colour properties are due to quadrivalent oxygen and quinquevalent nitrogen. p-Benzoquinone has been shown (com- pare Siegmund Abstr. 1909 i 109 ; Meyer ibid. i 395) to combine both with one and with two molecules of mono- and di-hydroxy- phenols. H The evidence in favour of the formula O:C,H,:O<O,C .OH for quinhydrone is discussed. Two more must be added to the characteristics of the quinhydrones already enumerated namely they are composed of quinonoid and benzenoid sections and they have the power of forming salts.The entry of substituting groups particularly those of a strongly negative nature into the quinone molecule materially lessens the basic properties of tho oxygen atom and in consequence prevents salt and quinhydrone formation. Thirteen cornpounds are enumerated of six main types which are quinb ydrone compounds of pphenylenediamine benzidine and p-benzo- quinonedichlorodi-imine. It is considered that the simple oxygen atom generally behaves as a quadrivalent atom. Preparation of N-Alkyl- and N-Arylaryl-sulphaminoanthra- quinones. FRITZ ULLMANN (D.R.-P. 227324).-By the action of alkylsulphon~mides of the general formula R*NH*SO,-R (R = alkyl or aryl ; R = aryl) on halogenated anthraquinonee condensation products are obtained.6 4 E. F. A. 1 -p Toluenesu Zphon ylphennyZaminoant?~rayu.inone CBH,<CO>CBH3*NPh*S0,. co C,H is prepared by heating together p-toluenesulphonylanilide and a-chloroanthraquinone in nitrobenzene solution in the presence of copper acetate and $odium carbonate ; i t crystallises from acetic acid in glistening yellow cryst>als m. p. 193’. 1 -p-l’oluenesuZ~honyI,rLetf~~Z~m~noanth~a~u~none yellow needles m. p. 192O is prepared in a similar manner from p-toluenesulphonylmethyl- amide and a-chloroant hraquinone. By treatment with concentrated sulphuric acid it yields a-methylaminoanthraquinone. Preparation of 6-Chloro-l-hydroxynaphthacenequinone and of 6-Chloro-1-hydroxynaphthacenequinone-4-sulphonic Acid.ANILINFAHBEN arid EXTRACT-FABHHEN VORM. J. R. GEIGY (D.R.-P. 226230).-!Che work of Weiamann and others has shown that o-1-hydroxy-P-napbthoylbenzoic acid when heated with concen- trated sulphuric acid and boric acid is converted quantitatively into 1-hydroxynaphthacenequinone (Trans. 1906,90 116 ; 1907,91 41 1 j F. M. G. 1sI.ORGANIC CHEMISTRY. i. 137 1909 93 279) ; this reaction has now been extended t o 4'-chloro-1'- hydroxy-/?-naphthoyl-o-benzoic acid (Abstr. 1910 i 746) and its sulphonic acids. 6-Chloro - 1 - T~ydroxynaphthacenequinone (annexed formula) was prepared by dissolving crystallised boric acid (6 part,s) in 80 parts of concentrated sulphuric acid (25% SO,) slowly adding the 4'-chloro - 1'-hydroxy - /? - naphthoyl- /"-vCo/'/\ benzoic acid (20 parts) and heating a t '70" until I 1 I 1 sodium hydroxide ceased to produce a yellow \/'"'\k\/ coloration.The product after cryatallisation from benzene formed long reddish-yellow needles m. p. 307' and seems not t o be identical with the 6-chloro-1-hydroxy- naphthacenequinone m. p. 290-293' (Trans. 1907 91 418). The sodium salt is insoluble in water. 6-ChZoro-1-~,ydrox~~zn~hthacenequinone-4-suZphonic acid was isolated in the form of its monosodium salt a brick-red powder by boiling with a saturated solution of sodium chloride; it is soluble in water with a yellow coloration; the disodium salt was obtained as a dark red gelatinous precipitate soluble in water with a blue coloration.OH F. M. G. M. Preparation of Alkyloxyacetyl Derivatives of M e n thole. ALFRED EINHORN (D.R.-P. 225821).-The interaction of ethoxyacetic acid and mentholcarboxyl chloride in a cooled ethereal solution yields menthol ethoxyacetate a colourless oil b. p. 144'/14 mm. The reaction is a general one €or the alkyloxyacetic acids and mentholcarboxyl halides. P. M. G. M. Preparation of Santalyl Alkylaminoacetates. FARBENFABRIKEN VOEM. FRIEDR. BAYER & Co. (D.R.-P. 226229)-It is found tbat santalyl alkylaminoacetates of therapeutic importance can be prepared by treating chloroacetylsantalol with a secondary amine. Chloroacetyl- santalol a viscous yellow oil was prepared by treating santalol with chloroacetyl chloride in the presence of pyridine or with chloroacetic acid pyridine and carbonyl chloride.This product was isolated mixed with a solution of dimethylamine in benzene and left during twenty-four hours ; the scmtaZyl dimethylaminoacetate was extracted with hydrochloric acid and on rendering the solution alkaline with sodium carbonate separated as a yellow odourless oil which hydrolyses readily with alkalis into its components. It forms well characterised salts ; the hydrochlokle crystalliees from acetone in odourless colour- less needles m. p. 154". Analogous compounds can be prepared with diethylamine or piperidine. F. M. G. M. CataIytic Reactions at High Temperatures and Pressures. XXII. Reduction of Terpenes. WLADIMIR IPATIEFF (Bei.. 19 10 43,3546-3553. Compare Sabntier and Senderens Abstr. 1901 i 459 ; Vavon Abstr.1910 i 52 400).-By reducing I-limonene with hydrogen a t 280-300' under 110-120 atmospheres' pressure using cupric oxide as the catalyst an unsaturated hydrocarbon CI0Hl8 b. p. varying from 172" t o 17Cio is obtained. The same hydrocarbon is alsoi. 138 ABSTRACTS OF CHEMICAL PAPERS. produced when copper is used but a higher temperature is necessary. Further reduction of this hydrocarbon leads to the formation of p-menthane. [With D ~ ~ c ~ u s s o ~ ~ . ] - F r e n c h I-pinene in the presence of iron is not reduced but undergoes isomerisation to dipentene. A t 265O with cupric oxide as catalyst it is reduced to a hydrocarbon C10H,8 whilst repeated reduction a t 280-290' yields a hydrocarbon C,,H, b.. p. 163-170° D20 0.7949. Similar results were also obtained with metallic copper.With nickel oxide the reduction takes place with great rapidity and at a lower temperature than with cupric oxide C,,H2 being formed. It is considered probable that the hydrocarbon C10H20 obtained from I-pinene consists of a mixture of 0- and p-menthanes. For the purpose of comparison menthane was prepared from cymene by reducing with hydrogen nickel oxide being used as a catalyst ; it had b. p. 167-170' DZo 0.8038. Peppermint Oil Prepared from Dry Leaves of Mentha piperite. J. MURAOUR (BUZZ. SOC. chirn. 1911 [iv] QJ66-67).-Dry leaves which had fallen naturally from mint plants during cultivation gave a yield of from 400 to 500 grams of oil per 100 kilos. of leaves. This oil was yellow and had an odour recalling that of Japanese peppermint oil.Two samples gave the following constants D15 0.91 1 to 0,913 aD= - 38'18' to - 40°4' solubility 1 in 1.5 to 2.5 vols. of alcohol at 80° and contained 33.16 to 40.31% of esters and 43.99 to 45.67% of total menthol. The results of examination of commercial peppermint oils indicated that some of these products consisted of true peppermint oil of French origin mixed with oil from the fallen leaves. F. B. T. A. H. Essential Oils. I. Orange Flower Oil. 11. Schinus molle Oil. G. LALOUE (Bull. Soc. chim. 1910 [iv] 7 1101-1107 1107-1 109).-a more detailed account of work already published (Abstr. 1910 i 755; 1909 i 817). Gildemeister and Stephan's observation (Abetr. 1897 i 81) that Schinus moZZe oil contains pinene and phellandrene is confirmed and there is probably also about 20% of sesquiterpenes present. Oil distilled from branches and leaves obtained a t Grasse was richer in pinene than oil from leaves and branches obtained in Algeria.HEINRICH KILIANI (Ber. 1910 43 3574-3579. Compare Abstr. 1897 i 9 I).-Seligmann (Abstr. 1903 ii 314) obtained from the juice of A. toxicaria procured from Sarawak an antiarin differing from t h a t previously described. It is now found with juice obtained from Java that two antiarins exist the new /?-form being present in the larger proportion. They differ in crystalline form melting point water of hydration and composition although there is no difference in their toxic character. a- Antiarin C2tH,20,,,4H20 crystallises in glistening plates or leaflets m. p. 220-225' P-Antiarirz C,7H3s0,0,3H,0 or C28H38010 3H20 crystallises in slender needles or bunches of columnar needles m.p. 206-207'. T. A. H. Milk Sap of Antiaris toxicaris.OBGANIC CHEMISTRY. i. 139 Emulsin is without action on either glucoside; the products of hydrolysis of /3-antiarin have not been characterised. Digitonin Digitogenic Acid and their Oxidation Products HEINRICH KILIANI (Ber. 1910 43 3562-3574. Compare Abstr. 1904 i 505).-A further study of the oxidation products of digitogenin shows that digitic acid has the composition C2sH42011. Molecular weight determinations are particularly di5cult to carry out in the case of oxidation products of digitogenic acid. It has not been found possible so to conduct oxidation as to obtain simple products of known constitution; even with ozone the chief product is an acid l o prepare digitonin German digitalis is extracted with alcohol ether tLe insoluble residue is dissolved in water the vessel placed in a bath of water at 70' a small quantity of amyl alcohol added and after inoculation the whole is allowed to cool slowly until crystallisation is complete.Digitic acid is tri basic the barium salt being (C2SH41012)2Ba3,18H20. The normal potassium salt is hygroscopic and the acid salt admixed with free acid; the calcium salt is amorphous so that neither is suitable for analysis. The by-products of the oxidation consisted of acids miscible with sodium chloride solution from which no chemical individual could be isolated and of acids insoluble in salt solution. When further oxidised with permanganate in strongly alkaline solution a definitely crystalline calcium salt C19H2s07Ca,8H20 was obtained (compare Kiliani and Baylen Abstr.1895 1 65). The acid is indefinitely crystalline m. p. 170" (decomp.). Anhydrodigitic acid when oxidised with potassium permanganate in neutral solution forms an acid C2,H,,07 crystallising in crusts of small pyramids m. p. 196-200O; the magnesium salt crystallises in needles and small pyramids. From the products of oxidation of digitog6nic acid by hot permanganate in neutral solution a new tribasic acid C,,H,,Oll has been isolated; it crystallises in leaflets m. p. 155" (decomp.). The barium salt C2sH,oOllEa,10H20 crystallises in aggregates of closely- packed needles and is strongly acid. The acid is isomeric with digitic acid.On oxidation of digitogenic acid with ozone more than 60% of an acid C2,H4,07 is obtained ; this crystallises in clusters of pyramids m. p. 2%2". A magnesium salt C2,H,,07Mp,l 1 H20 crystallises also in tiny pyramids. It has not been established in what form the two atoms of carbon are eliminated during the Oxidation. MAX GONNERMANN (Pjiiger's Archiv 1911 137 453-469).-Sinigrin is not acted on by any enzyme with the exception of myrosin. The enzymes investigated under varying conditions of solvent etc. were of both animal and vegetable origin; bacteria including those in the intestine have no effect in liberating allyltbiocarbimide. This confirms Kobert's statement. Various details E. P. A. c2!3H4007* E. F. A. Saponiflcation of Sinigrin. regarding the mode of preparation of this glucoside are given.yV. D. H.i. 140 AI3STlUCTS OF CHEMICAL PAPERS. A Saponin-Cholesterol Compound. S. YAGI (Arch. exp. Path. Pharm. 1910 64 141-146).-Ransom having shown that cholesterol inhibits the haemolytic power of saponin Windaus Found that certain saponins form additive products with cholesterol ; the digitonin- cholesterol compound for instance is crystnllisable and has the formula C82H140029 that is a combination of one molecule of each substance (C55H,4028 + C,7H,,0). Other cholesterides have been separated by the same author. The present paper gives details of the preparation and properties of another crystallisable choles t eride namely that of dioscine in which three molecules unite with two of cholesterol 3C24H,80,,2C,7H,,0 1 or 3H,O a microcrystalhe powder m.p. 223O ; this is inactive on blood corpuscles. The feeble haemolytics such as Merck's saponin sapotoxin and dioscorea-sapotoxin need about an equimolecular amount of cholesterol t o render them inactive ; half the amount leaves them still partly active ; the feeble members of the group therefore do not contain active mixed with inactive molecules. W. D. H. Action of Nitric Acid on Aloins; Production of Tetra- nitroaloe-emodin and of 2 4 6-Trinitro-3-hydroxybenzoic Acid. EUQBNE L~GER (Compt. rend. 1910 151 1128-1131 ; BuEZ. SOC. chim. 1911 9 SS-97).-It has long been known that chrys- animic acid and picric acid are amongst the products OF the action of nitric acid on the aloins. It is now shown that the production of these compounds is preceded by the formation of two other substances which are then converted into these acids by the further action of nitric acid.Tetncnitroaloe-ernodin C,,H,O,(NO,) arises from the action of nitric acid (D 1.2) on barbaloin or zsobarba,loin a t the temperature OF the water-bath. It occurs in slender golden needles m. p. about 285O with deflagrakion. On long boiling with nitric acid (D 1-32) it is converted into chrysammic acid. The mother liquor from the tetranitroaloe-emodin contains 2 4 6- trinitro-3-hydroxybenzoic acid (Griess Annalen 186 1 11'7 28) ; this crystallises from ether in almost colourless efflorescent rhombic Iamellz n1. p. 1855-186-5° (corr.). It loses carbon dioxide when heated with nitric acid and forms picric acid. Tetranitrorhein C,4H02(N02)4(0H)2*C02H is probably an inter- mediate product in the conversion of tetranitroaloe-emodin into chrysammic acid It has been isolated as short efflorescent prisms. w.0. w. Chlorophyll. X. Comparative Investigation of Chloro- phyll from Different Plants. 