57 0 r g an i c C hem i s t ry. Theory of the Grignard Reactions. RICRARD ABEQG (Be?.. 1905 38 4113-4116. Compare Abstr. 1906 ii 475).-1t has been already suggested that alkyl groups are amphoteric in character ; in compounds such as ethyl chloride they have electro-positive properties and on hydrolysis yield alcohols whilst in metallic alkyl compounds such as zinc ethyl they have electro-negative properties and on hydrolysis yield hydrides (paraffins). The Grignard reactions permit of similar conclusions being drawn with reference to the electro- chemical character of other organic radicles and nine examples of different types are discussed from this point of view. Attention is called to the close analogy between the influence of electrical polarity in determining the direction of chemical change in electro- lytes and in non-electrolytes and to the fact that evidence of feeble ionisation has been obtained in the case of a few compounds generally regarded as non-electrolytes for example sugar alcohol ethyl malonate and oxonium compounds.T. M. L. Decomposition of Chloroform under the Influence of Light and Air. NICOLAAS SCHOORL and L. M. VAN DEN BERG (Chem. Centr. 1905 ii 1623 ; from Pharm. Weekblcd 42 S77-SSB).-&uantitative experiments have shown that when chloroform is decomposed by the action of light in the presence of an excess of oxygen carbon dioxide water and chlorine are formed but that when insufficient oxygen is present carbon oxychloride and hydrogen chloride are produced in molecular proportion. The latter conditions usually obtain in prac- tice.E. W. W. Readineas of Formation of Cyclic Compounds. PAVEL Iw. PETRENKO-KRITSCHENKO and,A. KONSCHIN (Annulen 1905,342,5 1-59). -After surveying the known data bearing on the Eormation of closed rings from open chains the conclusion is drawn that the readiness or better the velocity of formation of cyclic compounds from open chains depends on two factors the work necessary to bring the open chain into a cyclic position and the work required to actually close the ring. The velocities of the reaction between potassium hydroxide and various glycol monochlorohydrins and between dibromides and zinc dust are measured. The investigation of ethylene chlorohydrin tri- methylene chlorohydrin y-pentylene chlorohydrin and 6-hexylene chlorohydrin shows that there is a marked difference in the velocity of the reaction between the a-compounds and the P-compounds whilst the remainder of the substances investigated behave in much the same way.The velocity of decomposition of y-pentylene chlorohydrin is slightly greater than that of the others. The velocity of the reaction of the dibromides with zinc dust is expressed as a percentage of the material which has been decom- VOL. XC. i. f58 ABSTRACTS OF CHEMICAL PAPERS. posed in one hour ethylene dibromide 19-87 ; propylene dibromide 20.87 ; trimethylene bromide 2.02 ; y-pentylene dibromide 1-80 ; pentamethylene dibromide 1.25 ; 6-hexylene dibromide 1.92. The opinion is expressed that in the case of the compounds investi- gated unlike the acid compounds the '' tension " of the ring which is formed does not play an important part in determining the velocity of the reaction.Action of Dilute Sulphuric Acid on the Pinacone formed from Ethyl Propyl Ketone. FELIX GOLDBERGER and RUDOLF TAN- DLER (Monatsh. 1905 26 1473-1485. compare Zumpfe Abstr. 1904 i 291 ; Lieben Abstr. 1905 i 167 ; Kohn ibid.).-The pinacone obtained in a yield of 28 per cent. of the theoretical by reduction of ethyl propyl ketone with sodium and water or in poorer yield by electrolytic reduction in dilute sulphuric acid solution with a current density of 8 amperes per square decimetre boils a t 125-126' under 11 mm. or at 254-255' under the atmospheric pressure (Oechsner de Coninck A bstr. 1876 i 694). When heated with 20-30 per cent. sulphuric acid in a sealed tube a t 170-180' for six hours it yields an unsaturated hydrocarbon and an oxide.K. J. P. 0. . . I The hydrocarbon (?HMe'gPr (P) is a colourless oil which has an CHMe* CPr odour of camphor boils a t 75-76' under 11 mm. or a t 194-195" under the atmospheric pressure forms a dark resinous additive com- pound with 1 mol. of bromine in carbon disulphide solution and when oxidised with nitric acid of sp. gr. 1.5 under cooling or with alkaline permanganate solution at 60° yields carbon dioxide and an acid ; this is volatile with steam and forms a silver salt C,H702Ag The oxide C,,H,,O is a slightly yellow liquid having a burning odour which boils a t 105-106' under 11 mm. or a t 225' under atmospheric pressure and is easily soluble in ether alcohol or chloro- form.It does not form an oxime a sodium hydrogen sulphite additive compound or an acetyl derivative when boiled with acetyl chloride; it remains unchanged when boiled with sodium i n an atmosphere of hydrogen or when heated with zinc ethyl in a sealed tube a t 150' for three hours or with water under pressure a t 180-200'. It must be therefore an ay- or an a6-oxide. It is not reduced by alcohol and sodium and does not interact with magnesium ethyl iodide ; when oxidised with alkaline permanganate solution it yields a mixture of acids which forms silver butyrate and a silver salt C7H1,02 Ag crystallising in white needles. Synthesis in the s-Heptane-a6q-triol Series. JULES L. HAMONET (Compt. rend. 1905 141 1244-1245).-a~-Dirnethoxyheptane-6-ol OH*CH(CH,*CH,*CH,*OMe) prepared by the action of ethyl formate on the magnesium derivative of y-iodo-a-methoxypropane (compare Abstr.1904 i 467) is a colourless slightly odorous liquid with a very bitter taste which boils at 141-142' under 21 mm. or at 246-248' under the ordinary pressure has a sp. gr. 0.969 a t 18' and does not crystallise when cooled in a mixture of solid carbon dioxide and acetone. 6-C?iZoro-ay-dirnethoxyheptarze C7H,,Cl(OMe) prepared by the action of phosphorus trichloride on the alcohol is a colourless G. Y.ORGANIC CHEMISTRY. 59 mobile liquid with an agreeable odour boiling at 120" under 16 mrn. pressure and having a sp. gr. 1.001 at 18". a6q-Tribromoheptane C7HlaBr8 prepared by heating the alcohol with acetic acid and hydrobromic acid in sealed tubes a t loo" is a viscous liquid solidify- ing in a mixture of solid carbonic acid and acetone boiling at 184-185" under 19 min.pressure and having a sp. gr. 1.775 a t 18". a8qTri-iodoheptane C7HI3I3 obtained by the action of hydrogen iodide in the cold on the alcohol is a slightly coloured viscous liquid having a sp. gr. 2.343 at 18" which cannot be distilled without decom- posit ion. M. A. W. Halogenated Aliphatic Acids. WILHELM LOSSEN (Annalen 1905 342 112-155 157-190)..-It has been shown (Abstr. 1893 i 142) that both dibromosuccinic acid and isodibromosuccinic acid the latter more easily are converted by the action of alkali hydroxides into acetylenedicarboxylic acid a fact which is not in agreement with Wisllcenus's views as to the stereoisomerism of the two dibromosuc- cinic acids.A new series of experiments has been undertaken with the object of throwing light on this difference. [With ROBERT EICHLOFF.] -Chloro- and bromo-acetic acids were con- verted by aqueous or alkaline solutions into glycollic acid a t different temperatures and the velocity of the hydrolysis measured. The change is accelerated by raising the temperature and the velocity is greater in solutions containing molecular proportions of the acid and the base than in aqueous solutions. Increase however in the concen- tration of the alkali greatly hastens the velocity of the reaction. I n dilute solution the free acid decomposes far more rapidly than in con- centrated solution but in presence of alkali the reverse is the case. Bromoscetic acid under all conditions decomposes more rapidly than chloroacetic acid.Chloroacetic acid yields not only glycollic acid but also diglycollic acid when boiled with bases the particular reaction depending on the nature and quality of the base. Bromoacetic acid was investigated. Normal sodium hydroxide yields only glycollic acid concentrated sodium hydroxide (1 molecule of base to 1 of acid) gives also glycollic acid but 2 molecules of the concentrated base yield diglycollic acid and glycollic acid in the proportion of 1 2.8 and 3 molecules of the base gave the two acids in the proportion of 1 1.7. I t is noteworthy that potassium hydroxide in place of sodium hydroxide increases the proportion of diglycollic acid. Barium hydroxide in neutral solution converts the bromoacetic acid into glycollic acid but if two equivalents of the base are present for every equivalent of acid 76 per cent.of diglycollic acid is formed. When boiled with water both trichloro- and tribromo-acetic acids are decomposed into chloroform and carbon dioxide. If the decomposition is effected by sodium hydroxide in the proportion of 6 molecules of base to 1 of acid the reaction is represented by the equation CCl,*CO,H + CiNaOH = 3NaC1+ HC0,Na + Na2C03 + 3H,O. If less sodium hydroxide is used the two reactions occur together. and acrylic acids behaving in the manner above stated. [With EUGEN Ko~s~~.]