11. RICHARD WILLSTATTER and ALFRED O P P ~ (Annalen 19 10 3'78 1-1 8. Compare Willstatter Hocheder and Hug Abstr. 191 0 ii 150).-An examioation of the leaves of 200 species of plants has shown that the chlorophyll present is the so-called amorphous or wax-like form which yields phytol. The phaeophytin obtained from the dried leaves gives a 33% yield of phytol provided the extraction is carried out rapidly. I nORGANIC CHEMISTRY. i. 141 many cases for example grass and plantains good yields of pbytol are also obtained when a slow method of extraction is used but in others the amount of phytol isolated diminishes as length of time taken for the extraction is increased.Thus the yields OF phytol from Hermleurra spondylium are 6.0 when the extraction takes twenty-four hours 20.2 for one hour and 31.5% for three-quarters of an hour. It is evident that the chlorophyll loses its phytol when its alcoholic solution is left in contact with the plant tissues and this loss is due to enzyme action (Willstatter and Stoll next abstract). The results account for the low percentages of phytol obtained in previous experiments (Zoc. ci".) as the slow method of extraction was used. The increase observed in the amount of phytol when the dried material is kept can be accounted for by the enzyme losing its activity with age.The one consists in rubbing the leaf powder with chalk and sufficient alcohol to form a thick paste (about 1 litre per kilo. of leaf powder) leaving for five minutes filtering under pressure and washing with small amounts of alcohol. The second method consists in making a much stiffer paste 300 C.C. of alcohol for 1 kilo. of powder and placing on a percolator and using low pressures. This second metbod is the better when comparatively concentrated solutions of chlorophyll are required. The phzeophytin was obtained by the addition of oxalic acid to the extract. When chlorophyll had not undergone decomposition a fine compact precipitate of phaeophytin mixed with oxalates was obtained but if much phytol has been formed the precipitate had a voluminous coagulated appearance.Phytochlorin-e and phytorhodin-g have been isolated from the phEophytin from 125 different plant species. The amount OF phyto- rhodin-g diminishes as the boiling with the alcoholic potassium hydroxide is increased or as the concentzation of the alkali is increased. I n many cases a phytochlorin somewhat more feebly- basic than phytochlorin-e was isolated. The usual method of hydrolysis was boiling for two to three hours with 24% methyl-alcoholic potassium hydroxide using 5 C.C. of solution for 1 gram of phzeophytin. J. J. S. Chlorophyll. XI. Chlorophyllase. RICHARD WILLSTATTER and ARTHUR STOLL (Annulen 1910 3'78 18-72).-Willstatter and Oppe (preceding abstract) have shown that the conversion of amorphous chlorophyll into crystallised chlorophyll is accompanied by the elimination of a phytol group and that the change occurs when the process of extraction is slow but can be avoided by using a rapid method of extraction.It is now shown that crystallised chlorophyll contains one methoxy- and one ethoxy-group and not two methoxy- groups (Willstgtter Hocheder and Hug Abstr. 1910 ii 150) and that the amorphous chlorophyll contains one methoxy- and one phytyl group; it is proved that the change of the amorphous into the crystallised chlorophyll is a process of alcoholysis and in each stage of the change the phytol eliminated is equivalent to the ethyl alcohol Two quick methods of extraction are described.i 142 ABSTRACTS OF CHEMICAL PAPERS. entering the molecule.equation The reaction which is represented by the C,,H,*OH + C0,H*C,1H,,N411g( CO,Me).CO,Et takes place in the presence of a specific enzyme chlorophyllase which belongs to the group of esterases. Other substances of the same group for example lipsse from linseed or pancreas lipase cannot bring about the same change. The enzyme reacts slowly with pbEophytin and does not react at all with waxes of an ester nature. It is highly probable that the enzyme brings about the formation of phytyl esters in the plant. Working with methyl alcohol it has been found possible to replace the pbytoxyl groups by methoxyl (methanolysis) and in the presence of moist ether to replace the phytoxyl group by hydroxyl (hydrolysis). Lipases on the other hand produce hydrolysis but do not appear able to induce alcoholysis.The following system of nomenclature is suggested for chlorophyll derivatives the tricarboxylic acid C31H29T4Mg( CO,H) from which chlorophyll is derived is called chlorophyllan ; the monomethyl ester obtained by the hydrolysis of chlorophyll is termed chlorophyllicle ; amorphous chlorophyll is phytylchZorophylEide ; Borodin’s crystallised chlorophyll is ethylchlorophyllide ; the magnesium-free compound is termed phcceophor6ide; phaeophytin is thus phytylphccenphorbide and the compound hitherto called phaeophorbin is ethylphaeophwbide. A rapid method for the extraction of chlorophyll is described which differs somewhat from those recommended by Willstatter and Oppe (preceding abstract). It consists in moistening 1 kilo. of the leaf meal for five minutes with 0.5 litre of alcohol (96%) then spreading on a thimble and applying suction for a short time.The addition of alcohol and suction are used alternately until a further litre of alcohol has been added; in the course of twenty minutes 1 litre of solution is obtained; by washing with alcohol a further 0.9 litre of extract is obtained in thirty-five minutes more. The amount of chlorophyll in the two extracts is 80% of the total present. The solutions although dilute are purer than those obtained by the methods already described and therefore yield more phaeophytin. For the estimations of phytol the method already described (Abstr. 1910 ii 150) has been used. The amount of chlorophyll transformed into ethylchlorophyllide by means of chlorophyllase has been deter- mined both by the estimation of the phytol liberated and by determining the amount of silver iodide obtained from the product by Zeisel’s method.Details for the calculations are given. The results obtained by the two methods agree indicating t h a t the ethyl groups ent2ring the molecule are equivalent to phytyl groups removed. It is highly probable that the reaction is a direct exchange of alkyl for phytyl groups and that it does not consist in the hydrolysis of the phytyl ester to the acid and the subsequent conversion of this into the ethyl ester. The enzyme was in the form of leaf meal from which the chlorophyll had been extracted and was used whilst moist with alcohol. The reaction was most rapid when the mixture was kept well shaken and in eachexperiment the flasks were well corked in order to prevent (:0,H*C,,H,,N,n~g(C02Me)*C0,*C20H3 + EtOH = C,IH31N4(C02H)R,ORGANIC CHEMISTRY. i.143 the admission of moisture. Although the reaction mixture is non- homogeneous i t is probable that the diffusion phenomena are such that the mixture behaves as if it were a homogeneous one. The values of K however when calculated by means of the equation for a iinimolecular reaction are not constant but diminish as t increases. This is shown t o be due partly to the fact that the enzyme tends to become less active when kept for some time. With varying amounts of enzyme Schutz's rule p = K JKt holds good approximately. With chlorophyll solutions of different concentrations the amount transformed in a given time is roughly proportional to the concentration.The addition of water to the alcoholic solutions accelerates the activity of the chlorophyllase; thus the value of I l x lo3 after ten hours varies from 28 to 3'7 using 92% alcohol but with 80% alcohol K x 1013 has the values 175 166 and 80. Even in 80% alcohol the reaction is a true alcoholpsis and not hydrolysis. The activity of the enzyme is less at 35' than a t 25'; when boiled with alcohol the enzyme is gradually destroyed and in drying leaves for the preparation of the enzyme i t is necessary to avoid high temperatures. Calcium carbonate has no effect on the alcoholysis whereas magnesium hydroxide has an appreciable retarding effect. Young leaves appear to contain a smaller amount of enzyme than older ones and the amount tends to increase as the chlorophyll increases.The methylchlorophyllide obtained by using methyl in place of ethyl alcohol is formed much less readily and its isolation is rendered difficult by the readiness with which it is transformed into readily soluble derivatives. The reaction proceeds more readily in the presence of a small amount of water for example in 92% methyl alcohol but the best results are obtained by treating fresh leaves with 50-60% methyl alcohol. The product varies with the species of plant used ; that obtained from Eeruclewm C7,H7,01,N,Mg2 crystallises from ether in which it is sparingly soluble in steel-blue glistening prisms. The corresponding methylphaeophorbide C7,H7,O1,N forms glistening spindle-shaped crystals with a metallic lustre.The methyl- chlorophyllide from stinging nettles is somewhat more readily soluble in ether and crystallises in triangular and hexagonal plates. Chlorophyllide CO,Me*C,,H,,N,Mg(CO,H) may be obtained by the action of the enzyme on a moist ethereal solution of chlorophyll in the absence of alcohol. It forms green plates and is extremely unstable and is transformed readily into the isomeric magnesium phaeophorbide C0,Me*C,~H,l(C02)zMg which forms black crystals readily decomposed by acid. The synthesis of chlorophyll from chlorophyllide and phytol can be accomplishsd by means of chlorophyllase but the yields are small. Chlorophyll always appears to be accompanied by chlorophyllase ; in Soybus aucupuria Mellitis melissoph. Stachys silvitica Lamium maculatum and Herudeurn the amount of enzyme is comparatively large.The presence of the enzyme in stinging nettles grass Sambucus Aspidium Equisetum Taxua Avena and Platanus can be demonstrated by the prolonged action of the tissue on the chlorophyll extract when products are obtained which contain but little combined ph ytol. Extracts of stinging nettles and of PZatanus react with the enzymei. 144 ABSTRACTS OF CHEMICAL PAPERS. from Glxleopsi.9 or Heracleuin more readily than with their own enzymes but the alcoholysis does not proceed to completion. Under conditions which result in the complete alcoholysis of the chlorophyll of Galeopsis or Herudeurn only 66% of the chlorophyll of stinging nettles is decomposed. The chlorophyll of Herudeurn reacts only slowly with stinging-nettle meal but the rate is greater than that between stinging-nettle meal and the chlorophyll from stinging-nettle ex tract.J. J. S. Chlorophyll. XII. Phytol I. RICHARD WILLSTATTER ERWIN W. MAYER and ERNST HUNI (Annulen 1910,378,73-152. Compare Willstatter and Hocheder (Abstr. 1907 i 7S4).-Crude phytol and the distilled product are not identical but isomeric and the process of distillation appears to produce a shifting of a double linking. The two are termed respectfully a- and P-phytol. An examination of the products of oxidation shows that the a-compound has the olefine linking between carbons 5 and 6 as it yields a ketone Cl,H3,0 whereas P-phytol yields a ketone C,,H260 and contains a n olefine linking between carbons 7 and 8. The chief oxidation products isolated are the following ketones and acids.(1) Ketone C,,H,,O obtained from a-phytol by means of chromic anhydride or from the a-ozonide. (2) Ketone C,,H,,O from P-phytol by means of chromic anhydride from the P-ozonide or from the acid C14H2s02 by means of chromic acid. (3) Ketone C,,H,,O from trihydroxyphytan and chromic acid or by the action of ozone on the ketones 1 and 2. (4) Ketone C,H,,O by the action of ozone on any of the other ketones. ( 5 ) Acid C14H,,02 from a-phytol and ozone from trihydroxyphytan and chromic acid or from the ozonide of the olefine C15€€30. (6) Acid C12H2,02 from the ketone C,,H,,O and ozone from the ketom C13H,,0 and chromic acid or from the acid C14H2802 and chromic acid. (7) Acid Cl0H2,O2 from the ketone C15H,o0 and ozone and from the ozonide of the olefine C,,H,,. The first two ketones are easily obtained in a state of purity but the two lower ones are more difficult to prepare.They are all methyl ketones altbough they yield only traces of bromoform with hypo- bromite and only small amounts of methylamine by the Beckmann transformation. The presence of the acetyl group in the ketone C,,H,,O can be demonstrated by the following series of reactions C,,H27*CH(OH)*CH2*OH -+ C,,H,7*C02H. The four ketones resemble one another in physical properties. They are pale yellowish- green oils with relatively high b. p.’s and it is suggested that the compounds especially the lower members have the tautoineric enolic structure. The acids are saturated and do not decolorise bromine but react readily with permanganate.They do not crystallise and resemble phgtol in physical properties. The reduction products of phytol and also numerous esters have been prepared. a-Phytol contains the double linking in the Pa-position with respect to the CH2*OH-group as the phytenic acid obtained by oxidising with chromic acid is an up-unsaturated acid and the following structural C,,H,?