-a-~romopropionic acid yields both lactic Barium f 260 ABSTRACTS OF CHEMICAL PAPERS. hydroxide has a somewhat different action from sodium hydroxide giving other proportions of the two acids.P-Bromopropionic acid yields hydracrylic and acrylic acids the latter forming a larger proportion of the product than in the case of a-bromopropionic acid. The decomposition also takes place more rapidly. This fact is not in agreement with Wislicenus' theory as t o the mechanism of the elimination of hydrogen haloids from organic compounds. a-Bromopropionic acid H*6-6-H should yield acrylic acid more easily than P-bromopropionic acid which has either H Br H bO,H E H Br H the configuration H.6-6-H or H*61-6-H ; the first configura- . . . . l3r CO,H H CO,H tion alone would yield acrylic acid whilst the second would give ethylene carbon dioxide and sodium bromide. act-Dibromopropionic acid gives pyruvic and a-bromoacrylic acids and the so-called acryl-colloid ; the velocity of the decomposition is affected by bases in the same way as with the foregoing substances.The proportion of a-bromoacrylic acid decreases with increasing dilution ; it crystallises in readily volatile plates melting a t 68" and is decomposed by exposure to the air or by treatment with sodium hydroxide into acetylene. The acryl-colloid is formed only in acid solution; it consists of a jelly which when dry has the composition C3nH41203n and is completely insoluble in water but soluble in alkali hydroxides. It is probably a polymeride of pyruvic acid since ether extracts from the alkaline solution after acidification a syrup which combines with phenylhydrazine yielding the phenylhydrazide of pyruvic acid. up-Dibromopropionic acid decomposes more rapidly than the aa-iso- meride yielding glyceric acid and a-bromohydracrylic acid together with small quantities of pyruvic acid or in acid solution of acryl-col- loid.According to Wislicenus' theory the aa- should decompose more rapidly than the &acid since it can exist in only one configuration namely that which mould yield bromohydracrylic acid. [With HUGO sM~L~us.]-The main product of the decomposition of a-bromobutyric acid is hydroxybutyric acid but both crotonic acid and s-dietl~yZdigE~collic (butodiglycollic) acid CO,H*CHEt*O*CHEt*CO,H are also formed. The latter is best prepared by dropping bromo- butyric acid on to solid sodium hydroxide mixing and after acidify- ing with dilute sulphuric acid separating the oily layer which consists mainly of crotonic acid and then extracting the new acid with ether and purifying in the form of the barium salt.The acid crystallises at a low temperature and melts a t 26'; it boils a t 117' under 11 mm. pressure. The normal potassium salt C,H,,O,K crystallises in hygroscopic needles whilst the potassium hydrogen salt C8H,,05K,iH,0 forms rectangular plates. The normal sodium salt C8H1205Na2 crys- tallises in leaflets or needles and the acid salt 3C8H1,O,Na,C,~:,,O,,I-I,O,ORGANIC CHEMISTRY. 61 forms needles. The amnzoniunlz salt crystallises in anhydrous needles the calcium salt C,H,,O,Ca,H,O forms microscopic prisms the barium salt C8H,,0,Ba,~H,0 prisms and the copper salt C,H,,O,Cu,H,O pale blue needles ; when anhydrous the latter is deep azure blue.The silver salt C,H,,O5Ag crystallises in quadratic prisms and the lead salt C,H,,O,Pb is amorphous. s-DietiLyldiglycollim,ide C,H120,:NH is prepared by dry distillation of the ammonium salt and is a fusible solid distilling a t 200-215°. s-Diethyldiglycollic acid can be distilled under diminished pressure but a t the ordinary pressure decomposes into carbon monoxide and propaldehyde and an acid which appears to be metameric with a-hydroxybutyric acid. When reduced with 50 per cent. hydriodic acid s-diethyldiglycollic acid yields butyric acid and hydroxybutyric acid. [With OSCAR G ~ ~ ~ a c ~ . ] - w h e n a-bromoisobutyric mid is decom- posed by treatment with water a t the ordinary temperature a process which requires eighteen months h ydroxyisobutyric acid is alone produced whereas by boiling with water S per cent.of methylacrylic acid is also formed ; 14.8 per cent. of methylacrylic acid is formed mhon 1 mol. of NNaOH is used a t B temperature of SOo and 75 per cent. when 4 mols. of 25 per cent. sodium hydroxide are employed. P-Bromoisobutyric acid yields only methylacrylic acid under all conditions. Wislicenus' theory indicates that the a-bromo-acid would yield met hylacrylic acid rather than the /I-bromo-acid. Zinc nzethylacrylkate ( C4H,02),Zn crystallises in prisms and readily polgmerises when heated. The cadmium salt forms small aggregates the sirontiunz salt needles and the lead salt prisms or plates which polymerise on heating; the copper salt is a pale blue insoluble precipitate. [With FRITZ MORSCH~CK and CARL ~o~~o.]-~romomethylacrylic acid is formed when citradibromomethylsuccinic acid is boiled with three parts of water for four hours.Both bromo- and isobromo-meth- acrylic acids are formed when a neutral solution of mesodihromo- methylsuccinic acid is warmed at 60° care being taken that the solution remains neutral. The bromo-acid separates first whilst the isobromo-acid can be extracted with ether. isoBromomethylacrylic acid crystallises in leaflets melting a t 68O. Both acids decompose on heating' into hydrogen bromide carbon dioxide and allene. When boiled for a short time the isobromomethylacrglic acid is converted into bromomethylacrylic acid but on prolonged boiling with aqueous sodium hydroxide both acids are decomposed the iso-acid more slowly into allylene.Heating of the calcium salts produces allene and allylene the iso-acid being first transformed into brornomethylacrylic acid. This change is also effected by exposure of the chloroform solution to which a trace of bromine has been added to sunlight. The silver salts of both acids are decomposed on boiling with water that of bromomethylacrylic acid yielding silver bromide silver carbon dioxide and propaldehyde. The silver salt of the iso-acid changes more rapidly than the other according t o the equation C,H,O,BrAg + H,O = CSH,,O + CO + AgBr. Permanganate oxidises both acids to acetic acid ; a similar behaviour of the two acids is also observed when reduced or electrolysed.62 ABSTRACTS OF CHEMICAL PAPERS. [With CARL Do~~o.]-Allene yields a compound with aqueous mer- curic chloride which has the composition CGH80,C1,Hg and seems to be identical with the substance obtained from allylene by Kutscheroff (Bey.1884,17,13). I n order to distinguish the two gases dependence is especially to be placed on the fact that allylene precipitates ammoniacal silver and cuprous solutions whilst allene does not. With alkaline meroury solutions allylene gives a precipitate (C,H,),Hg ; allene does not. The tetrabromide of allylene is liquid and that of allene a solid melting at 0'. Action of Cyanoacetic Acid on Crotonaldehyde. HUGO HAERDTL (Moncctsh. 1905 26 1391-1402. Compare Braun Abstr. 1896 i 594 ; Doebner Abstr. 1'300 i 536).-a-Cyanosorbic acid CHMe:CH*CH:C(CN)*CO,H is formed by heating a molecular mixture of crotonaldehyde and cyanoacetic acid in an atmosphere of carbon dioxide in a reflux apparatus in a boiling water-bath for six hours.It crystallises from water in stont yellow needles 6-8 mm. long softens and loses carbon dioxide at 150' or melts and decom- poses at 163' when quickly heated. crystallises in nodular aggregates. With bromine in chloroform solution the cyano-acid forms the additive compound C7H70,NBr2 which separates as a fine white crystalline powder and melts at 154-156". When heated in small quantities a t 150-160° until the evolution of carbon dioxide ceases the cyano-acid forms sorbortitde CHMe:CH-CH:CH.CN which when freshly distilled is a clear mobile liquid; i t boils at 50-60' under 1 2 mm. pressure and gradually decomposes in a closed vessel with formation of a brown resin.When boiled with 10-12 per cent. aqueous potassium hydr- oxide in a reflux apparatus the cyano-acid yields a brown amorphous aubeta.ice C,H,O:(?) which is soluble in pyridine or glaeial acetic acid but is insoluble in aqueous sodium carbonate and when boiled with aqueous baryta forms a barium salt (C,H,O,),Ba whilst no definite product of hydrolysis could be obtained by heating the cyano-acid with alcoholic potassium hydroxide dilute hydrochloric acid or 40 per cent. sulphuric acid. G. Y. General Method of Synthesising a/?-Trisubstituted Glycidic Esters and Ketones. GEORGES DARZENS (Compt. rend. 1905 141 766-7'68. Compare Abstr. 1905 i 11 6).-Ethyl a-chloropro- pionate readily condenses with ketones in the presence of sodium ethoxide to form the ethyl esters of the up-trisubstituted glycidic These are colourless liquids with acids of the type O< I a faint odour yielding on hydrolysis the corresponding acids which are unstable and readily break down into carbon dioxide and the corresponding ketone the latter being formed probably from an intermediate oxide by the migration of' a hydrogen atom (compare Pourneau and Tiffeneau this vol.i 20) according to the equations K. J. P. 0. The burium salt (CI7H,02N)2Ba,4H,O CRR' CMe*CO,Et'ORGAKIC CHEMISTRY. 63 I n the following table are given the boiling points of the new ethyl trisubstituted glycidates and of the ketones prepared from them together with the melting points of the semicarbazides of the latter. Melting Boiling point of point corresponding Roiling point of of semi- Ketone.ethyl glycidate. ketone. carbazide. Pressure. Pressure. - - Acetone. ... .._ .. . ... ... ... 80-82" under 20 mm. Methyl ethyl ketone ... 90-93 22 Methyl n-propyl ketone 100-102 16 Methyl n-hexyl 152 28 100-103" under 26 mm. 86-87" Methyl n-heptyl 148-150 16 101-103 15 168-169 Methyl n-nonyl 174-175 15 132-135 15 78-79 Acetophenone ... ... . . .. . 151-154 22 102-104 20 172-173 p-Tolyl methyl ketone,. 160-162 19 116-118 22 184-185 - - - - M. A. W. Preparation of Pure Ethyl Alkylmalonates. ARTHUR MICHAEL ( L p r . Chem. 1905 [ii] 72 537-554. Compare Abstr. 1905 i 564 S55).-0n adding ethyl malonate to the equivalent amount of 50 per cent. aqueous potassium hydroxide cooled to - lo" the mixture solidifies owing to the formation of ethyl potassiomalonate which rapidly decomposes to ethyl potassium malonate and alcohol.This change takes place immediately when ethyl malonate is shaken with 1 per cent. aqueous potassium hydroxide. The partial hydrolysis of ethyl ethylmalonate takes place in less than one minute with 1 per cent. in three minutes with 4 per cent. in thirty minutes with 1 2 per cent. and only to the extent of 20 per cent. in thirty minutes with 25 per cent. aqueous potassium hydr- oxide. When shaken with 25 per cent. aqueous potassium hydroxide a mixture of ethyl ethylmalonate and ethyl malonate develops heat and if extracted with ether after one minute yields 86 per cent. of the ethyl ethylmalonate in a state of purity. Ethyl diethylmalonate undergoes only slight hydrolysis when heated with 50 per cent.aqueous potassium hydroxide. The propylmalonates resemble the ethylmalonates in their stability towards alkali hydroxides whilst the methylmalonates undergo hydrolysis more easily ethyl dimethylmalonate being hydrolysed rapidly with 50 per cent. aqueous potassium hydroxide. These differences in behaviour are utilised in the detection of ethyl malonate and ethylmalonate the presence of 1 and 2 per cent. of which respectively causes the formation of a white precipitate when ethyl diethylmalonate is shaken with 50 per cent. aqueous potassium hydroxide and of ethyl diethylmalonate small percentages of which appear as drops of oil when ethyl ethylmalonate or malonate is shaken with dilute potassium hydroxide.Application of these tests to the ethyl ethylmalonates obtained by the methods used by previous authors shows that these contain varying quantities of ethyl diethylmalonate which cannot be removed by fractional distillation or by Schey's method of purification (Rec. TTCCV. chirn. 1897 16 357).64 ABSTRACTS OF CHEMICAL PAPERS. To prepare pure ethyl ethylmalonate the crude product is shaken with 25 per cent. aqueous potassium hydroxide .and the resulting oil boiled with an excess of the same reagent in a reflux apparatus. After extracting the ethyl diethylmalonate with ether the solution is again boiled with a further quantity of potassium hydroxide neutralised with hydrochloric acid and treated with calcium chloride. The calcium salt obtained in this manner yields pure ethyl ethyl- malonate which boils at 92" under 10 mm.or a t 211' (corr.) under 748 mm. pressure and has a sp. gr. 1.004 a t 20". Ethyl diethylmalonate is purified by boiling with 50 per cent. aqueous potassium hydroxide ; it boils a t 228*5-229.5° (corr.). Ethyl methylmalonate prepared by the action of methyl iodide on ethyl sodiomalonate and purified in the same manner as ethyl ethyl- malonate boils at 198.5-199' (corr.) under 765 mm. pressure. Ethyl dimethylmalonate purified by shaking with a small quantity of 25 per cent. aqueous potassium hydroxide boils at 196-196-5O (corr.) under 753 mm. pressure. Ethyl propylmalonate boils a t 225-5-226' (corr.) under '771 mm. pressiire and has a sp. gr. 0,9897 at 25'125'. Xthyl dipropylmalonate boils at 248-249' (corr.).Ethyl methylmalonate and ethylmalonate are obtained in yields of 90 and 70 per cent of the ethyl malonate used when mixtures of ethyl malonate and methyl and ethyl iodide respectively are shaken with finely-divided potassium hydroxide. Ethyl dimethylmalonate is formed in the same manner from ethyl methylmalonate. When shaken with ethyl iodide and powdered potassium hydroxide ethyl acetoacetate forms ethyl ethylacetoacetate in a yield of 70-80 per cent. of its own weight but in small yields in presence of water. The action of ethyl iodide and potassium hydroxide on ethyl ethyl- acetoacetate takes place only slowly and incompletely. G. Y. Synthesis of Dihydrocamphoric Acid. GUSTAVE BLANC (Compt. rend. 1905 141 1030-1032).-The author has confirmed the con- stitution ascribed by Martine (Abstr. 1902 i 629) to dihydro- camphoric acid namely ~-methyl-6-isopropyladipic acid (compare Perkin and Crossley Trans.1898 '73 23) by its synthesis from iso- propylsuccinic anhydride (Abstr. 1904 i 369 647 ; 1905 i 631). iso- Propylsuccinic anhydride on reduction yields a mixture of a- and P-isopropylbutyrolactones from which on treatment with phosphorus pentabromide and subsequently with alcohol a mixture of ethyl y-bromo- a- and -/I-isopropylbutyrates is obtained of which the a-isomeride condenses with ethyl sodiomethylmalonate to form a tricarboxylic ester. The corresponding free acid melts at 158" losing carbon dioxide and forming a-methyl-6-isopropyladipic acid according to the equations >O -+ C0,Et CHPrP*CH,*CH,Br -+ FHPrs*CO CH,-CH CO,Et*CHPrfi*CH,*CH,*CMe(CO,Et) -+ CO,H.CHPrWH,* CH,-CMe( CO,H) -+ CO2H*CHPr~*C,H,-CHMe*CO2H.ORGANIC CHEMISTRY.65 a-Methyl-6isopropyladipic acid has all the properties of dihydro- camphoric acid except that it is racemic ; dihydrocamphoric acid con- trary to the statement of Perkin and Crossley is optically active having [ a ] 8'30' according to measurements made by Martine a t the author's request. a-isoPropyladipic acid melting at 63' is obtained when ethyl sodiomalonate is substituted for ethyl sodiomethylmalonate in the above series of reactions. M. A. W. Iron Citrates. GIUSEPPE SIBONI (Chem. Centr. 