*CO*CH -+ C,,H,i*CH(OH)*CH -+ C,,H2r*CH:CH -+ORGANIC CHEMISTRY. i. 145 formula is suggested CHMe,'[CH31e],*C;Me:CMe.CHMe*CHMe*CH2*OH. It is possible that a-phytol is a condensation product of isoprene 4C5H8 + H,O + 3 8 = C20H400. The formula suggested for P-phytol is CHMe,fCHMe]4*CMe:CMe*[C€lMe]2*CH2*OH. a-Phytol has DF 0.856 and ng1.46364 and P-phytol D," Oms52 and n 1.46380.It can be distilled in portions of 10-30 grams from Claisen flasks and has b. p. 203-204"/9-10 mm. Both compounds give the same iodine number. A good test for the presence of phytol for example in phaeophytin preparations is the formation of a stable colourless oil by heating for a short time with concentrated nitric acid. When the boiling is prolonged a nitrogenous acid is formed the alkaline solutions of which have an intense yellow colour. Many phytol preparations both crude and didtilled undergo autoxidation (Engler and Weissberg Abstr. 1899 i 189) when kept for several months in corked vessels. A sharp penetrating odour with an acid reaction is noticeable and the oil becomes limpid and a t the same time distinctly acid. The formation of a peroxide can be detected by Engler's method.The rate of autoxidation varies considerably with different samples and it is probable that small amounts of some impurity present in both the crude and the distilled products act as a catalyst. The acid formed. is not homogeneous and is unsaturated; the analytical numbers indicate that it may be a mixture of equal amounts of phytenic acid and a saturated acid with 10 carbon atoms. Phytyl hydq*oyen p~~thulates COzH*C,H4*C0,*C,,H,q are formed when the phytol and phthalic anhydride are boiled for five hours with benzene and can be isolated by making use OF the fact that their sodium salts are very sparingly soluble in water but are soluble in ether. The a-phytyl ester is a syrup readily soluble in most organic solvents ; it yields an oily dibromide which is unstable and a silver salt C,,H,,O,Ag in the form of minute flat prisms m.p. 119" ; the isomeric stlver P-phytyl phthalute crystallises in prisms m. p. 116'. Cetyl hydrogen p?&alute C0,H-C6H4*C0,*C1,€I, forms indefinite crystals of a waxy consistency and has m. p. 61-62' The silver salt C,,H,70 A g crystallises from benzene. Phytyl ether 0(C70H39)2 obtained by the action of concentrated sulphuric acid on a glacial acetic acid solution of the alcohol is a viscid oil sparingly souluble in glacial acetic acid or in methyl alcohol and forms a dibromide. Phytol cannot be reduced by means of sodium and ethyl or amyl alcohol but by electrolytic reduction in cold alcoholic sulphuric acid solution using platinised platinurn electrodes with a voltage of 6 and a curreut density of 3 ampere per sq.m. and an earthenware diaphragm the saturated alcohol phytanol (dihydrophytol) C,? H,,O is obtained together with the hydrocarbon phytan. Phytanol is readily prepared by reduckg phytol with hydrogen in ethereal solution using platinum- black as catalyst; a slow stream of hydrogen is passed through for about three weeks when 40 grams of phytol are used. The reduction is ruuch quicker when the hydrogen is used under slight pressure and the apparatus is shaken continuously. It is a colourless odourless oil has b. p. 20165-2020/9-5 mm. is miscible with all organici. 146 ABSTRACTS OF CHEMICAL PAPERS. solvents and is isomeric with arachyl alcohol (Haller Abstr. 1907 i 377). It forms a sodium derivative C,,H,,*ONa in the form of a viscid oil soluble in ether or light petroleum.The phenylurethane NHPh*CO*O*C20H+l obtained by the combina- tion of the alcohol with phenylcarbimide is also a thick oil. Phytanyl hydrogen phthalate C0,H*C6H,*C02*C,,H41 is a syrup and ibs silver salt C,,H,,O,Ag has m p. 1 06-106450. Phytanyl pyruuate CH,* CO*CO,*C,,H, obtained by heating the components a t 110-120° or more readily by shaking the alcohol for a long time at the ordinary temperature with five times its weight of pyruvic acid and removing the excess of acid by means of water has b. p. 219-220°/10 mm.; its aemiccwbazone C23H4703N3 cryatallises from methyl alcohol in needles m. p. 88-91'. Cetyl pyruvate has m. p. 26*5-27.5" and its semicarbazone C,,H,,O,N,. crystallises in flat prisms m.p. 140-141'. The esterification of P-phytol by means of glacial acetic acid at 155' has been studied ; at the end of one hour 3445% of the acid is trans- formed into ester but after one hundred and forty-four hours the yield has fallen to 6*9% owing to decomposition of the ester into phytndiene. Geraniol and nerol react in much the same manner with glacial acetic acid at 155". The initial rates of esterification with acetic acid a t 155' of the following unsaturated alcohols have been determined oleyl alcohol erucyl alcohol geraniol nerol cholesterol and the values obtained are smaller than those for the corresponding saturated alcohols. Erucyl ulcohol C22H440 prepared by reducing ethyl erucate with boiling amyl alcohol and sodium has b. p. 240*5-241-5°/10 mm.and forms rhombohedra1 crystals m. p. 34.5-35-5". Its dibromide C,?H,,OBr forms glistening prisms m. p. 45-45-54 When reduced with hydrogen in the presence of finely- divided platinum the unsaturated alcohol yields docosyl alcohol C,,H,,O which crystallises from chloroform in glistening prisms m. p. 71-71.5° ; the phenplurethane C,,H,,O,N crystallises from ethyl acetate in glistening prisms m. p. 86-86-5'. The percentages of acetic acid transformed into ester at 155" are the following dihydrophytol '73 ; arachyl alcohol 76.2 ; tetrahydrogeraniol 68.5. These values are lower than those given by normal alcohols. Pliytanic acid C,,H,,02 is best prepared by oxidising dihydrophytol with an acetic acid solution of chromic acid in the presence of potassium hydrogen sulphate and forms a viscid oil b. p.221"/7.5 mm. The silver salt C,,H,,O,Ag darkens a t 165" and has m. p. 177-177.5". Ths umide C,,H,,*CU*NH crystallises when its solutions in methyl alcohol or light petroleum are well cooled and has m. p. 53-53'5'. AP-l'hytenic acid C,,H,O is formed together with the kebone C,,H,,.O when phytol is oxidised with an acetic acid solution of chromic anhydride (5 atoms of 0) in the presence of potassium hydrogen sulphate. It forms a yellow oil b. p. 210-220°/11.5 mm. and has D," 0.917 and 12;' 0,893. The position of the ethylene linking is established by the readiness with which it yields a y-lactone (Abstr. 1907 i 786) when heated with sulphuric acid and water The saturated hydrocarbon phytane is most readily obtained bg reducing pfiytene with hydrogen and platinum; it is a colourlesa,ORGANIC CHEMISTRY i 147 mobile oil with b.p 169650/9*5 mm. and Df 0.803 is only sparingly soluble in cold methyl alcohol and solidifies when cooled by liquid air. In t.he preparation of phytene (Abstr 1907 i 786) a di-iodo- derivative C2,H,,T2 is obtained in the form of a heavy oil and when this is reduced with zinc dust and glacial acetic acid or with zinc dust and hydriodic acid it yields impure phytene although the two iodiue atoms are not attached to adjacent carbon atoms. Phytadiene C2,H3* is formed when P-phytol phthalic anhydride ,and benzene are heated for a day in a Babo funnel owing t o the readiness with which the phytyl hydrogen phthalate decomposes into phytadiene and phthalic acid ; it has b.p. 186-187°/13 mm. and DF 0 826 and its iodine number points t o the presence of two olefine linkings. a-Phytol ozonide prepared by passing a current of 6% ozone into a dry chloroform solution of the alcohol and then removing the chloroform under reduced pressure at 20° forms a pale green syrup with a pungent odour and dissolves readily in most organic solvents. Methyl alcohol separates the crude ozonide into an insoluble “ motoxide,” C2,H4,0,0 and a soluble oxozonide C,,H,,O,O,. The yield of the ‘‘ moloxide ” is larger the shorter the time of ozonising and i t canbe obtained crystalline by well cooling its methyl alcoholic solution. It is a n oil at the ordinary temperature and when boiled with water yields the same products and in the same amounts as the oxozonide.Tbis latter when kept for some months under reduced pressure over phosphoric anhydride yields the normal oxonide C,,H,,O,O,. The best yields of the ketone C,,H,,O are obtained when a-phytol is oxidised with a glacial acetic acid solution of chromic anhydride in the presence of potassium hydrogen sulphate. With the theoretical amount of oxygen only a small amount of the alcohol is osidised ; but with 4 to 5 atoms of oxygen t o each molecule of alcohol a 73-97% yield of ketone can be obtained. The same ketone is also formed when either of the ozonides of a-phytol is boiled with water for three hours in a reflux apparatus using 25 grams at a time. The aqueous solution has a decided acid reaction and gives the ordinary reactions for aldehydes. Tho oily product consists of the ketone together with the acid C14H2802 (3*5%) phytenic acid the hydrocarbon C15Hi(2 and a small amount of a n ether.The acids can be removed by extraction with very dilute sodium hydroxide solution and the ketone purified by dis- tillation under reduced pressure. It forms a pale yellowish-green limpid oil which turns quite colourless in the course of two t o three weeks. It has b. p. 173-174’/9 mm. and 291*8-292*4O/722 mm. and is optically inactive. The oxime C,,H,,ON is a viscid oil with b. p. 201-202°/ 10 mm. and DS 0.885 ; the sernicarbaxone C,,H,,ON crystallises from alcohol i n woll-developed prisms m. p. 64*5O and the p-nitrophenyl- hydyazone C2,Ha502N3 forms a pale yellow oil. The ketone combines with bromine in chloroform solution yielding an unstable dibromide which is probably derived from the isomeric enolic compound Many ketones for example cholestanone and methyl ethyl ketone form colourless dibromides in solution (compare also Linnemann Annalen 1863 125 307; Lippmann Zeitsch.Chem. 1869 5 29). The ketone gives negative results with the following reagents for aldehydes sodium amalgam and diazobenzenesulphonic acid beuzenesulpho-i. 148 ABSTRACTS OF CHEMICAL PAPERS hydroxamic acid pyruvic acid and P-naphthylamine. It yields a Deroxide from which the ketones Cl3H2,O and Cl1H2,O are formed by Loiling with water. The alcohol C,,H,,O obtained by reducing the ketone with sodium and alcohol is a colourless viscid liquid with b. p. 178-180"/12 mm. or 173-174@/8 mm. Di 0.848 DY 0.838 and nz 1.44912.The saturated hydrocarbon C15H32 occurs in the first fraction obtained by distilling the crude ketone under diminished pressure and is deprived of the last traces of ketone by repeatedly shaking with three times its volume of glacial acetic acid in which the ketone is readily soluble. It has b. p. 260*5-263*5O/723 mm. (corr.) or 127-130°/9*5 mm. D 0.789 Di0 0.779 and nz 1.43322 and is also formed in small quantities when the ketone is reduced with zinc dust and glacial acetic acid. The oZe$ne CH,:CH*CHMe*C,,H, obtained by the action of phosphoric oxide on the alcohol C,,H,,O at 60-7O0 has b. p. 150-152°/11 mm. or 29O0(corr.)/724 mm. Dt 0.803 and Di0 0.790 and combines readily with bromine. Its ozonide Cl5H3,O4 is a viscid oil with a pale green colour.When the alcohol C,,H3,0 is heated at 150° for an hour with phosphoric oxide or when the above olefine is heated for several hours at 130° with the anhydride a product is formed which contains a small amount of a saturated (cyclic) hydrocarbon. The ketone C,,H,,O resembles its higher homologue ; it has b. p. 168-170°/10 uim. or 288-289O/722 mm. D 0.865 D:00+348 and is optically inactive. It is not oxidised so readily as its homologue C15H300. The ozime Cl,H,,ON is a viscid oil b. p. 196-19S0/11 mm. and Uq 0.891 and the semicccrbaxone Cl,H,,ON forms slender needles m. p. 62'. A 94% yield of the ketone is formed by oxidising P-phytol with a glacial acetic acid solution of chromium trioxide in the presence of potassium hydrogen sulphate and an 82% yield by boiling P-phytol- ozonide with water.It is formed together with the acid C1,H,,O (26-33%) by oxidising the ketone Ci5H,o0 with a glacial acetic acid solution of chromium trioxide in the presence of concentrated sulphuric acid. A by-product formed at the same time is the ether O(C,,H,i)2 which has b. p. 228-233O/722 mm. and DqO.836. Z~ihydroxyp~~yt~~rLe C20H39(OH)3 obtained by converting a-phytol dibromide into the acetate and subsequent hydrolysis is a viscid oil sparingly soluble in cold methyl alcohol and when oxidised with chromium trioxide in the presence of glacial acetic and concentrated sulphutic acids yields the ketone C,,H,,O as a colourless mobile oil b. p. 16S-17Oo/8 mm. together with the acid C1,H,,02; its semi- carbazone C,,H 250N3 crystallises from alcohol in needles m.p. 68-72'. The same ketone is formed when the product obtained by the prolonged action of ozone on the ketone Cl5H3,,0 is boiled with water. The ketone C9Hl8O is a limpid oil with b. p. 16S0/10 mm. or 282O/720 mm. and has l.); 0.836. The olefine dibrornide C,,H,,Br is a yellow oil and when shaken with silver acetate and glacial acetic acid at the ordinary temperature yields the bromoacetyl derivative C15HROBrAc as a viscid oil which reacts with silver acetate at loo" yielding the diucetate and this on bydrolysis with cold methyl-alcoholic potassium hydroxide yields an Its semicadaxone has m. p. 75'.ORGANIC CHEMISTRY. i. 149 ether oE the glycol (C,,H,,*OH)O as a brown viscid oil. The ether when oxidised with chromium trioxide glacial acetic and sulphuric acids yields as intermediate product a carbony1 compound C,,H,,O and ultimately the acid C,,H,802. The same acid is also formed when the olefine ozonide is boiled for five hours with water but appreciable amounts of the ester C,H17*C0,*C,,H, are also formed.The acid C14H2*02 is a colonrless comparatively viscid oil with b. p. 1 86-188°/ 8-9 mm. DS 0.887 and DJ"" 0.870. The siZver salt C,4H2702Ag is obtained crystalline by using alcoholic solutions and has m. p. The acid C,,H,,O is a colourless odourless,viscid oil b. p. 155-1 5S0/ 11 mm. and 261°/732 mm. D 0.956 Di0 0.936 and rtg 1.45205; it decolorises permanganate in glacial acetic acid solution after a short time. The silver salt CIqH,,O,Ag,. forms a crystalline precipitate and with benzene forms colloidal solutions.The ester C9H17*C02*C,oH,I forms a colourlesP mobile oil b. p. 175-176°/11 mm. Dj 0.889 and DSo 0*808. It is hydrolysed by a cold concentrated solution of potassium hydroxide in methyl alcohol. Electrical conductivity measurements of the acid C10H2002 phytanic acid and AP-phytenic acid were made in aqueous alcoholic solution. The unsaturated acid is a better electrolyte than the saturated acid and the acid C,,H,,,O conducts better than acetic acid. A distillation flask similar to that described by Michael (Abstr. 1902 i 70) is recommended for distillations under reduced pressure. Use is made of a column of glass beads but the capillary tube for introducing bubbles of air is passed through a side-tube fused into t h e body of the flask.186-188O. J. J. S. Condensation Products of 2-Coumaranone. KARL FRIES and W. PFAFFENDORF (Ber. 1911 44,114-124. Compare Abstr. 1910 i 186; also Fries and Fink Abstr. 1909 i 42,44).-By the condensation of 2-coumarone with sodium ethoxide solution in the absence of air i t has been found possible t o obtain two isomeric compounds C10H1003. The relative amounts of the two vary with the conditions but so far it has not been found possible t o ascertain the conditions which determine the proportions. Neither compound appears t o have t'he hydroxylic structure corresponding with the acetyl derivative already described (Abstr. 1910 i 186) as they are both very sparingly soluble in alkalis. They are represented as isomeric ketones and both yield 2 1'-diketo-A'* 2-1 2'-dicoumaran (" oxindirubin," '' 1 2-bis- coumaran-indigo") when mixed with a small amount of bromine in glacial acetic acid solution. 2- Keto-1 2'-coumurancounz arone C,H4<O>CH co C<Ee->O is the chief product obtained by condensing 2-coumaranone with a hot 3% sodium ethoxide solution and is also formed by t'he hydrolysis of the acetate (Zoc.cit.). It crystallises from methyl alcohol in compact. colourless needles m. p. 1 1 6 O and its solution in concentrated sulphuria acid has a yellowish-red colour with a strong yellowish-green fluor- escence. Its solutions especially in the presence of impurities are VOL. c. i. rni. 150 ABSTRACTS OF CHEMICAL PAPERS. unstable. It yields a somewhat unstable hydrobromide in the form of light red needles and with acetic anhydride and sodium acetate yields the acetate of the tau tomeric hydroxy-compound.The isomeric 2-~eto-Al:~-dicozcmurccn C,H4<-,->C:C<2Z2>0 co is more readily soluble in acetone and crystallises from methyl alcoh61 in brilliant coppery-red plates m. p. 141'. It is decomposed when boiled for some time with methyl alcohol yields a yellowish-red hydrochloride and is most readily obtained by condensing 2-coumarone with glacial acetic acid saturated with hydrogen bromide. When either of the ketones or the ,acetate m. p. 106' is heated for eight hours at 100' with a saturated solution of hydrogen chloride in glacial acetic acid a product C,,H1604 76H4*7=$!'V is obtained which crystallises from xylene in flesh- o-s $*C,B4 coloured needles. These are not molten at 340° y6114*F 7.Q but sublime in reddish plates with a metallic lustre.()-- C=C.C,H The annexed formula is suggested. Nitric acid con- verts it into a deep black-coloured substance the acetic acid solution of which has a reddish-violet colour. By the condensation of 5-methglcoumaranone with sodium ethoxide only one product is obtained namely 2-keto-5 5'-dimetlllyl-A1:2'-di- coumaran C,,H140,. This crystallises from alcohol in yellow prisms m.p 156'(when quickly heated) and is readily oxidised to 5 :5'-dirnethyl- leuco-oxindirubin. It undergoes decomposition when heated alone or with glacial acetic acid. The product C36H2404 obtained by heating the acetate m. p. 133' (Zoc. cit.) with a saturated solution of hydrogen chloride in glacial acetic acid crystallises from xylene in pale red needles which melt above 340'.When rubbed with a little nitric mid it yields a blue-black compound which dissolves in glacial acetic acid to brilliant violet-blue coloured solutions. 2 1'-Dihydroxy-1 2'-dicoumarone (" leuco-oxindirubin ") yields a phenylhydruxone C,,H,,O,N which crystallises from glacial acetic acid in pale red needles m. p 179' and when hydrolysed with hydrochloric acid yields oxindzrubm. The acetyl derivative of 2 1'-dihydroxy-1 2'-dicoumarone ClsHleOs crystallises in glistening plates m. p. 198'; when hydrolysed mlth alkalis it yields the leuco-compound but with hydrochloric acid yields oxindirubin The phenylhydraxonte of 2 l'-dihydroxy-5 5'-dimethyl-l 2'-di- coumarone C,,H,,O,N forms xed needles m. p.163'. The oxime C,,H1,O,N crystallises from methyl alcohol in yellow needles m. p. 194' and the acetyl derivative C2,H1,05 in yellow prisms m. p. 200'. J. J. S. Oxindigo [2 %Diket~-A~:~'-dicournaran]. KARL FRIES and A. HASSELBACH (Bey. 1911 44 124-128).-So far it has not been found possible to obtain ( 6 oxindigo " by the alkaline oxidation of %coumaranone or from halogen derivatives of coumaranone (com- pare Abstr. 1897 i 424; 1901 i 9 4 ; 1909 i 44 174). Attempts to prepare the oxygen compound of the action ofORGANIC CHEMISTRY. i. 151 ammonium sulphide on p-dimethylaminoanildiketocoumaran were also unsuccessful. By the condensation of the anil derivative with 2-coumaranone in boiling xylene a product C,,H,,O,N is formed and this when hydrolysed by means of a mixture of glacial acetic and concentrated sulphuric acid a t the ordinary temperature yields amino-dimethyl- aniline and '' oxindigo." 3- Keto-2-p-dimethylanainoanilcoumara~a c,H,<~:>c N* C,H,*NMe prepared by the action of an alcoholic solution of 2-coumnranone on an alcoholic solution of p-nitrosodimethylaniline in the presence of 2N-sodium hydroxide solution at 3' crystallises from benzene in large prisms with a blue-black lustre or from alcohol in dark brown glistening needles m.p. 185'. It is hydrolysed by strong acids to p-aminodimethylaniline and o-hydroxyphenylglyoxylic acid. The condensation product C,,H,,O,N probably C H ~ ~ ~ > C ( N H . C ~ H . N M ~ ) *cH<!>c,H~ crystallises from a mixture of benzene and light petroleum in flat prisms with a bronzy lustre m.p. 203' (decornp.) after sintering at 190'. The yield is 30% of the theoretical and the product dissolves in alkali hydroxides yielding reddish-brown solutions. 2 2-Diketo- Al 'lt-clicoumaran ( "oxindigo," L 6 1 1 -dicoumarone-indigo") - . C,H,<:>C:C<(>C,H crystalliees from glacial acetic acid or from xylene in long prisms with an intense lemon-yellow colour. It has m. p. 272' after sintering a t 250° and its solution in con- centrated sulphuric acid has a yellowish-red colour. It is decomposed by alcoholic sodium hydroxide solution and even by sodium carbonate in the presence of alcohol. J. J. S. A New Thiophen Compound C,,H,S and Some of its Derivatives M. LANFRY (Compt. rend. 1911 152 92-94).- The tarry product obtained when a mixture of sulphur and naphthalene vapour is passed through a red-hot iron tube contains 0.2-0*4% of a compound crystallising in ruby-red /\ \/\/\/ I II ti ii s s reaction with sulphuric acid and I - leaflets or clinorhombic prisms.The substance has m. p. 115.5' (corr.) b. p. 345' and in composition approximates to the formula C,,H,S,.; it is supposed to be benxdzthaophen (annexed formulae). It gives the thiopheu isatin. The 6romo-derivative ClOS,H,Br4 crystallises in silky orange needles m. p. 247-248'. The tet~anztro-derivative CI,S,H2(N0,) was obtained as an orange powder decomposing a t 300°; it has well-marked acid characters and forms highly-coloured compounds with cyclic hydrocarbons. On treating benzdithiophen with hydrogen peroxide in acetic acid solution it yields in the first place a compound C,OH,O@ slender m 2i.152 ABSTRACTS OF CHEMICAL PAPERS. rose-yellow needles m. p. 130' having the properties of a p-diphenol. On further oxidation a second compound Cl,H60,S is formed; this crystallises in radiating red needles m. p. about 125'; it is insoluble in aqueous alkalis and develops no coloration with sulphuric acid and isatin. w. 0. w. Silicotungstates of Coniceine Sparteine and Atropine. MAURICE JAVILLIEB (BUZZ. Sci. Phccrm. 1910,315-320. Compare Abstr. 1899 ii 456 ; 1909 ii 45O).-Coniceine silicotungstate 1 2W0,,Si0,,2H20,4C,Hl,N + 3H20 prepared by adding potassium silicotungstate to an aqueous solution of coniceine tartrate is an amorphous substance which becomes anhydrous at 120". I t is soluble in boiling water ; 100 C.C. of water a t 15' dissolve about 0.02 gram of the salt.Sparteine silicotungstate 12 WO Si0,,2H20,3C,,H,,N2 + 7H20 is amorphous and loses 6H,O at 120'. The precipitation of this salt is visible in aqueous solutions containiog 0.0002% of sparteine and consequently may be omployed in estimating the alkaloid. Atropine silicotungstate 12 W0,,Si02,2H20,4C ,HpO,N + 4H,O be- comes anhydrous at 120". It is less easy t o obtain pure than the foregoing owing to a tendency to undergo hydrolysis. Advantage has been taken of its sparing solubility (less than 1 in 40,000) to Preparation of Alkyl Halides and Alkyl Nitrates of Tropeine a n d ScGpoleine Alkaloids. A. GERBER (D.R.-P. 228204).-&1ethy3- atropiniurn methosulphite C,7H,3~0,NMe*S03Me is prepared by heat- ing atropine with rmthyl sulphite and methyl alcohol in a sealed tube a t 100"; thepZccti.nichloi.ide (C17H2,0,NMeC1),PtCI forms orange- coloured leaflets.Atropine methobromide m. p. 220° and atropine metho- witrate are formed respectively by evaporating the foregoing com- pound with aqueous potassium bromide or with potassium nitrate ; these compounds are soluble in water or alcohol sparingly so in ether or acetone. Dihydroberberine. JOHANNES GADAMER (Arch. Pharm. 191 0 248 670-681).-Faltis' evidence for the view that the action of potassium hydroxide on berberine results in the formation of oxy- berberine and tetrithydroberberine (Abstr. 1910 i 698) is reviewed and criticised and further facts are brought forward in support of the author's opinion that in this reaction oxyberberine and dihydro- berberine are formed (Abstr.1902 i 173 555 ; 1905 i 369 ; Freund and Beck 1905 i 151). Faltis' observation that by the action of zinc and acetic acid on oxyberberine the latter is rendered colourless could not be confirmed. Dihydroberberine hydrochloride prepared as already described (Zoc. cit.) crystallises with 4H20 but readily loses 1H20 on drying in a desiccator. Dihy droberberine is less basic than teti ahydroberberine and is less easily removed than the latter from solution in ether by agitation with dilute hydrochloric acid. Tetrahydroberberine is resolved by crystallisa tion of t h e d-bromocamphorsulphonate into d- and I-canadines but repetition of a similar fractional crystallisation estimate atropine in pharmaceutical preparations.w. 0. w. F. M. G. M.ORGANIC CREMISTKY. i. 153 of dihydroberberine d-bromocamphorsulphonate (Abstr. 1902 i 1'73) showed that no resolution of this base took place although tetrahydro- berberine was again easily resolved either alone or in admixture with di hydroberberine. Dihydroberberine furnishes a rnethiodide m. p. 205O which dissolves i n water forming a yellow solution giving no precipitate with ammonia but forming a white precipitate with much sodium hydroxide the liquid a t the same time developing a violet fluorescence; the pre- cipitate is not dissolved by ether. Tetraiqdroberberine methiodide m. p. 245-250° is colourle~s and soluble with difficulty. Oxyberber- ine fornis an additive product with methyl sulphate.Dihydroberberine is more poisonous to rabbits than tetrahydro- berberine. T. A. H. Corydalis Alkaloids. V. R-Corydaline and Phenylberberine. JOHANNES GADAMER (Arch. Phurrn 19 10 248 6S1-695).-A des- cription of direct and indirect attempts made to resolve optically in- active corydaline m. p. 135O into optically active forms (Abstr. 1902 i 306; 1905 i 463). fractionation of the tartrate quinate and d-bromocamphorsulphonate were unsuccessful. Natural d-corydaline does not give a crystalline salt with the last-mentioned acid. Attempts were then made to effect the resolution of a-methyl- dihydroberberine (Freund and Beck Abstr. 1905 i 151) and to reduce the d- and l-isomerides thus obtained so producing active forms which should differ from corydaline only in containing a dioxymethylene group in place of two methoxyls and should therefore correspond with the d- and Z-corydalines and to d- and Z-mesocorydaline (compare Freund and Mayer Abstr.1907 i 633). The resolution of r-a-methyldihydro- berberirie could not however be effected and this was also the case for pheny 1 berberine. Oxyberberine treated with magnesium ethyl iodide in benzene solution with dimethylaniline as a catalyst was recovered for the most part unchanged but small quantities of methylnoroxyberberine (Faltis Ahstr. 