1905 ii 1623-1624; from Boll. Ckim. Farm. 44 625-637).-Ferrous citrate prepared by boiling a solution of citric acid with iron turnings for several days and concentrating in a vacuum is sparingly soluble in water but does not crystallise readily owing to the formation of the more soluble ferric citrate.If oxidation is prevented the citrate separates out even in the presence of free citric acid (compare Martinotti and Cornelio Abstr. 1901 i 667). Ferrous citrate is very readily soluble in ammonia forming ferrous ammonium citrate (Zoc. cit.) which decomposes a t 120' and is readily oxidised in solution but is more stable in the presence of citric acid or an excess of acid ferrous citrate. Sodium ferrous citrate prepared by neutralising crystalline ferrous citrate with sodium hydroxide is more suitable for therapeutic application (compare Baroni Giorn. Farm. Chim. 53 145). Normal ferric citrate C,H,07Fe,3H,0 is obtained by digesting freshly precipitated ferric hydroxide with citric acid for twenty-four hours a t 60-65O filtering and evaporating the filtrate a t 50-60" ; an anhydrous salt separates from the aqueous solution in the form of a red powder on the addition of ether.Ferric citrate has an acid re- action and when treated with ammonia forms ammino- and ammonium salts. I The monoammino-salt 2C,H:,07Fe,NH3 forms a slightly deliquescent red powder which has an acid reaction and is not suitable for subcutaneous injection. 2C,H,07Fe 2NH3 prepared by the action of ammonia on an aqueous solution of the preceding salt or by the oxidat.ion of ferrous ammonium citrate is brown and more deliquescent than the monoammino-salt. The triam- mino-salt 2C,H,07Fe,3NH obtained by saturating a solution of ferric citrate with ammonia is neutral and better adapted for subcutaneous injection.E'erric ammonium citrcbte H,(NH,)Fe,( C6H50?)3 prepared by adding a solution of ammonia to a solution of ferric citrate forms thin yellowish-brown scales is very deliquescent and has a strong acid reaction. Ferric diammonium citrate H(NH,),Fe,( CGHR07)3 also obtained by the action of ammonia on a solution of ferric citrate forms yellowish-green scales and is very deliquescent. Ferric triammonium citrate (NH,),Fe,(C,H,O,) also separates in bright green scales and has an acid reaction. The tetra-ammonium salt prepared by neutralising a solution of ferric citrate with ammonia and evaporating at a low temperature crystallises in scales. This salt is contained in the preparation described in the German Pharmacopaeia ; the preparations of the Russian and Norwegian Pharmacopaias should contain 9.21 and 17.33 per cent.of iron respectively. The diammino-salt (NH,)3Fe?(C,H,07),,.Nq E. W. W.66 ABSTRACTS OF CHEMICAL PAPERS. Laboratory Notes. [Diisobutyl Ketone. isoNitrosobenzy1- acetone. isoButyry1- and iaovaleryl-phenylhydrazines. Erucic Acid.] GIACOMO PONZIO (Caxzettcc 1905 35 ii 394-398).- Diisobutyl ketone (valerone) CO(CH2*CHMe2)2 prepared by the action of zinc isobutyl on isovaleryl chloride boils a t 164-166" under 741 mm. pressure and gives a semicarbaxone C,,H,,ON crystallising from light petroleum in white plates melting at 115' (compare Schmidt Ber. 1872 5 600 ; Williams Trans. lS79 35 130).isoNitrosobenzylacetone can be obtained readily and in good yield by adding isoamyl nitrite and benzylacetone to alcoholic sodium ethoxide and subsequently washing the alkaline solution with ether and saturating i t with carbon dioxide. It crystallises from light petroleum in long shining needles melting at 80-81" (compare Ceresole Abstr. 1883 41). With phenylhydrazine isobutyryldinitroethane yields isobutyryl- phenylhydrazine whilst isovaleryldinitroethane gives isovalerylphenyl- hydrazine aa-dinitroethane being formed in both cases. On passing dry hydrogen bromide into a cold acetic acid solution of erucic acid the latter is converted partly into the isomeric plano- symmetric brassidic acid and partly into bromobehenic acid C22H4302Br which crystallises from alcohol in white prisms melting a t 39-40'.T. H. P. Digitoxose. HEINRICH KILIANI (Bey. 1905 38 4040-4043. Compare Abstr. 1899 i 932).-Digitoxose is considered now to have the constitution OH*CHMe*CH(OH)*CH(OH)*CH2*CH0. It is an aldehyde as on oxidation with bromine in aqueous solution and re- moval of the hydrogen bromide which is formed by means of silver oxide it yields a solution containing the Zactone of digitoxonic acid ; this when boiled with calcium carbonate forms calcium digitoxonate (C,H,,O,),Ca which is precipitated as a glutinous mass. As digitoxosecarboxylic acid also forms a lactone two of the hydroxyl groups of digitoxose must be in the /?- and y-positions whilst the &position of the third hydroxyl is shown by the conversion of calcium digitoxonate into ap-di7~ydroxygZutaric acid when it is oxidised with concentrated nitric acid under cooling with ice and finally at 35-37'".The acid is isolated in the form of its cccZcium salt C,H,O,Ca which is precipitated from its aqueous solution by means of alcohol and on liberation from this as its lactone C,H,O,. This is obtained as an oil which after some time solidifies when stirred; it commences to soften at about 115" melts a t 120" and differs from the previously known dihydroxyglutaric acids in that after cooling and resolidification it melts sharply a t 120" (compare Kiliani and Herold,Abstr. 1905 i '739; Kilianiand Loeffler ibid. 858); it is slightly dextrorotatory in 7.8 per cent. solution in a 2 dcm. tube. G. Y. Mineral Compounds which may possess the R61e like Diastase of Liquefying Malt.JULES WOLFF (Compt. rend. 1905 141 1046-1048).-Starch (25 grams) was treated with 50 C.C. of a solution containing 0.1 per cent. of potassium permanganate andORGANIC CHEMISTRY. 67 10-15 per cent. of sulphuric acid (or 6-7 per cent. of hydrochloric acid) for lfr to 3 hours washed with distilled water and dried a t 30'. The starch underwent no appreciable change in appearance or weight and when treated with malt or acids yielded the same products as ordinary starch. When however a small amount of a basic sub- stance (ammonia alkaline oxides &c.) is present and the temperature is raised to TOo it liquefies immediately. Acids neutral salts and acid phosphates have no action. When the starch treated as described is mixed with distilled water the liquid is slightly acid (to phenolphthalein).The liquefaction does not however occur exactly at the point when the acid is j u s t neutral- ised but may take place both in slightly acid and in slightly alkaline conditions. The change produced in the starch is not due to the removal of mineral salts. N. H. J. M. Liquefying and Saccharifying Actions on Starch. PAUL PETIT (Compt. rend. 1905 141 1247-1249. Compare preceding abstract).-Infusions of malt behave like guaiacol towards ferrous ferric manganous and manganic compounds. Ferric and manganic compounds of malt infusion are reduced by hydrogen. A known volume of sodium hydroxide solution is added to the infusion contain- ing the aluminium compound in an atmosphere of hydrogen. The soda is then exactly neutralised with acetic acid and tincture of guaiacol added.No colorat'ion is produced; addition of a drop of hydrogen peroxide a t once produces a strong blue colour. A solution of commercial albumin (0.25 per cent.) mas shaken with a mixture of equal parts of ferrous ferric and manganous oxides and filtered. The solution which after a time became turbid was again filtered. The clear liquid shows the same reaction with tincture of guaiacol as malt infusion and i t also liquefies starch the action being accelerated by addition of asparagine. I n presence of asparagine there is also a slight saccharification. ZDENKO H. SKRAUP [and in part E. GEINSPERGER E. VON KNAFFL-LENZ FRANZ MENTER and H. SIRK] (Monatsh. 