1910 i 698) and of a non-basic substance m. p. 165-166' separating from alcohol in bright yellow crystals were obtained. Oxyberberine reacts with magnesium phenyl bromide in ether to form (1) a tertiary buse which may be either a phenyltetra- hydrober berine or diphenyldihydroberberine and (2) phenylberberine.The latter furnishes a hydrochloride m. p. 255-257' (decomp.) which separates from alcohol or water in brownish-yellow crystals. The aurichloride m. p. 215-216" (decomp.) forms long brown needles from alcohol containing hydrochloric acid. The acid sulphate softens a t 270° but does not melt even at 278" and separates from dilute sulphuric acid in compact yellow crystals. The nitrate m. p. 268-270" (decomp.) is deposited from alcohol in compact brown crystals. On reduction with zinc and dilute sulphuric acid phenylberberine hydrochloride yields phenyltetrahydroberberine m. p. 222" which [With ERNST STEINBRECHER.]-AttemptE to eff eCt resolution byi. 154 ABSTRACTS OF CHEMICAL PAPERS.separates from a mixture of chloroform and alcohol in compact almost colourless crystals and may also be obtained by reduction of phenyldihydroberberine. The latter prepared by Freund and Beck's method (Abstr. 1905 i 151) on oxidation with iodine in alcohol fur- nished isophenylberberine which gives a hydrochloride m. p. 275-278' (decomp.) separating from water in silky bright yellow crystals. The aurichloride forms reddish-brown short needles sinters a t 250° but does not melt at 280' ; along with it was produced a second gold salt m. p. 223-225' which may be impure phenylberberine aurichloride (see above) since on decomposition with hydrogen sulphide it yielded some phenylberberine hydrochloride. This phenylberberine is probably produced in the initial oxidation along with isophenylberberine. The latter on reduction yielded a varnish from which no crystalline derivative could be obtained.The relationship between phenyl- berberine and isophenylberberine is uncertain 2nd it is regarded as improbable that the difference is due to hydrogenation of a different pyridine nucleus in each case. T. A. H. Preparation of Curarine. RUDOLF BOEHM (Pjiiger's Archiu 1910 138 203-207).-The action of curare is so uncertain because commercial specimens contain other substances in addition to its most active constituent curarine. The best kinds of curare contain only 3 to 9% of this alkaloid. Very small doses of curarine produce marked results. The methods of separating i t from curare have been dealt with in extenso in the author's previous writings (Abstr.1887 1125 ; 1898 i 283) and are brieflygiven in the present paper. W. D. H. Preparation of Alkylhalogen Derivatives of Morphine Alkaloids. A. GERBEH (D.R.-P. 228247).-The halogen double salts of the alkaloids and their quaternary compounds obtained by the action of alkyl halides and methyl sulphate have been pre- viously described (Abstr. 1.905 i 542 658; 1906 i 530 877; 1908 i 452) and the work has now been extended to the products obtained with methyl sulphite. Methylrnorphinium methosulphite C17Hl,0,NMe*S0,Me is prepared by heating morphine with methyl sulphite and methyl alcohol in a sealed tube at looo and subsequently evaporating in a vacuum; the amorphous faintly coloured hygroscopic product is rendered crystalline by dissolving in absolute alcohol and precipitating with ether ; when evaporated with a saturated solution of potassium bromide it is con- verted into morphine methobromide (m.p. 260'). Jlethylrtarcotinium methosulphite has similar properties and is analogckly prepared from nircotine ; its platinichloride ( C,,H,,07NMeC1),PtCI forms small orange crystals. Methylcodeinium methosulphite methylapomorphinium methosulphite metliylthe6anium methosulphite with their respective rnethobromides were also prepared ; thebaine methobromide has m. p. 185'. F M. G. M.ORGANIC CHEMISTRY. i. 155 Strychnine and Brucine. 11. ROBERTO CIUSA and G. SCAGLIAEINI (Atti R. Accad. Lincei 1910 [v] 19 ii 501-505. Compare Abstr. 1910 i 583).-When cacothelin is suspended in water acidified with hydrobromic acid and treated with bromine water until it has all dissolved it is converted into the hydvobromide of an acid C19H2206N2,HBr,2H20 which is obtained in yellow crystals by the evaporation of the solution The free acid Cl,H220,N2,2H,0 (com- pare Hanssen Abstr.1887 505) forms scales having a nacreous lustre. It is not toxic. The platinichloride (C1,H220,N2),H2PtC1 obtained in presence of hydrochloric acid crystallises in small yellow prisms. R. V. S. Identity of Vernine and Guanosine and Notes on Vicine and Convicine. ERNST SCHULZE and G. TRrEa (Zeitsch. physiol. Chem. 1910 70 143-151. Compare Abstr. 1910 ii 645).-The pentose (compare Schulze and Castoro Abstr. 1904 ii 506) obtained by the hydrolysis of vernine yields I-arabinose-p- bromophenylosazone (Levene and Jacobs Abstr.1909 i 858) and is presumably d-ribose. A detailed comparison of vernine with Levene and Jacobs' guanosine (Abstr. 1910 i 620) has proved that the two are identical. The following formula are suggested for vicine and convicine namely The hydrolysis of vicine is represented by the equations C2?H36015NS and CX)H!?5016N69 2H20' C20H36015NS + H2° = CSH1.404NS + 2C6H1206 Dwicin. Hexoses. (2) C,H,*O,Ns + 4H2O = C,H,oOsN4 + 4NH3 and that of convicine by the equation C20H2,016N6,2H,0 + 4H20 = CsH,0,N4,2H20 + 2C,H1206 + 2NH Alloxanthin. (compare Ritthausen Abstr. 1881 1158 ; 1899 i 715). hexoses with pyrimidine derivatives. The two compounds are thus glucosides formed by the condensation of J. J. S. Indole in Coal Tar. RUDOLF WEISSGERBER (Ber. 1910 43 3520-3528).-The sodium derivative of indole C,H,<G!;>cH is obtained in the form of a brown amorphous mass m.p. 140° by heating indole with sodamide at 150-160° or with sodium at 170-180O ; it reacts with methyl iodide yielding 1-methylindole together with small quantities of 2-methylindole and 3-methylindole. On warming with benzoyl chloride in benzene solution it yields benxoylindole C6H4<gE>cH ; the latter crystallises from alcohol in compact rhombic plates m. p. 67-68O b. p. 213'/16 mm. and is readily hydrolysed by aqueous sodium hydroxide. The potassium derivative of indole is obtained as a light-coloured mass by heating indole with potassium hydroxide. The formation of the potassium compound furnishes a ready means of separating indole from coal tar.The fraction b. p. 240-260° freed from phenols and bases by shaking with alkali hydroxide and dilute sulphuric acid is heated with potassium hydroxide at 1 90-200°,i. 156 ABSTRACTS OF CHEMICAL PAPERS. the unattacked oil removed by washing with benzene and the potassium indole decomposed by water ; the separation may also be effected by means of sodium or sodamide. The crude indole may be purified by converting it into the bisulphite compound (Hesse Abstr. 1900 i 48) or into the sodium salt of indolecarboxylic acid (compare Zatti and Ferratini Abstr. 1890 i 202) by heating with sodium at 190-200" in a stream of carbon dioxide. The free acid obtained from the sodium salt by acidification loses carbon dioxide when heated in n vacuum a t 230-250° and yields indole.E. B. Preparation of Halogenindoxylic Acids and their Esters. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 226689).-The conversion by alkalis of phenylglycine-o-carboxylic acids into derivatives of indoxyl has been described (compare Abstr. 1908 i 974 1019) and it is now found that the reaction can be applied successfully to halogenated derivatives of the acid. Methyl 5 7-dichZoroindoxyZcarboxyZate C,H,Cl<-NH->C*C02Me colourless needles m. p. 1959 is prepared by boiling dimethyl 4 6-di- clr Zorophen ylglyc ine -2 - carboxy Zate m . p. 7 7-7 8O in t ol uene solution with sodium or sodium methoxide; the toluene can be replaced by other indifferent solvents. Dimethyl 6-chZoro-4-bromoplien~ZyZycie-2-carboxylate m. p. 81 - 83' (obtained from 6-chloro-4-bromopheoylglycine-2-carboxylic acid m.p. 23S0 in the usual manner) yielded on similar treatment methyl 7 - C h h ~ O - 5-brornoindoxylcarboxyZate7 C,H,CIBr<-N H->C*CO,Me long needles m. p. 203-205". Methyt 4 6-dichZorophenyZglycine-2-carboxylate colourless needles m. p. 133-134' on treatment with sodium ethoxide yielded sodium 5 7-dichloroirndoxy~carboxy~c~te a yellow powder which is readily con- verted into 5 7 5' 7'-tetrachloroindigotin by the action of air and water E. M. G. M. W H ) C W ) Betaine Formation and S teric Hindrance. ALFRED KIRPAL (.Monatsh. 1910 31 969-979. Compare Abstr. 1908 i 679).- Nicotinic isonicotinic and cinchomeronic acids interact with chloro- acetic acid in neutral solution giving almost theoretical yields of the corresponding betaines ; picolinic and quinolinic acids under the same conditions react incompletely whilst dipicolinic acid remains un- changed.The author suggests that these results may be explained on the assumption that the carboxyl group in the a-position exerts a negative influence on the nitrogen atom which therefore shows less tendency to assume the quinquevalent condition. This explanation is however not applicable to quinaldine and 2 6-dimethylpyridine both of which on treatment with chloroacetic acid do not yield betaine but are converted into their hydrochlorides ; the non-formation of betaines in these cases is referred to steric influences. isor'Vicotinic acid betaine C,H70,N prepared by heating isonicotiqiqORGANIC CHEMISTRY. i. 157 acid and chloroacetic acid in faintly alkaline aqueous solution crystallises in needles m.p. 262' (decomp.). Nicotinic acid betaine forms monoclinic prisms or octahedral crystals and has m. p. 190' (decomp.). Picolinic acid betaine crystzllises in short pointed prisms m. p. 1 6 5 O (decomp.) ; the hydyochloride has m. p. 181'. Cinchomeronic acid betuine C,H70,N forms rhombic plates m. p. 180° (decomp.). Quinolinic acid betaine C,H70,N,H2O crystallises in colourless prisms which when heated at loo" lose their water of crystallisation and carbon dioxide yielding nicotinic acid betaine ; the same decom- position also takes place on boiling its aqueous solution ; the hydro- chloride is readily hydrolysed aqueous solutions rapidly depositing the free betaine. a-Yicolinebetaine C,H,O,N prepared by heating a-picoline with chloroacetic acid on the water-bath and isolated by means of its platinichloride crystallises in colourless hygroscopic needles which turn brown at 100' and decompose at 162'; the platinichloride forms yellow prisms m.p. 212' (decomp.) ; the hydrochloride has m. p. 188' (decomp.). F. B. Derivatives of 2-Phenylquinoline. 11. ERNET MURMANN (Nonatsh. 1910 31 1303-1306. Compare Abstr. 1892 1003).- Disulphonic acids can be obtained by heating 1 -phenylquinoline with four times its weight of commercial fuming sulphuric acid on the water-bath until a test drop gives no crystals (monosulphonic acid) when heated with five drops of water and no turbidity on addition of aqueous ammonia. The mass is diluted with five times its weight of water and a small amount of monosulphonic acid separates during the course of a day.After further dilution boiling with animal charcoal and neutralising with barium carbonate crystals of a barium salt C,,H,O,NS,Ba 6 H20 in the form of long colourless needles are obtained. The culcium salt C,,H,0,NS,Ca,6H20 forms slender yeIlow needles sparingly soluble in water and the zinc salt crystallises with 5H20 in large felted needles. The filtrate from the barium salt contains an isomeric salt which is sparingly soluble in alcohol and crystallises with 12H,O. The first barium salt when fused with potassium hydroxide yields a red phenol m. p. 140-141'. J. J. S. Formation of Acyl Derivatives of Phenylhydrazine in Aqueous Solution. STEPHAN JAROSCHY (Monutsh. 1910 31 95 1-967).-The phenylhydrazides of formic acetic propionic butyric and isobutyric acids are readily formed by heating the acids with phenylhydrazine in aqueous solution.The relative velocities of formation of these hydrazides under various conditions at 100' have been investigated by estimating the amount of unchanged acid by titration with barium hydroxide With the same concentration of acidi. 158 ABSTRACTS OF CHEMICAL PAPERS. and of base it is found that the rates of formation stand in the same order as the magnitude of the dissociation constants of the acids The effect of temperature was studied in the case of the formyl derivative. Increase of temperature is accompanied by an increase in the relative velocity and the same effect is produced by increasing the concentration of the acid.The addition of a small quantity of hydrochloric acid was found to diminish the rate of formation of the acetyl derivative. The author suggests that this is to be referred to the diminution in the ionisation of the acetic acid; on this assumption the acylation is due t o the anions. F. B. Oxidation of Methyluracil. ROBERT BEHREND and KARL BTRUVE (Annalen 1910 378 153-169. Compare Behrend and Dietrich Abstr. 1900 i 120 ; Behrend and Grunewald Abstr. 1902 i 834 ; Behrend and Fricke Abstr. 1903 i 739 ; Behrend and Osten Abstr. 1906 i 309 ; Behrend and Hufschmidt Abstr. 1906 i 310 ; Hobel Abstr. 1907 i 557; Offe ibid. 645).