1903,26,1415-1472).-Soluble starch was suspended in eight times its weight of acetic anhydride saturated with hydrogen chloride a t - 20'; after fourteen days at the laboratory temperature the chief product was chlorononadeca-acetylerythrodextrin ; after two months an amorphous substance having the composition of acetyl- chloromaltose ; and after four months tetra-acetylchlorodextrose.CiLlorononccdeca-cLcetylel.ythrodeztrir (C,H70,),ClAc, is soluble in benzene but insoluble in light petroleum has [.ID + 1t36*2Oo and when treated with silver acetate in glacial acetic acid solution yields the icosa-acetyl derivative ~C,H~0,)5(C,H70,)Ac, which sinters at 110' and has [ a ] D + 145.3". When hydrolysed by means of 2 f l alcoholic potassium hydroxide under cooling with snow it yields erythrodextrin having [a] + 160*S0.The product obtained on shak- ing soluble starch with acetic anhydride saturated with hydrogen chloride at 0'. for seven hours in a sealed tube at 40' is a mixture of N. H. J. M. Starch Glycogen and Cellulose.68 ABSTRACTS OF CHEMICAL PAPERS. acetylchloro-derivatives of the starch and its decomposition products. When purified by precipitation from its benzene solution by light petroleum and by ether the acetylchloro-derivative of soluble starch contains 0.268 per cent. of chlorine from which its molecular weight is calculated as 13230. It sinters at 170° becomes brown at 240-250" decomposes with evolution of a gas a t 270° does not give a coloration with iodine and when hydrolysed with 2 N alcoholic potassium hydroxide yields soluble starch. The minimum formula for soluble starch must be therefore ( C6H1005)46-50. When heated on the water-bath with silver acetate in glacial acetic acid solution the acetylchloro-derivative of soluble starch yields Pregl's triacetyl-soluble starch (Abstr.1902 i 136) and a substance which has [a]D 151" and must contain acetyl derivatives of the decomposition products of soluble starch as on hydrolysis it yields a substance which gives a violet coloration with iodine. The action of acetic anhydride saturated with hydrogen chloride at - 12" on glycogen at the laboratory temperature for twenty hours leads to the formation of an acetylchloro-compound which contains 0.15 per cent. of chlorine and has the molecular weight calculated 23630 observed about 25000. It is a white amorphous substance is readily soluble in benzene chloroform glacial acetic acid ethyl acetate or acetone and when shaken with silver acetate in glacial acetic acid solution forms the triacet9Z derivative ( C6H7O5Ac& which sin ters a t 165O becomes opaque at lSOo and melts at 240'.It has [.In + 132*34' and on hydrolysis yields a substance (C,jHIo05),oo which has [ ajD 192.1° and is more soluble than glycogen which has [ u ] ~ 196.6'. The action of acetic anhydride saturated with hydrogen chloride a t - 15' on cellulose (a) for forty-eight hours leads to the formation of a brown amorphous derivative (C,H,O,),,(OAc),o,C1 which on hydrolysis with alcoholic potassium hydroxide yields cellulose (C6H1005)34 (6) or for fourteen days leads t,o the formation of hepta- acetylchlorocellobiose which melts a t 195" and has [ + 75.21".Hepta-acetylchlorocellobiose prepared from cellobiose acetate (Skraup and Konig Abstr. 1902 i 35) melts a t 195" and has [a],+ 74.87". When warmed with silver acetate and glacial acetic acid it yields an acetate which melts a t 200° has [a] - 3045O and is not identical with cellobiose acetate which melts a t 228" and has [a],+43-64". On hydrolysis with alcoholic potassium hydroxide the acetate melting a t 200" yields a brown mass which does not deposit cellobiose on solution in water and addition of a cryhtal of that substance. G. Y. Decomposition of Nitrocellulose at Temperatures below that of Ignition. ALEXIS V. SAPOSCHNIKOFF and W. JAGELLOWITSCH (J. Buss. Phys. Chern. Soc. 1905 37 S23-S3S. Compare Abstr. 1904 i 799).-The authors have determined the velocities of decom- position a t different temperatures below that OF ignition of ordinary pyroxylin having the composition C2~H29(N0,),10 by measuring the volumes of gas evolved in definite time intervals.The volnme-time curves for temperatures from 120" to 135O are widely different in character from those obtained at 140-150° but both exhibit points ofORGANIC CHEMISTRY. 69 inflexion corresponding with maximal values of dvldt (v = volume of gas and t = time) ; the relation between these maximal velocities and the temperature is expressed by the following equations (1) between 120° and 1 3 5 O (du/dt),,,,. = - 2.22 + 0.0192T ; (2) between 135' and 150' (dv/dt),,,, = - 64.22 + 0*48T. A t 150° the decomposition of the pyroxylin is represented by the equation C2,H,,(N0,),,09 = 6'27C0 + S-5SCO + 5.37NO + 2-71N2 + 8H,O + C,,~,,H,,O,,~,N0,, and at 120' the products are 2.31C0 + 1.75CO + 2*06NO + 2-7N2 + 14*41H2O + C,B.,,H,.,0,8,16N3,5(At temperatures above 135O the solid residue contains practically no nitrogen whilst at lower temperatures about 35-30 per cent.ofy the nitrogen but very little hydrogen remains in the undecornposed matter. T. H. P. Behaviour of Vegetable and Animal Textile Fibres with Solutions of Metallic Salts. W. SCHELLENS (Arch. Pharm. 1905 243 617-627).-0ne gram of the fibre was allowed to remain for several days in 50 C.C. of the solution of the metallic salt. The total amount of salt taken up was in part merely adsorbed by the fibre ; this was removed by washing and boiling with water until the wash-water no longer gave any reaction of either constituent of the salt; the amount then remaining '' fixed " in the fibre was determined if possible (compare Zacharias Abstr.1902 i 725). The amounts are expressed as percentages of the weight of the fibre. As a rule i t is either the base or the acid of the salt that is taken up ; proportionately more is taken up out of dilute solutions as compared with strong ones and the amount taken up is greater as the extent to which the salt is hydrolysed is greater; in no case was a coloration of the fibre observed. With ferric chloride the following results were obtained in which tho numbers refer to the weight of iron fixed from solutions containing 1 and 0.1 per cent of iron respectively cotton-wool 0.112 0.112 ; filter-paper 0.23 0.123 ; precipitated cellulose 0.1 12 0.1 12 ; woolly fibre from the seeds of Eriodendron cmfructuosum 1.01 0.56 ; jute 0.56 0.44; raw silk 0.67 0.67 ; yellow Japanese silk (organsin) 0.67 0.615 ; precipitated silk 0.24 ; wool 0.84 0.36.From alco- holic ferric chloride and from aqueous ferric acetate more iron is fixed corresponding with the greater hydrolysis (Schaer Abstr. 1901 ii 603). The case of wool and ferric acetate is exceptional however less iron being fixed than from aqueous ferric chloride of equivalent strength. l\iIercury is taken up by the fibres from aqueous mercuric chloride and also from aquaous mercuric cyanide t o a smaller extent ; only a small portion is fixed however. From aqueous mercuric acetate large quantities of mercury are taken up amounting to 12.3 in the case of wool.Lead is also taken up from the aqueous nitrate; some of it is fixed in the case of Eriodendron silk and wool none in the case of cotton-wool and paper. Chromium trioxide is taken up from aqueous potassium dichromate and iodine (iodide 1) from aqueous potassium iodide. Potassium nitrate in aqueous solution is reduced to nitriteor even further; in the case of silk and wool in a 0.01 per cent.70 ABSTRACTS OF CHEMICAL PAPERS solution neither nitrate nor nitrite could be detected after eight days and in the first case the solution had become alkaline not so in the other. C. F. B. Mixed Triammine Cobalt Salts containing Ethylenediamine and Ammonia. ALFRED WERNER and AD.GRUN (Ber. 1905 38 4033-4040. Compare Werner Zeit. anorg. Chem. 1895 8 1'74; Jorgensen Abstr. 1897 ii 41 453).-17rinitrocobaltethylenediccnzine- ammine (KO,),CO(NH,)C,H,(NI~)~ is prepared by adding ethylene- diamine to a solution o'r' Erdmann's sodium tetranitrodiamminecobalt a t 60' ; it crystallises in brown leaflets or long broad feathery needles is stable towards cold hydrochloric acid but when warmed with the acid is converted into dichloi~oaqzcocobaltethylenediccminea~mine chloride [CI,(OH,)CO(NH,)C,H~(NH~)~]C~ which crystallises iu small greenish- black slightly dichroic needles dissolves in ice-cold water to form a green solution which becomes blue and on dilution red ; silver nitrate precipitates the total chlorine from the aqueous solution as silver chloride.When heated the neutral aqueous solution deposits cobalt hydroxide ; hot hydrochloric acid decomposes the chloride with formation of '' ethylenediamine chlorocobaltoate," which separates in blue leaflets. The action of sodium nitrite on the chloride leads to the formation of trinitrocobaltethylenediamineammine. The nitrate [Cl2(OH,)Co(XH3)C2H,(NH,),]NO is formed by treating the chloride with nitric acid of sp. gr. 1.4 ; it crystallises in green scales having a metallic lustre and is extremely soluble in water. Chlorodiaquocobaltet~ylenediamineu~~~~i~~e oxalate [C1(OH,),Co(NH3)C2H,(NH2)21C,0 is formed by heating t'he chloride of the dichloroaquo-compound with oxalic acid in aqueous alcoholic solution ; it crystallises in glistening blue leaflets is moderately soluble in hot wat8er when treated with hydrochloric acid in aqueous solution yields the dichloroaquochloride from which i t is formed and gives a precipitate of calcium oxalate with calcium chloride in ammoniacal solution.It forms silver chloride only slowly with silver nitrate in aqueous solution and when heated at 105' loses H,O. Chloro6romoaquocobaItethyZenediami?zeammine bs*omide [C~B~(OH,)CO(NH~)U,H,(NH,)~] Br formed by the action of hydrobromic acid of sp. gr. 1.49 on the dichloro- aquochloride crystallises in small olive-green needles sinters and loses H,O at 1 0 5 O forming a yellow crust which dissolves in water to form a yellow solution and forms a sparingly soluble iodide with aqueous potassium iodide and an easily soluble light green nitrate with concentrated nitric acid.When warmed with water and treated with an equal volume of hydrobromic acid of sp. gr. 1.49 it forms dibromoaquocobaZtet?~yZenediamineummine hromide which crystallises in small stellate aggregates of needles showing strong dichroism from bluish-black to brown forms a green powder when fiuely divided and dissolves in water to a brown solution. [ Br,( OH,)Co(NqC,H,( NH,)2]Br G. Y.ORGANIC CHEMISTRY. 71 Amides of a- and p-Aminopropionic Acids. ANTOINE P. N. FRANCHIMOKT and H. FRIEDMANN (Proc. R. Akad. Wetensch. Amster- dum 1905 8 475-477).-a-A~nino~o~ionamide NH,. CHMe* COaNH crystallises from alcohol in needles is very soluble and hygroscopic and melts at 6 2 O ; it gives a crystalline hydrochloyide a crystalline orange-red platinichtoride and a yellow picyate melting a t 199'.P-Aminopropionamide NH,*CH2*CH2.CO*NH2 is very hygroscopic and soluble but was purified by precipitating the methyl-alcoholic solu- tion with ether and forms beautiful crystals melting at 41'. Neither compound is identical with the supposed aminopropionamide isolated from urine by Baumstark in 1873. T. M. L. Configuration of Stereoisomeric Chromium Salts. PAUL PFEIFFER [with A. TRIESCHMANN] (dnnulen 1905 342 283-305. Compare Abstr. 1905 i 33).-It was shown (Zoc. cit.) that two series of isomeric chromium compounds could be obtained and converted into two corresponding series of stereoisomeric oxalates by treatment with potassium oxalate. Thus violet dichlorodiethylenediaminechromium chloride yields red crystals of an oxalate Cr,(C,O,),,SEn where En = ethylenediamine.The isomeric green salt on the other hand gives a violet compound Cr2C12(C,0,),,3En. A constitution for the red salt Cr,(C,O,),,SEn may be obtained by considering it as formed from any two of the complex ions (En,Cr)"' (En2CrC,0,)' [EnCr(C,O,),]' or rCr(C204)3]"' ; four formule are pos- sible (En,Cr)[Cr(C,O,),] (En,CrC204)[EnCr(C,04),1 and two formulze which imply a double molecular weight (En3Cr)[EnCr(C20,)2]3 and (En,CrC,O,),[ Cr( C2O4),]. Since however the red salt reacts with concentrated hydrobromic acid yielding the oxalodiethylenediaminechromiurn bromide (En2CrC20,)Br identical with the salt described by Werner and Schwarz the formulze (En,CrC20,)[EnCr(C,04),1 and ( En2CrC2O4),[Cr(C2O4)J are alone possible.I f the red salt is treated with potassium iodide the in- soluble oxalodiethylenediaminechromium iodide (En,CrC,O,)I separ- ates whilst the soluble potassium dioxaloethylenediaminechromate [EnCr(C,O,),]K remains in solution and on adding excess of potassium iodide solution is thrown down as the double salt [EnCr(C,04),]K,KI,2H20. These facts are in favour of the formula (En,CrC,04)[EnCr(C204)z] for the red salt. The red salt was then synthesised from the oxalodiethylenedi- aminechromium bromide (En2CrCz04)Br and the potassium salt [EnCr( C,O,),]K which were mixed in concentrated aqueous solution ; the red salt must therefore be called oxccZodiethyZe~ediamircechromium dioxuZoetl~y Zene~ium~nechromate. The isomeric salt (En3Cr)[Cr(C204)3] was obtained from triethylene- diaminechromium chloride (En,Cr)Cl and potassium oxalochromate [Cr(C204),]K,; it crystallised i n green lustrous leaflets with 6 or 7H,O,.and was decomposed by a concentrated solution of potass- ium iodide into the iodide (En,Cr)I and the oxalochromate [Cr(C204)31K 372 ABSTRACTS OF CHEMICAL PAPERS. The violet salt Cr,CI,( C,04),,3En has an analogous constitu- tion (En2CrC1,)[EnCr(C,04),] and is dichlorodiethylenediamine- chromium dioxaloetl~ylenediaminechrornat~. With concentrated nitric acid it yielded the green nitrate (En,CrCl,)NO and it can be synthesised from dichlorodiethylenediaminechromium chloride and potassium dioxaloethylenediaminechromate (En2CrC12)C1 + [EnCr(C,O,),]K = (En2CrC1,)[EnCr(C,0,),1 + KC1. Further the analogous violet cobalt salt (E~,COC~,)[E~C~(C,O,)~] was prepared and crystallised in leaflets.The reactions between potassium oxalate and the violet dichloro- diethylenediaminechromium salts is thus represented (En2CrC1,)* + (C,O,)" = (En,CrC,O,)' + 2Cl' ; (En,CrC,O,)' + (C204)" = [EnCr(C,O,),-J' + En ; (En,CrC,O,)' + [EnCr(C,O,),]' = ( En,CrC,O,)[EnCr( C204)J The reactions between potassium oxalate and the green dichloro- salt are on the other hand to be represented (En,CrCI,)' + 2(C2O,j" = [EnCr(C,O,),]' + 2Cl' + En ; (En,CrCl,)' + [EnCr(C,O,),]' = ( En2CrC1,)[EnCr(C20,)21. I n the case of both salts the oxalo-group replaces the chlorine of the positive ion En,CrC1 in the green salt converting it into the negative dioxalo-ion EnCr(C204) but in the case of the violet salt also giving the mono-oxalo-positive ion En,CrC,O,.It is pointed out that all these observations are in agreement with the view that the two series of salts are stereoisomeric. K J. P. 0. Resolution of Leucine into its Optically Active Components by means of its Formyl Derivative. EMIL FISCHER and OTTO WARBURG (Ber. 1905 38 3997-4005. Compare Abstr. 1900 i 646).