-When oxidised with potassium ferricyanide in ammoniacal solution methyluracil yields the amide of uracilcarboxylic acid CO<NH,cMe>CH NH-CO + NH + 3 0 = co<NH*C(CO *NH,) ">CH+2H20.This appears to be the first instance recorded of the oxidation of a -CH to a -CO*NH group. The reaction does not consist in the oxidation of the methyl to a carboxylic group and the conversion of the latter into the -CO*NH group by means of ammonia as it is shown that a temperature of 240" is required for the latter reaction. It is possible that an aldehyde group is first formed and that this yields an aldehyde-ammonia -CH<gE- which is then oxidised to the -CH< group. When the oxidation takes place in the presence of potassium hydroxide the product is uracilcarboxylic acid. I n the preparation of the amide the mixture is heated a t 50-60° for five to six hours and allowed to cool when potassium ferrocyanide separates; this is removed and the filtrate heated until all the ammonia is driven off and an odour of hydrogen cyanide is noticed.The solution is filtered hot and kept for one to two days a t the ordinary temperature when methyluracil separates as octahedra or needles and in the course of a week or so the amide separates in a crystalline form. It is most readily freed from uracil by conversion into its sparingly soluble potassium derivative C,H,03N3K,2H,0 which crystallises from hot water in well-developed prisms. Its solution has an alkaline reaction. The arnide C,H,O,N H,O crystallises in small lancet- shaped plates dissolves in 110 parts of boiling water and in 2000 parts of water at 20°. When boiled with alkalis it yields uracil- curboxylic acid NH- C(CO,H) ">CH,H,O in the form of rhombic plates which lose their water of hydration at 120'.The anhydrous compound decomposes above 300' without melting. The hydrated compound dissolves in '70 parts of water at 100" and in 500 parts at IS' NH-- 0 NH2ORGANIC CHEMISTRY. i. 159 The addition of acetic acid to a solution of the carboxylic acid in potassium hydroxide solution precipitates potassium uracilcarboxykate C,H,O,N,K. The ammonium salt C,H70,N,,H,0 crystallises in small six-sided plates. The acid is identical with the product obtained by hydrolysing the ester described by Muller (Abstr. 1897 i 549). When methyluracil is oxidised with potassium ferricyanide in the presence of potassium hydroxide solution i t is best to leave the mix- ture for twenty days at the ordinary temperature and then to acidify with acetic acid when potsssium uracilcarboxylate is precipitated.It has not been found possible to oxidise the carboxylic acid with potassium ferricyanide but wibh permanganate (30) at 15’ the acid yields oxaluric and oxalic acids. J. J. S. Oxidation of a- and P-Dimethyluracils. PAUL HENKEL (Annalen 1910 378 170-18’7. Compare Behrend and Grunewald Abstr. 1902 i 834)-The oxidation of a- and P-dimethyluracils is analogous t o that of methgluracil (compare table given by Osten Annalen 1905 343 151). Methylparabanic acid can be isolated from the oxidation products of both compounds under conditions such that its formation from methyloxaluric acid is excluded. The two dimethylurscils have been transformed into corresponding a- and P-tribydroxydimethyl- dihydrouracils by Osten’s method (Abstr.1906 i 309). These hydroxy- derivatives exist in only one form whereas the corresponding tri- hydroxymethyldihydrouracil exists in two forms (Abstr. 1908 i 840). Although it has not been found possible to isolate an acetylmethylallan- turic acid by the action of alkali on the trihydroxy-derivatives it is shown that a conversion of the six-membered ring into a five-membered ring must take place under the influence of alkalis since when oxidised with permanganate in the presence of excess of potassium hydrogen carbonate the a-trihydroxy-derivative yields methylparabanic acid together with methyloxaluric acid but no trace of acetylmethylcarb- amide. Trihydroxy-/3-dimethyldihydrouracil is oxidised much less readily and under similar conditions yields s - acetglmethylcarb- amide together with methyloxaluric acid and met hylparabanic acid ; but when the solution of the hydroxy-compound is left in contact with the potassium hydrogen carbonate for twenty-four hours before the addition of the permanganate the products obtained are methylpara- bank acid and methyloxaluric acid.Acetylmethyloxaluric acid is not formed during the oxidation in the presence of the carbonate. Nitro -a-dimethyluracil (5 - nitro - 2 6 - dioxy-3 4-dimethyldihydro- pyrimidine) C 0 < ~ ~ ~ ~ ~ ~ $ 2 0 N O 2 prepared by Osten’s method (Zoc. cit.) crystallises from water in yellow plates m. p. 249-250° and when reduced by Behrend and Griinewald’s method (Zoc. cit.) yields the corresponding amino-derivative C6H902N3 in the form of yellow crystals m.p. 281-282’. Trihydroxy-a-dimethyldihydrouracil (4 5 5- trihydroxy-2 6 - dioxy- cO>C(OH) ob- 3 4-dinzet~yldihydrop~ri~zidine) CO<NMe.CMe(OH) NH- tained by oxidking the amino-a-dimethyluracil with bromine water at low temperatures crystallises when its aqueous solution is concentratedi. 160 ABSTRACTS OF CHEMICAL PAPERS. at the ordinary temperature under 4 mm. pressure and decomposes at 120O. When heated at 70-80° for fifteen minutes with ethyl alcohol which crystallises from alcohol arid has m. p. 114-llii". ' X t r o - p - dimeth-yluracil (5-nitro - 2 6 - dioxy - 1 4-dimethy2dihydro- p y r i m i d i n e ) C O ~ ~ f ~ ~ ~ ~ ~ C * N 0 2 crystallises from water in pale yeliow prisms m.p. 229-230' (decomp.) ; the corresponding amino- derivative has m. p. 256-257' (decomp.) and t~il~ydroxy-P-dimeth?/Z- dihydrouracil (4 5 5 - trihydroxy - 2 6 - dioxy - 1 4 - dimethyldihydro- co>C(OH) crystallises from dilute Bromo-P-dimethyluracil C O < ~ ~ ~ ~ ~ e > C B r is sometimes formed as a by-product ; i t has m. p. 243'. 4-Hydroxy-5 5-diethoxy-2 6-dioxy- 1 4-dinzethyldiiiydropyri~id~ne C,,H,,O,N crystallises from alcohol has m. p. 124-126' (decomp.) and dissolves in 20 parts of cold absolute alcohol. Methylparabanic acid is readily transformed into methyloxaluric acid when its alcoholic solution is made alkaline with N/5-alcoholic potash and kept for an hour. It has not been found possible to obtain either of the above- mentioned nitro-derivatives by the action of methyl iodide and alkali on nitromethyluracil. J.J. S. Action of Potassium Permanganate and of Bromine on 1 4 5-Trimethylwracil. KARL BREMER (AnnuZen 19 10 378 188-209).-By analogy with methyluracil (Abstr. 1906 i 310) i t was thought probable t h a t by the oxidation of 1 4 5-trimethyluracil with cold permanganate methylacetylcarbamide and pyruvic acid would be formed and that with warm permanganate acetyldimethylhydantoin or its oxidation products would be obtained. Actual experiment has shown that the products are the same at both temperatures using 2 atoms of oxygen ; in both cases only acetylmethylcarbamide and a syrup are formed. No trace of pyruvic acid can be detected in the syrup and the only product so far isolated from the syrup is oxalic acid.Dihydroxytrimethyldihydrouracil has been prepared by Behrend Osten and Beer's method (Abstr. 1906 i 309) but it has not been settled definitely whether the compound has the con- stitution of the uracil (I) or whether it is the isomeric acetyldimethyl hydantoin (2). NMe-- wrimidine) CO<NH.CjyJe(()H) acetic acid and decomposes at 133". I n favour of the latter formula are the facts that it is not readiG oxidised and does not appear to be affected by alkalis. Attempts to oxidise 1-phenyl-4 5-dimethyluracil were unsuccessful owing t o the slight solubility of the compound in water. Behrend and Hennicke's method (Abstr. 1906 i 314) for the preparation of thiontrimethyluracil gives a 25% and not an 80% yield. A 45-50% yield is obtained when a mixture of equivalentORGANIC CHEMISTRY.i. 161 quantities of methyl thiocarbimide and ethyl P-amino-a-methyl croton- ate is heated to 55-60' and then kept for twenty-four hours in an ice chest ; after removing the crystals the filtrate is heated to 70° and on cooling gives a further crop of crystals. The desulphurisation is accomplished most readily by heating the ,compound in a reflux apparatus with 65% sulphuric acid for about forty-five minutes at 150-160" and subsequent dilution with three times the volume of water. The yield of trimethyluracil is 80%; it crystallises from hot water and has m. p. 222-223'. 1-Phenyl-4 5-dimethyluracil C,,H,,O,N is formed when ethyl phenylcarbamidomethylcrotonate (A-bstr. 1901 i 136) prepared from ethyl p-amino-a-methylcrotonate and phenylcarbimide is hydrolysed with 5% potassium hydroxide so!ution and the solution acidified with hydrochloric acid; it has m.p. 235'. 4-B~onzo-5 -hgdrox!j-l 4 5-trimeth~WihgdrourclciI obtained by the action of water and an excess of bromine on trimethyl- uracil at the temperature of the water-bath crystallises from hot water in needles m. p. 127' after sintering a t 120'. When heated with alcohol or by itself at 95' and then at 115' it loses water and yields 4-bromo- 1 4-dimethgZ-5-methyZenedihydrouracil co<NH* NMe-- CMeBr ">C:CH which crystallises from benzene or dilute alcohol and has m. p. 195O after sintering at 170'. This unsaturated compound reacts with bromine water yielding 4-bromo-5-hydroxy-1 4-dimethyZ-5- bi*ornomethyldihydrouraciZ C O < ~ ~ ~ ~ & ~ > C ( C H B r ) * O H m.p. 150-151' after sintering at 145'. and this. when heated at v 90-100' for three hours yields 4-bronzo-1 4-dirneth&B-bron~o- meth y leltedihydrouraciZ CO< NMe--C H. CMeEr O>c CH I' in the form of well-developed needles m. p. 1 75-178' which again react with bromine water yielding 4- bronzo-5-hydroxy - 1 4-climethyl-5-dibromometl~~/ldi- hydrouracii c0<NH.CMeBr N Me-- "o>C(CHBr2)*OH as colourless crystals. DibromohydroxymethyIdihydrouracil does not yield an unsaturated compound when heated at 150'. Chlorohydroxytrimethy Idihydrouracil C,H ,0,N2CI obtained by the action of chlorine water on trimethyluracil crystallises from hot water and has m. p. 154-155'. 4-Bromo-5 -hydroxy - 1 -phenyl- 4 5 -dimeth yldih ydyouraci! has m.p. 195'. 4 5-Dihydroxy-1 4 5-trimetliyIdi~ydl.ouraciZ C7H1,0,N prepared from the bromohydroxy-compound by Behrend and Grunewald's method crystallises from water in large prisms m. p. 165O. It reacts with boiling acetic anhydride yielding an acetyl derivative C9H,,0,N m. p. 135-150' and with phenyldydrazine yields a pl~enylhydraxzde Cl3HI8O3N4 in the form of needles m. p. 155-158O after sintering at 145'. J. J. S. c PHI 3OP2 Br,i. 162 ABSTRACTS OF CHEMICAL PAPERS. Quinazolines. XXVI. Synthesis of Some Stilbazoles Hydrazones and Schiff Bases in the k4-Quinazolone Group. MARSTON T. BOGERT GEORGE DENTON BELL and CARL GUSTAVE AMEND (J. Arner. Ghem. Xoc. 1910 32 1654-1664).-1t has been shown in earlier papers (Bogert and Gortner Abstr.1909 i 679; Bogert Amend and Chambers Abstr. 1910 i 893) that derivatives of 4-qujnazolone can be easily prepared which contain a 2-methyl group and amino-groups attached t o either or both the benzene and metadiazine portions of the nucleus. A study has been made of the behaviour of these different groups towards aldehydes and the results show that with reference to their reactivity with benzaIdehyde they may be arranged in the following order (1) the 3-amino-group (in the metadiazine nucleus) ; (2) the 2-methyl group; and (3) the 7-amino- group (in the benzene nucleus). When 2-methvl- 4 - auinazolone is boiled for ten minutes with benzaldehyde it is converted into the stilbazole namely 2-styryl-4- N=$? *C€I:CHPh CO*NH quinaxolone (2-styryZ-4-hydroxyquinaxoline) C,H,< N--(? *CH:cHPh m.p. 252-253' (corr.) which forms -- or 'cH4<c( OH N colourless silky needles and yields a brorno-derivative. 2-0-lI9droxy- N=(? CH CH* C,H;OH styryl- 4 -quirzaxoZone C,H,<CO. m. p. 301' (decomp.) obtained by the action of salicylaldehyde on 2-methyl-4-quin- azolone crystallisesinminute pale yellow needles and yields bright yellow salts with hydrochloric acid and potassium hydroxide. 8-p-llydyoxy-m- N= (? CH CH C6H3( OH) OMe methoxystyryl - 4 - quinnxolone CsH4<U0.NH 9 m. p. 280' (corr.) forms minute pale yellow needles and gives dark yellow alkali salts. When 2 3-dimethyl-4-quinazolone is boiled with benzaldehyde m. p. 170" 2-st yry I- 3 -metii yZ-4-puinaaolone CGHh< (corr.) is produced which forms light yellow slender needles.3-Amino-2-methyl-4-quinazolone was prepared by the action of hydrazine hydrate on acetylanthranil (Bogert and Gortner loc. cit.). I n one experiment a compound m. p. 193" (corr.) was isolated which crystallises in prisms and is probably acetylanthrnnylcccetyliL?/draxide NHA c*C,H,-CO*NH*NHAc. The hydrazone 3-benzylideneamino-2- rnethyl-4-quinazolone obtained by boiling 3-amino-2-methyl-4-quin- azolone (1 mol.) with benzaldehyde (1 mol.) has m. p. 187' (corr.) and not 183" as stated by Bogert and Gortner (Ioc. cit.) ; its hydrochloride softens at 220° and decomposes without melting a t about 300'. When 3-amino-2-methyl-4-quinazolone (1 mol.) is boiled with benzaldehyde (2 mols.) 3-bernxy~~deneamino-~-~tyry~-~-qu~nazo~one N=$l*CH:CHPh CO*NMe N=$I *CH:CHPh C ~ H 4 < ~ 0 - 1 ; $ .~ ~ ~ ~ h 9 m. p. 155' (corr.) is obtained which forms minute nearly colourless stellate groups of crystals ; its hydrochloride does not melt below 3 0 0 O . When this substance is treated with boiling dilute hydrochloric acidORGANIC CHEMISTRY. i. I63 and the product distilled with steam benzaldehyde passes over with the distillate and 3-amino-2-styryl-4-quinazolone m. p. 164O (corr.) is obtained which cristallises in plates or broad needles and when heated with benzaldehyde is reconverted into its benzylidene derivative ; the benxoyl derivative has m. p. 195' (corr.). When 3-amino-2-methyl-4-quinazolone is heated with cinnamnldehyde salicylaldehyde or vanillaldehyde the methyl group is not affected but condensation takes place only with the amino-group.3-Cinnarnyl- ideneamino-'2-methyl-4-quinazolone m. p. 148-14 9" (corr.) forms bright yellow needles. The corresponding salicylidene derivative m. p. 1 7 1 O (corr.) crystallises in short pale yellow needles yields a bright yellow potassium salt and a hydrochloride m. p. 250' (decornp.) and is hydrolysed by hydrochloric acid or potassium hydroxide with formation of salicylaldehyde. Although the salicylidene compound refuses to condense with a second mol. of salicylaldehyde it condenses readily with benzaldehyde with forxnation of 3-salicylidenearnino-2- - N=$l *CH:CHPh m. p. 232-233' C0.N.N CH CGH,*OH' styryl-4-quinaxoZone C,H,< (corr,) which crystallises in yellow needles. 