-B'ormyZ-leucine C7HI3O3N prepared by heating leucine repeatedly with 93.5 per cent. formic acid and washing carefully so as t o remove unchanged leucine softens at about 112' and melts at 115-1 16" (corr.) ; it crystallises from water in microscopic octahedra and is converted by phosphorus pentachloride into a formyl- leucyl cldoride C,H,*CH(NH*CHO)*COCl which is a colourless indistinctly crystallme powder.B'ormylglycine CHO*NH*CH,*CO,H p.repared by the action of formic acid on aminoacetic acid crystallises from water or alcohol softens at 149' and melts and decomposes a t 153-154" (corr.). When formyl-leucine is heated with an alcoholic solution of brucine the brwine salt of formyl-d-leucine separates in a nearly pure state and on decomposing the latter with N-sodium hydroxide formyl-d- Zeucine is obtained ; it crystallises from water in long thin prisms melts at 141-144' (corr.) and has [.ID i-18.8' a t 20" in 10 per cent. alcoholic solution. B'ormyl-1-leucine prepared by decomposing the more soluble brucine salt has the same melting point as the d-form and [.ID - 18.5' at 20'. To hydrolyse the formyl-derivatives they are heated with 10 per cent. hydrochloric acid the excess of hydrochloric acid and the formic acid removed by distilling under reduced pressure and the active amino-ORGANIC CHEMISTRY.73 acid separated by adding the calculated quantity of lithium hydroxide in alcoholic solution. d-Leucine has [ a ] - 15.6" at 20° whilst 1-leucine has [.a] + 15.6" at the same temperature. These values agree fairly closely with those obtained with the active leucines prepared from the benzoyl-leucines (Fischer loc. cit. ) but a specimen of 1-leucine prepared from proteids by E. Schulze had [ a ] D + 16.9". On the other hand d- leucine obtained from the urine of a rabbit to which inactive leucine had been administered had [ a ] - 15.5" a t 20'. If the value obtained with Schulze's product corresponds with the true active leucine the products prepared from the formyl and benzoyl derivatives must con- tain about 10 per cent.of the racemic foim. W. A. D. Synthesis of Polypeptides. X. Polypeptides of the Diamino- and Hydroxyamino-acids. EMIL FISCHER and UMETARO SUZUKI (Ber. 1905 38 4173-4196. Compare Abstr. 1905 i 121).-Diamino- propionic acid dipeptide is obtained as a tough gummy mass with an alkaline reaction on heating the hydrochloride of the dimethyl ester with water at 80" ; the picyate is a citron-yellow crystalline powder which sinters at 200" and melts and decomposes a t 222" (corr.); the crystalline ?hydrochloride decomposes above 250'. Inactive Zysyl-lgsine C12H2603N4 forms a yellow crystalline picrate which sinters a t 170° melts a t 1 8 5 O (corr.) to a bright brownish-red oil and decomposes on further heating ; the hydrochloride crystallises in short twin prisms melting at about 205" (corr.). Histidine anhydride forms a picrute separating in stellar aggregates of citron-yellow flat crystals which when heated become brown at 235" (corr.) and decompose at 255" (corr.) ; the ILydrochZoride crystallises in thin colourless prisms aggregated in star-like clusters which melt and decompose at about 320" (corr.).Histidylhistidine C,,H,,O,N forms a picrate crystallising in citron- yellow prisms which melt at 165-175". Arginine methyl ester forms a citron-yellow crystalline picrate which becomes brown at 200" and melts and decomposes at about 21s' (corr.) and a nitrate crystallising in large prisms and melting a t 189' (corr.). isoSey9lisoserine methyl ester C7HI4O5N2 forms large crystals which begin to change a t 100' and are completely melted a t 180".isoXerylisoserine is a colourless powder which sinters at 220" and decomposes at a higher temperature ; its aqueous solution has an acid reaction. Serine nzetlbyl ester is a colourless strongly alkaline syrup; the hydrocldoride forms colourless transparent hexagonal plates melting a t about 114' (corr.) and decomposing above this temperature. Serine anhydride C6HI0O4N2 is obtained either as microscopic four-sided oblique plates which become brown at 265" (corr.) and decompose at 280" (corr.) or in long narrow pointed prisms melting at 226' (corr.). Xerylserine is obtained as a mixture of two isomerides; the one present in greater quantity crystallises in stellate leaflets and on heat- ing becomes brown a t 200' and decomposes at 210" (corr.).The aqueous solution is strongly acid and dissolves copper oxide to form a blue 9 VOL. xc. i.74 ABSTRACTS OF CHEMICAL PAPERS. solution. The hycZrocMorkZe of the ester crystallises in star-like aggregates of pointed needles A method of preparing arginine from edestin is described. E. F. A. Action of Carbamide on Compounds of Cyanoacetic Acid. GUSTAV FRERICHS and L. HARTWIG (J. pr. Chem. 1905 [ii] 72 489-51O).-When boiled together carbamide and ethyl cyanoacetate interact to form an ester CO<NH>C*CH2*C02Et N which crystallises from water in long colourless needles melts and decomposes at 1 6 2 O has the solubility 1:8333 in water at 2 4 O and gives a blood-red coloration with traces of aqueous ferric chloride.It has acidic properties liberates carbonic and acetic acids from their salts and in hot aqueous solution dissolves metallic zinc with evolution of hydrogen. The potassium C6H703N,K,2 H20 ammonium silver and copper (C6H70,N2),Cu,2H20 derivatives are described ; the aniline compound C6H,03N2,C6H7N crystallises in needles and melts and decomposes at 144-145' ; the m-tohidine compound crystallises in white leaflets and melts and decomposes at 143O ; the strychnine compound C6H803N2,C21H2202N2 crystallises in sheaves of flat needles and melts and decomposes at 188". The ester does not interact with benzaldehyde formaldehyde or hydroxylamine ; on hydrolysis with alcoholic potassium hydroxide or aqueous ammonia it yields carbon dioxide alcohol ammonia and acetic acid ; when heated with 25 per cent.hydrochloric acid in a reflux apparatus it yields pure ammonium chloride but when warmed with dilute nitric acid a mixture of ammonium nitrate and oxalate. With bromine in aqueous solution it forms an unstable oily additiwe compound which is soluble in ether and liberates iodine from potassium iodide. The corresponding methyl ester COGg>C*CH2*C02Me is formed by heating carbamide with methyl cyanoacetate ; it crystallises from water in colourless leaflets containing l$H20 melts a t 1 1 6 O or when anhydrous at 128O gives a red coloration with aqueous ferric chloride and is slightly more soluble than the ethyl ester which it resembles in its chemical properties. The potassium C,H,O,N,K ammonium C5H5O3N2NH and copper (C5H503N2)2Cu,~H,0 derivatives are described ; the aniline compound C,H603N,.,C6H7N cry stallises in white leaflets and melts at 120' the m-toluadzne compound C6H703N,NH4 c13H1703N89 C6H803N2Br2 c12H1503N3) forms sheaves of slender needles and melts and decomposes at 120-121° ; the strychnine compound C26H2,05N4 crystailises in flat white needles and melts and decomposes at 2119 The methyl ester forms an unstable bromine derivative similar to that obtained from the ethyl ester.G. Y.ORGANIC CHEMISTRY. 75 Mercuric Oxycyanide. KARL HOLDERMANN (Arch. Pharm. 1905 243 600-617. Compare Holdermann Abstr. 1904 i 301 and Richard J. J’harm. Chim. 1903 18 553).-Sy dissolving mercuric oxide in aqueous mercuric cyanide and cryqtallising the solution fractionally it was shown that only one oxycyanide is formed; this has the composition Hg(CN),,HgO.It is never possible to convert mercuric cyanide quantitatively into this compound ; the most con- venient method of separation is to mix the cyanide and oxide in equivalent proportions and moisten the mixture with a little water in a conical flask ; heat the mixture for four hours on the water-bath replacing the water as it evaporates ; extract the mass with boiling water (500 C.C. for 13.5 grains of cyanide and 11.5 grams of oxide); filter the solution and allow it to crystnllise; in these circum- stances about 80 per cent. of the cyanide is obtained as oxycyanide. The amount of oxide in a sample of mercuric oxycyanide can be determined very readily and accurately by adding sodium chloride t o a solution of the sample and titrating the oxide with N/10 hydro- chloric acid with methyl-orange as indicator.Commercial oxycyanide contains but a small proportion of oxide. The pure oxycyanide in aqueous solution gives no yellow coloration with potassium iodide but a n almost colourless crystalline precipitate which dissolves in excess of the aqueous potassium iodide forming a colourless solution. Its electrolytic conductivity is even less than that of mercuric cyanide. The antiseptic action ascribed t o it has been observed with very impure samples and may not belong to the pure substance a t all. Methods of analysing samples of mercuric oxycyanide and tabloids containing it and sodium hydrogen carbonate are described in detail. C.F. B. Blue Iron-cyanogen Compounds and the Cause of their Colour. 