3 - Vanillyliderzeamino-2- methyl-4-quinaxolone m.p. 21 5-21 6" (corr.) forms small yellow prisms or needles and gives deep yellow salts with hydrochloric acid and potassium hydroxide. I n the case of 7-amino-2-methyl-4-quinazolone as in that of the 3-amino-derivative condensation is possible with either the methyl or amino-group or with both The amino-group however is differently situated being in the benzene instead of the metadiazine nucleus and attached to a carbon instead of a nitrogen atom. Aldehydes con- densing with the $'-amino-group should therefore yield true Schiff bases instead of hydrazones. I n one experiment a benaylidene derivative m. p. 324' (corr.) was obtained which seemed to be the Schiff base since it was hydrolysed by potassium hydroxide with formation of benzaldehyde and the quinazolone but this compound could not be obtained subsequently; its acetyl derivative has m.p. 2 74-2 7 6' (corr.). 7- Acetylcmino-2-styryl-4-quint~cxolone N=C *CH:CHPh N=~C*C6H,<Co.$JH m. p. 323-324' (corr.) obtained by boiling 7-acetylamino-2-methyl-4- quinazolone with benzaldehyde forms short colourless needles. 7-Amino-2 3-dimethyl-4-auinazolone condenses with benzaldehyde " A to form 7-arnino-2-styryl-3-methyl-4-quinaxolone N=y *CH:CHPh NH,*C6H8<C0 .NMe 9 m. p. 229*5-230° (corr.) which crystallises in yellow prisms ; its acetyl derivative has m. p. 272' (corr.). When 3 7-diamino-2-methyl-4-quinazolone is boiled with an excess of ben zalde h y de 3 7-dibenx ylideneamino-2-st yv y I - 4-quinaxolone N=C -CH:CHPh CHPh:N*C6H,<(T0. &.N:CHp) 9 m.D. 238' (corr.) is produced together with small quantities of twoi. 164 ABSTRACTS OF CHEMICAL PAPERS. other substances m. p. 196" (corr.) and 172" (corr.) which seem to be isomeric dibenzylidene derivatives. ~-~cety~ccm~no-~-be~zzy~~deneum~2-styryl-4-quinazoZone m. p. 261" (corr.) obtained by boiling 3-amino- 7-acetylamino-2-methyl-4-quinazolone with excess of benzaldehyde forms yellow needles ; its solution in alcohol has a green fluorescence. 3 7-Diacetylamino-2-methyl-4-quinazolone condenses with benzalde- hyde with formation of 3 7-diacetyZamino-3-styryl-4-quinaxoZone m. p. 283-284" (corr.). 3-Amino- 6-ace tylamino-2-methyl-4 -quinszolone condenses similarly with lenzaldehyde with production of 6-acetyZarnino-3-benzyZiJeneam~no- 2-styryZ-4-puinaxolo~e m.p. 238-239' (corr.) which forms short silky yell0 w needles. E. G. Constitution of Indirubin. I. and 11. ANDRI~ WAHL and P. BAGARD (BUZZ. Soc. chim. 1910 [iv] '7 1090-1101; 1911 9 56-83. Compare Abstr. 1909 i 330 735).-I. Maillard's objection (Abstr. 1910 i 138) to the view that the authors' new synthesis of indirubin (Abstr. 1909 i 330) supports von Baeyer's formula for this substance is based on two main contentions: (a) that proof of the formation of indirubin was insufficient ; ( b ) that molecular transforma- tion may have occurred in the reaction. I n regard to (a) it is now shown that the synthetic indirubin like commercial indirubin yields Schunk and Marchlew ski's colourless crystalline compound m. p. 204" when reduced with zinc and acetic anhydride in presence of anhydrous sodium acetate (Abstr.1895 i 288). Contention (b) implies that both oxindole and indoxyl should condense with isatin chloride to give indirubiu but actual trial shows that when the reaction is conducted in presence of pyridine to remove the hydrogen chloride formed indoxyl gives indigotin and no indirubin whereas oxindole gives indirubin as chief product. 11. m-Bromoisatin chloride condenses with oxindole to furnish a bromoindirubin which is isomeric with but different from that obtained by condensing m-bromoisatin with indoxylic acid. The production of isomerides in these two reactions can be explained easily from von Bseyer's but only with difficulty from Maillard's formula. nt-Bromoisatin chloride condenses with oxindole in benzene solution to form a bromoindirubin having the formula It forms dichroic triclinic crystals showing oblique extinction and angle ph'= 126'.Its solubility is 0.192-0.199 gram in 100 grams of acetic acid a t 2 5 O . The bromoindirubin obtained by condensing m-bromoisatin with indoxylic acid has the formula C6H4<~~>C:c<,,>NHv C,H,Br and has been prepared already by von Baeyer (Abstr. 1882 198). It forms dichroic crystals which belong to the monoclinic system and show right extinction and angleyh' = 101". Its solubility is 0.042-0,052 gram in 100 grams of acetic acid a t 25". T. A. H.ORGANIC CHEMISTRY. i. 165 Quindoline and ‘‘ Thioquindoline.” EMILIO NOELTING and 0. R. STEUER (Ber. 1910 43 351 2-351 7).-Indoxylic acid condenses with 0-aminobenznldehyde in hydrochIoric acid solution yielding quindoline (compare Fichter and Bohringer Abstr.1907 i 92; Fichter and Rohner this vol. i 85). / \ - c / m This is identical with indoline described by I I I I Schutzenberger (this Journ. 1877 ii 898). \/\/‘\/\/ By heating indigotin with an alkaline solution NH C of sodium thiosulphate Geraud (Abstr. 1879 Since the same compound is also produced by the condensation of indoxyl and isatin in alkaline solution it must be a quindolinecarboxylic acid of the annexed structure. N CO,H I 936; 1881 51) obtained a substance to which he assigned the formula C3,Hz403N4. pared by the condensation of o-nitrobenzaldehyde and indoxylic acid in aqueous acetic acid solution crystallises in red needles m. p. 217’; on reduction with zinc dust and acetic acid it yields quindoline.By condensing indoxylic acid with o-aminobenzaldehyde in the presence of a little hydrochloric acid 2-o-aminobenxyZidene-indoxyl C6H,<~~>C:CH*C,H4*NH is produced ; if the condensation is carried out in more acid solution quindoline hydrochloride is obtained. 3-Keto-2-o-rtitrobenxylidene-thionaphthen C,H4<- CO ,->C CH*C,H,*NO prepared from o-nitrobenzaldehyde and 3-hydroxythionaphthen-2- carboxylic acid i n acetic acid solution crystal- /\ c=N- \ lises from alcohol in orange-yellow needles I f I m p. 171’; on reduction it yields “thio- \/(/b‘CH-\/ quzndoline ” (annexed formula). The latter crystallises in almost colourless needles m. p. 169O and with concentra5ed acids forms yellow salts which are decomposed by water ; the hydrochloride and picrate are described.Quindoline and ‘ 6 thioquindoline ” dye tannin-mordanted wool silk and cotton pale yellow ; with quindolinecarboxylic acid the shade is somewhat deeper. J?. B. Anthraquinone-1-carboxylic Acid. FRITZ ULLMANN and WILLEM VAN DER SCHALK (Be?*. 1911 44 128-129) -Anhydro- anthrapuinone-9-h ydraxone-1 -carboxylic acid (pyridaxonanthrone) (I) obtained by the action of hydr- NH o azine hydrate on the chloride of anthraquinone-1-carboxylic acid Nj/\Co crystallises in needles which are /\/\/\ sparingly soluble in the usual I I solvents but dissolve in sodium \/v tions. hydroxide Phenylhydrazine to orange-yellow gives solu- the (1.1 (11.1 corresponding N-phmylpyridazon- anthrone. Anthraquinone- 1 -carb- S /\/\/\ ’()\,\ I I 1 GO VOL.c. 1. ni. 166 ABSTRACTS OF CHEMICAL PAPERS. oxylic acid reacts readily with hydroxplamine in the presence of sodium acetate solution yielding oxaxonanthrone (11) in the form of pale yellow needles m. p. 247'. Method for Preparing Aromatic Acylguanidines. PAUL PIERRON (Compt. rend. 1910 151 1364-1366. Compare Wheeler and Johnson Abstr. 1902 i 27).-Aromatic acylguanidines are best prepared by boiling the aromatic acylcyanamides with the hydro- chloride of an aromatic amine in alcoholic solution; thus benzoyl- cyanamide and aniline hydrochloride yield benzoylphenylguanidine the hydrochloride of which has m. p. 159'. Benxoyl-m-tolylguanidine C;H,*NH*C(NHBz):NH cryfitallises in needles or leaflets m. p. 71" ; the hydrochloride has m. p. 1709 CHPh:CH*CO*NH*C(NHPh):NH forms prismatic needles m.p. 140' ; benzoyl-$-curnidylguanidine CI7Hl90N3 occurs in prismatic needles m. p. 140-141'. On boiling acylcyanamides with o-phenylenediamine in alcoholic solution an acylaminobenziminazole is produced. The arylcyanamides do not readily undergo this condensation. Cinnamoyl-o-phnylene- guanidine [2-cinnamoylimi~oben~~minaxoZe~~ J. J. S. Cinnamoylphenylguanidine C,H,<,N~>C:N*CO*CH:CHPh crysta.llisqs in needles m. p. 262'. w 0. w. Pechmann's Isomeric Hydrazidines. HENRY L. WHEELER and TREAT B. JOHNSON (Bey. 1911 44 15l).-The authors have already shown (Abstr. 1904 i 628) that the formulse suggested by Busch and Ruppenthal (this vol. i 86) for Pechmann's hydrazidines (Abstr. 1896 i 31) namely NH,*NPh*CPh NPh and NHPh*NH*CPh:NPh are correct.J. J. S. Preparation of 4-isoValerylamino- 1 - phenyl-2 3-dimethyl- 5-pyrazolone and of 4-~-Bromoisovctl~rylamino-l-phenyl-2 3- dimethyl-5-pyrasolone. KNOLL & Co. (D.R.-P. 22701 3).-Com- pounds possessing valuable therapeutic properties are obtained by introducing isovaleryl or substituted isovaleryl residues into 4-amino- 1-phenyl-2 3-dimethyld-pyrazolone. 4-isoVnle~*ylamino-l -phenyl-2 3-dimethyl-5-pyraxolone m. p. 203' odourless and with a bitter taste is prepared by heating 4-amino- 1 -phenyl-2 3-dimet hyl-5-pyrazolone with isovaleric acid and phosphorus trichloride at 125' during half an hour treating with sodium carbonate and crystallising the dried product from benzene; its aqueous solutions give a blood-red coloration with ferric chloride.4-a-Bromoisoualerylamino-1 -phenyl-2 3-dimelhyl-5-pyrazolorns is ob- tained when a-bromoisovaleryl bromide is substituted for the isovaleric acid and phosphorus trichloride in the foregoing preparation ; it forms glistening colourless needles ra. p. 206' (decornp.) is odourless but has a bitter taste and forms crystalline salts with acids and a yellow coloration with ferric chloride. Preparation of 4-Imino-5.oximino-2 6-diketopyrimidine and its 3-Alkyl Derivative. EMANUEL MERCK (D.R.-P. 227390).-The action of nitrous acid on a hot dilute acetic acid solution of cyano- F. M. G . M.ORGANIC CHEMISTRY. i. 167 acetylmethrlcarbamide NHMe*CO*NH*C0*CH,.CN yields oximino- cyanoacet ylmethylcarbamide NHMe*CO*NH*CO*C( NOH).CN colour- less crystals m.p. 218' (decomp.). When this substance is warmed with 30% sodium hydroxide (4 parts) an orange-yellow precipitate slowly separates which on the addition of acetic acid is converted into the characteristic red crystals of 4-imino-5-oximino-2 6-diketo- 3-me th ylpyrimidine N H<gg ~ ~ ~ ~ ~ > C NH. Analogous results are obtained when cyanoacetylcarbamide is employed in the foregoing reaction ; a yellow crystalline sodium derivative separates on treatment with sodium nitrite yielding on acidification oximinocyanoacetyl- carbamide glistening colourless crystals m. p. 220° which are readily converted into the corresponding 4-imino- 5 -0ximino - 2 6-diketo- pyrimidine. The sodium hydroxide can in this reaction be replaced by sodamide sodium ethoxide or an alkylcarbamide.Preparation of Anthrapyrimidines and Anthrapyrimidones. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 225982).-The reaction between aminoanthraquinones and acid amides has been previously described (Abstr. 1910 i 445); the same result is now obtained with acylaminoanthraquinones and ammonia 1 -anthra- pyrimidone (Zoc. cit. ) having been prepared by heating aminoanthra- quinoneurethane with ammonium hydroxide at 150° ; likewise 1 4-diaminoanthraquinonemonourethane yields 4-amino-1 -ccnthra- pyrimidone brown crystals and 2-bromo-4-arnino-l-p-methykanthra- pyrimidine a brown powder is obtained from 2 4-dibromo-1-acetyl- aminoanthraquinone. A tabulated description of the following compounds with the coloure of their solutions in various solvents is given in the original 1-amino- anthraquinoneurethanc greenish -yellow crystals ; 1 -amircoanthva - quinonecarbsmide chloride orange crystals ; 1 4 -diaminoanthra - pinonemonourethane garnet-red crystals ; 4-chloro-l-ccminoanthra- quinoneurethane golden-yellow crystals ; 2 4-dibromo-1 -acetyZamino- snthraquinone brownish-jellow crystals ; 4-amino-1-anthrapyrimidone dark brown crystals.F. M. G. M. 4-Dibromo-1 2 3- triaaol-5-one-1-acetamide. TREODOR CURTIUS and ERNST WELDE (Ber. 1910 43 857-862).-The dibromo-deriv- ative mentioned previously (Abstr. 1907 i 450) is shown to be 4-dibromo-l 2 3-triaxole-5-one-l-aceramide. F. M. G. M. - C Br,*CO -N>N*CH2*CO*NH2. Its formation from the a&monium salt of 5-hydroxr-1 2 3-triazole- 1-acetamide is represented by means of the equation C H C( 0 NH,) C4H402N,Br + HBr + NH,Br and its formation from the nitroso-derivative by the equation C,H80aN5 + 2Br = C,H,O,N,Br + NOBr + NH,Br the nitrosyl bromide formed immediately yielding nitrous and hydro- bromic acids.n 2 y===-.N >C*CH,*CO*NH + 2Br2 =i. 168 ABSTRACTS OF CHEMICAL PAPERS. The dibromo-derivative crystallises from hot alcohol in colourless glistening needles m. p. 151O (decomp.) after turning brown at 120O. It changes colour when exposed to the air for several hours and then has a n odour of bromine. When boiled with dilute sulphuric acid it is hydrolysed to nitrogen ammonia glycine and dibromoglycollic acid the last of which is further hydrolysed to hydrobromic and oxalic acids. The same decomposition occum only more slowly when the bromo-derivative is boiled with water.J. J. S. Derivatives of isoUrio Acid. HEINRICH BILTZ (Bey. 1910 43 3553-3562).-1t has been shown (Abstr. 1909 i 740) that diethoxy- 4 5-diphenyldihydroglyoxalone is converted on heating at the m. p. into 5-ethoxy-4 5-diphenylisoglyoxalone. Diethoxy-1 3 7-trimethyl- uric acid might be expected to behave similarly but it does not change a t the m. p. However on boiling it in glacial acetic acid solution 5-ethoxy-trimethyEisouric acid formed. This can be crystallised from cold alcohol without change but on boiling with alcohol containing a little acid the diethoxy- derivative is regenerated. On reduction with zinc and acetic acid hydrogen is added at positions 4 and 9 that in 4 is immediately eliminated with the ethoxyl group in position 5 and trimethyluric acid is obtained 5-Er hoxytrimethylisouric acid is completely analogous to 5-ethoxy- diphenylisoglyoxalone and the conclusion is drawn that the ethoxyl group in position 4 and the imino-hydrogen in position 9 are on opposite sides of the plane of the glyoxalone ring.By the action of chlorine on trimethyluric acid in chloroform solu- tion a dichloride is first formed soluble in chloroform chlorine being added in positions 4 and 5 . This is unstable hydrogens chloride being eliminated between positions 4 and 9 and a chlorine derivative OF isouric acid is obtained y M e * C O * q O w >N& is C 0 NMe*C N CO >co. ~Me*CO*FCl*N'Me>CO -~ rMe*CO*yCL*NMe C O*NISle*CCl-NH C O*NMe-C N Alcohol converts this chloride into 5-ethoxy-1 3 7-trimethylisouric acid ; water readily converts it into apocaffeine.5-Ethoxy-1 3 7-t~imethylieouric acid forms long thin colourless needles m. p. 174-176O. 5-Methoxy-1 3 7-trimethylisouric acid crystallises in obliquely cut six-sided columnar forms m. p. 205'. 5-Chlovo-1 3 7-trimethylisouric acid separates in colourless flat needles or prisms with oblique end faces and a rectangular cross sectioq m. p. 158' (decomp.). The corresponding 5-bromo-compound could not be obtained. E. F. A. Hydroxyaeo-compounds and Ketohydrazones. I.-111. KARL AUWERS [and in part HUGO DANNEHL and A. BOENNECRE] (Annalen 1910 3'78 210-260. Compare Auwers Abstr. 1908 i 47C).-The results of previous investigations indicate that when possible the phenylhydrazones of benzoquinones and naphthaquinones undergoORGANIC CHEMISTRY.i. 169 molecular rearrangement into azo-compounds whereas with mixed azo- derivatives the reverie process takes place. Phenanthraquinonephenylhydrazone (Zincke Abstr. 1883 1 135 ; Werner Annalen 1902,321 304) when benzoylated in the presence of pyridine yields a benzoyl derivative which is identical with the product obtained by condensing phenanthraquinone with as-benzoyl- phenylhydrazine in the presence of mineral acids From the readiness with which it is hydrolysed and from the fact that when reduced with zinc dust and cold acetic acid the chief products are aniline and 9-benzoylamino-l O-hydroxyphenanthrene (87%. yield) the conclusion is drawn that the benzoyl compound is an 0-derivative + N I3,Ph.y6H4'G' N:NPh 13;'6H,*G*NHBz -+ C,H,*C* OBz C6H4' c* O H I n the condensation of phenanthraquinone with benzoylphenyl- hydrazine a wandering of the benzoyl group from nitrogen to oxygen occurs a wandering analogous to that observed in the condensation of P-naphthaquinone with benzoylphenylhydrazine. The same 0-acetyl derivative is obtained by acety lating phennn t b raq uinonephenyl- hydrazone and by condensing phensnthraquinone with as-acetyl- phenylhydrazine. This acetyl derivative is so readily hydrolysed that it is difficult to purify. The general conclusion drawn is that phenanthraquinonephenylhydrazone is 9-benzeneazo- 10-phenanthrol. 9- Benxeneaxo-lO-phenanthryl benzoate C,? HI8O2N2 crystallises from glacial acetic acid in glistening red plates m.p. 193-194'. 9-Benzoyl- amino- 10-phenanthrol C,,H,,O,N crystallises from glacial acetic acid in glistening flat needles m. p. 848-249'. 9-Benaeneaxo-lO-p~e~nthr~Z acetate C,,HI,0,N2 crystallises from light petroleum in brilliant red plates m. p. 139-140° and is hydrolysed when warmed with alcohol or acetic acid. The question as to the constitution of Khorr's 4-benzeneazo-5- keto-1-phenyl-3-methylpyrazolone has been investigated (Knorr Abstr. 1887 678; 1888 724 ; Japp and Klingemann Trans. 1888 53 519; Wedekind Annalen 1897 295 330 ; Biilow Abstr. 1899 i 355 ; Eibner Abstr. 1903 i 8'71). The siime benzoyl derivat.ive is obtained by (1) the action of benzoyl chloride on the sodium derivative suspended in dry e,ther ; (2) the action of benzoyl chloride and sodium hydroxide solution on an aqueous acetone solution of the pyrazolone; (3) the con- densation of ke tophen yl me thy1 py razolone with as-phen yl benzoy 1- hydrazine hydrochloride in dilute alcohol.It is regarded as the - ,OMe*s.N :NPh 0-benzoyl derivative X< since when reduccd-with zinc NPh*C*OBa dust and cold acetic acid it yields appreciable amounts of aniline together with benzanilide and rubazonic acid. It has not been found possible to isolate the N-bensoyl derivative of the aminohydroxy phenp lmethylpyrazole.i. 170 ABSTRACTS OF CHEMICAL PAPERS. Knorr's compound is thus a true azo-derivative and as it dissolves ,CMe*E*N:NPh Nc<NPh*C*OH ' and is 4-beazeneazo-5-hydroxy-1 -phenyl- 3-methy1pyrazoIe. When the p-phenylhjdrazone of up-diketobutyric acid is condensed with benzoglphenylhydrazine mat,er is eliminated and Knorr's azo- compound and ethyl benzoate are obtained instead of the exDected readily in alkalis it is represented by the enolic formula CMe*$XN*NPhBz L .The free hydroxy- N'NPh*CO N-benzoyl derivative pyrazole is also formed (1) when the benzoylated osazone of the diketo- butyric acid is warmed with benzene and phosphoric oxide; (2) when the /I-phenylhydrazone of ethyl ap-diketobutyrate is condensed with as- benzoyl phenylhy drazine hydrochloride in alcoholic solution both with and without the addition of sodium acetate and (3) when the dibenzoyl derivative of the osazone of the ethyl diketobutyrate is warmed with alcoholic potassium hydroxide. The methyl derivative obtained by condensing ketophenylmethyl- pyrazolone with as-phenglmethylhgdrazine must be the N-methyl ether as alkyl groups do not wander under these NeN Ph C 0 conditions.This constitution is confirmed by t,he fact that when reduced with zinc and acetic acid methylaniline is obtained but no trace of aniline. The same metbyl etker together with a small amount of the CRle*$XN*NMePh - isomeric 0-metbyl ether N<CMe'E" :Nph is formed when Knorr's NPh* C OMe azo-compound is methylated by means of methyl iodide or sulphate and alkali. When reduced the 0-metbyl ether yields appreciable amounts of aniline. The N-methyl ether is readily hydrolysed to the monomethyl derivative of ethyl diketobutyrate osazone whereas the 0-ether is not acted upon when boiled with alcoholic potassium hydroxide.The benzoyl derivative of 4-benzeneazo-5-h ydroxy- 1-phenyl-3-metb yl- pyrazole C,,H,,O?N crystallises from alcohol in long yellow glistening needles or from light petroleum in quadratic plates m. p. 137O which are readily hydrolysed when boiled wit,h 50% acetic acid. The dibenzoyl derivative of 4-amirto-5-l~ydroxy-l-phenyl-3-methyl- pyrnxole N<Nph.g.oBZ prepared by benzoylating thecorresponding amine cry stallises from dilute alcohol in colourless glistening needles ID. p. 196q and on hydrolysis yields a colourless compound m. p. 110-1 159 probably the acid NHPh*N:CMe*CH(NHBz)*CO,H which CMe*QH*NHBz when heated yields the N-benxoyl :derivative 9 m. p. 1839 Keto-1 -phenyl-3-methylpyrazolone prepared by Snchs and Barschall's method (Abstr.1902 i 504) has m. p. 121'. The mono- benzoylosctxone of up-diketobutgric acid NHPhON :CNe*C(CO,H):N*NBzPh crystallises from light petroleum in slender pale yellow needles m. p. CMe*C*NHBz NqNPh*COORGANIC CHEMISTRY. i. 171 110-11 lo and dissolves in cold sodium hydroxide solution without undergoing hydrolysis. Ethyl ap-diketobutyrate and benzoylphenyl- hydrazine yield the dibenxopEccted osaxone C32H,8~04N4 even in the presence OF an excess of ester. I t crystallises from dilute methyl alcohol in long colourless prisms m. p. 190'. Ethyl afl-diketobntyrate and phenylmethylhydrazine yield the dimethylosaxone NMePh-N CMe*C(CO,Ft):N*NMePh which crystallises from alcohol in pale yellow glistening prisms m. p. 103-104°. The phenylmEthylhydruzoiie of 4-keto-1-phenyl-3-methyl- 5-pyrazolone C17H160N4 crystallises from dilute alcohol in glistening orange-yellow felted needles m.p. 144' and is insoluble in alkalis ; the isomeric O-methyl ether forms compact yellow prisms m. p. 78". It has not been found possible to acetylate or benzoylate Graebe and Gfeller's acenaphthenequinonephenylhydraz me ( A bstr. 1893 i 657) but the benzoyl derivative C25H1602N2 can be prepared by con- densing the quinone with benzoylphenylbydrazine hydrochloride and alcohol. It crystallises in glistening orange-red needles m. p. 170° and is readily hydrolysed by cold alcoholic sodium hydroxide. When reduced with zinc and acetic acid it yields no trace of aniline and is therefore a N-benz y l derivative and the phenylhydrazone probably has the hydrazone and not the azo-structure.Acenap?ifhenequinowphenylrnethylhydvazone C19H140N2 crystallises from acetone in dark red needles m. p. 1144 and when reduced yields methylaniline and no trace of aniline. Camphorquinonephenylhydrazone cannot be directly acylated but the benzoyl derivative C23H2402N2 can be obtained by condensing the quinone with benzoylphenylhydrazine in the form of colourless felted needles m. p. 153'. This is also a N-benzoyl derivative and the parent substance a hydrazone which exists in one form only (compare Lapworth and Hann Trans. 1902 81 1514). The two N-benzoyl derivatives unlike most other N-benzoylated compounds are readily hydrolysed. The following new N-benzoyl derivatives prepared by condensing the ketones with benzoylphenyl- hydrazine are not readily hydrolysed by alkalis Ethyl acetoacetate benzoyZphenylhydi*axone C19H,,03N2 forms compact colourless quadratic crystals m. p. 144-145' and with alcoholic potash yields the benxoylphenylhydruxone of acetoacetic acid Cl7Hl6O3N2 in the form of small colourless prisms m. p. 203'. Diacstyldibenxoylosaxone C30H2602K4 crystallise's from boiling glacial acetic acid in slender needles m. p. 249" and is formed even at - 15' i n the presence of an excess of the ketone. Benzil-benxoylphenyl- hydrazone C27H2002N2 crystallises from light petroleum in slender prismatic needles m. p. 176". Baeyer and Claisen's phenylazoscetylacetone (Abstr. 1888 828) is best prepared by the gradual addition of a solution of phenyl- diazonium chloride exactly neutralised with sodium carbonate t o a cold solution of acetylacetone (1 mol.) in sodium carbonate (0.5 mol.). The benzoyl derivative (Pechmann Abstr. 1893 i 84) is most Teadily prepared by the Schotten-Baumann method; it has m. p. 160-161' is readily hydrolysed by alkalis and is sometimes accom- panied by an ismeride m. p. 134'. When reduced the benzoyli. 172 ABSTRACTS OF CHEMICAL PAPERS. derivative yields benzanilide but no trace of aniline. The compound is thus a N-benzoyl derivative and the parent substance a y-phenyl- hydrazone of py8-triketopentane and not an azo-derivative. Benzoylacetylacetone in the form of its sodium derivative reacts with a neutralised solution of phenyldiazonium chloride yielding 0-6enzeneazodiacet?/l6elzxoylmetliane NPh:N*O*CMe:CBzAc which crystallises from methyl alcohol in golden-yellow prismatic needles m. p. 77-78O. The compound is not affected when boiled with alcohol ; with cold alkalis or with an ethereal solution of hydrogen chloride it yields the phenylhydrazone of phenyl methyl triketone and when boiled with glacial acetic acid yields benzoylacetone. The reaction with hydrogen chloride is similar to that described by Dimroth and Hartmann as characteristic of 0-azo-compounds (Abstr. 1909 i 66). The azo-compound (m. p. 77-78') reacts with an alcoholic solution of P-naphthol yielding benzeneazo-P-naphthol and benzoylacetylacetone. When reduced with zinc dust and acetic acid the azo-compound yields appreciable amounts of aniline. The isomeric acetylphenylhydrazone of phenyl methyl triketone CAcBz:N*NAcPh is formed when the 0-azo-compound is boiled for four hours with toluene; it separates from alcohol in colourless crystals m. p. 15S0 and when reduced yields acetanilide but no trace of aniline. The compound is isomeric with the benzoyl derivative of phenylazoacetylacetone m. p. 160'. These results agree with Pechmann's view that the compounds derived from diazo-compounds and aliphatic ketones with the reactive -CO*CH,* group are not azo-compounds but hydrazones. Generalisations based on the constitution of N-benaoyl derivatives and the readiness with which they are hydrolysed cannot be drawn. J. J. 5. Method for Determining the Individuality or Plurality of Diastases in a Liquid. PIERRE ACHALME and BRESSON (Compt. rend. 1910 151 1369-1372).-1n order to ascertain whether a particular liquid contains one or more enzymes the authors suggest that it should be allowed t o act under identical conditions on solutions of two different substances capable of being hydrolysed by it and on a solution containing a mixture of the same two substances. If two diastases are present the action on the mixture should be the sum of the action on the two substances taken individually whilst if only one enzyme is present the action on the mixture should not exceed that on either substance alone. The results of illustrative experiments are given in tabular form. It is found that the time taken to effect hydrolysis in the three solutions is the same if two diastases are present but that when only one enzyme is acting a longer period is Chlorophyll. XI. Chlorophyllase. RICHARD WILLSTATTES and ARTHUR STOLL (Annnlen 1910,378,18-72).-See this vol. i 141. required to hydrolyse the mixture. w. 0. w.