111. KARL A. HOFMANN and F. RESENSCHECK (Annalem 1905 342 364-374. Compare Abstr. 1905 i 756).-1t has been shown (Zoc. cit.) that the blue iron-cyano-compounds formed either from ferric salts and ferrocyanides or ferrous salts and ferricyanides are to be regarded as derivatives of potassium ferrocyanide in which potassium is either wholly or partly replaced by tervalent iron. The substances obtained on oxidising the compounds formed from ferrous salts and ferrocyanides do not belong to this class. The material so prepared from potassium ferroqanide and a ferrous salt in molecular proportions in acid solution is quite different from the soluble Prussian blue but identical with Williamson’s violet (Pe”( CN),jFe”’K,nH20 which is produced on oxidation of the residue (Fe”(CN),}Fe”K left in the preparation of hydrocyanic acid.A third blue cornpourLd (Fe(C“),)FeK,H,O isomeric with William- son’s violet is formed when molecular proportions of a ferrous salt and potassium ferrocyanide are brought together in neutral solution a t the ordinary temperature and then oxidised with hydrogen peroxide. It has up to the present been confused with the soluble Prussian blue; it has a greenish-blue colour in aqueous solution is stable76 ABSTRACTS OF CHEMICAL PAPERS. towards a 5 per cent. solution of ammonium carbonate but rapidly decomposed by 4 per cent. ammonia. It is completely insoluble in oxalic acid and in aqueous solution is converted by dilute sulphuric acid into an insoluble blue compound.The constitutional formula (Fe"( CN),)(Fe"'OH)KH is suggested for this compound. The cause of the colour of the iron-cyanogen compounds is discussed ; it is pointed out that the colour is associated with the presence of both bivalent and tervalent iron in the same molecule. Similarly red lead contains both bivalent and tervalent lead; and the deep indigo-blue sulphur sesquioxide although the other oxides of sulphur are colour- less also contains sulphur showing two degrees of valency. This peculiar relation between constitution and colour will be discussed in a later communication. K. J. P. 0. S o m e Derivatives of Octahydroanthracene and Perhydro- anthracene. MARCEL GODCHOT (Compt. rend. 1905,141,1028-1030.Compare Abstr. 1904 i 987 ; 1905 i 201).-Bexal~yd~*oantl~rone oxime C14Hi6:N*OH obtained by heating hexahydroanthrone and hydroxylamine acetate crystallises from alcohol in small colourless needles melting a t 1 4 3 O readily soluble in alcohol ether or light petroleum and reduced by sodium in alcoholic solution to octahydro- anthramine C,,H,?*NH a yellow liquid boiling a t 182' under 12 mm. pressure and having strongly basic properties? combining with the carbon dioxide of the air ; the hydrochloride C,,H,7*NH,,HCl forms colourless prisms decomposing without fusion at 188" and readily soluble in water or alcohol ; the piwate forms yellow needles melting at 212O readily soluble in alcohol less so in ether or light petroleum ; the ucetyl derivative Cl4Hl7* N HAc crystallises from alcohol in beautiful colourless needles melting at 183" and soluble in benzene ether or chloroform.Perhydroanthracene C14H24 prepared by reducing anthracene with hydrogen iodide and phosphorus (compare Lucas Abstr. 1888 120l) can be obtained more readily by the action of hydrogen iodide and red phosphorus on octahydroanthracene in sealed tubes at 250" or by the direct hydrogenation of octahydro- anthracene in the presence of reduced nickel at 180° a liquid hydro- carbon probably dodecahydroantlwacene CI4H2 being formed a t the same time. 31. A. W. Fluorene Compounds. FRITZ ULLMANN and R. VON WURS- TEMBERGER (Ber. 1905 38 41 05-41 lo).-9 9-Diphenyvuorene [clil.lhen~lbip?~enyZenemet?~ane] 76H4>CPh prepared by the action of bromobenzene and magnesium on methyl diphenyl-2-carboxylate crystadlises from acetic acid in colourless prisms melts at 222' (corr.) and boils without decomposition above 400'.C6H4 C H BiphenylenemethyZcarbinol[9-met?~ylJEuorene alcohol] I 4>CMeoOH CAH prepared by the action of methyl iodide and magnesiu; 0 fluorenone crystallises from benzene in glistening prisms and melts at 174.5'.ORGANIC CHEMISTRY. 77 The corresponding ethyl compound yGH4>CEt OH crystallises from light petroleum and melts at 101'. Biphenylenepropylene [9-ethylidene~%orene] y6H4>C:CHMe pre- C6H4 C J L pared by the action of acetic and hydrochloric addcon the preceding compound crystallises from acetic acid and melk a t 104'. Bipheny Zene benxylcarbino E [9- benxy Yuorene a Zcolhol] 7GH4 OH C,H4>c<CH,Ph ' separates from a mixture of benzene and light petroleum in large crystals and melts at 139O.Biphenylenephenyletliylene [9-benxylidene- fluorene] yeH4>C:CHPh separates as a yellow oil which crystallises and melts at 76'. C6H4 Bipheny Zene - a-naphth y Zcarbino I [9-a-naphth yljluorene alcohol] OH F"H">C<C 10 H ' 7 C6H4 crystallises from a mixture of benzene and light petroleum and melts at 151.5'. It is reduced by zinc and acetic acid to 6iphenyZene-a- naphthylmethane [ 9-~-naphthylJEuorene] C23H16 which separates from alcohol in colourless needles and melts a t 103.5'. Biphenylene-p- aminophenyl-a-naphthy Zmethane [9-p-arninopherql-9 -a-naphth yljluorene] prepared by the action of aniline on the FsH4>c<; C H ; *NH carbinol separates from alcohol in small white strongly electric crystals and melts at 145'.The hydrochloride C,,H,,N,HCl is a white crystalline powder and melts and decomposes at 225-5230'. CtjH 10 7 T. M. L. Acetylene Linking. FRITZ STRAUS (Annalen 1905 342 190-265).-Phenylacetylene together with copper phenylacetylide and diphenyldiacetylene are formed when copper phen ylpropiolate (CPhiC*CO,),Cu,4 H,O is heated. Solutions of sodium phenylpropiolate and cupric chloride are mixed and steam passed into the mixture when the hydrocarbon distils over. If copper phenplpropiolate is treated with pyridine 01' quinoline only copper phenylacetylide and diphenyldiacetylene are formed . Copper phenylacetylide dissolves in boiling acetic acid with an orange-yellow coloration no appreciable quantity of hydrocarbon being evolved.The solution deposits on cooling or on addition of ice-cold water the double salt CPhiCCu,CH,-CO,Cu which crystal- lises in orange-yellow leaflets ; this substance oxidises very readily its solution in organic solvents being decomposed by contact with air copper phenylacetylide being formed. If air is passed through its boiling solution in acetic acid diphenyl buteninene is formed a reaction which is thought to indicate the presence of more than one bydro- carbon radicle in the molecule of the copper compound,78 ABSTRACTS OF CEEMICAL PAPERS. Diphenyldiacetylene CPhiC*CiCPh is prepared by treating copper phenylacetylide with an aqueoiis solution of potassium ferricyanide made alkaline by potassium hydroxide or by warming copper phenyl- propiolate with pyridine ; it is crystallised from methyl alcohol and melts at 86-87'.Diphenylbuteninene CHPh:CH*CiCPh prepared by dissolving copper phenylacetylide in acetic acid in a flask from which the air has been expelled boiling and then sucking air through the mixture crystallises in colourless prisms melting a t 96.5 - - 9 7 O . The solution in acetic acid becomes blue on the addition of sulphuric acid and then forms a dichroic violet-red liquid. [With RUDOLF MULLER.]-~ chloroform or carbon disulphide solution diphenyldiacetylene yields a mixture of stereoisomeric tetra- bromides CPhBr:CBr*CBr:CPhBr from which the hydrocarbon is re- generated by reduction with zinc dust in acetone solution. It is note- worthy that more than four atoms of bromine cannot be added to the molecule.A dibromide CPhBr.:C:C:CPhBr (?) is formed as an inter- mediate product crystallising in yellow rhombs melting a t 142'. The mixture of tetrabromides melts at 120-140° and a tetrubyomide (m. p. 172') can be isolated from this mixture by cryetallisation from petroleum. When diphenyldiacetylene in acetic acid is treated with excess of bromine a tribrorno-derivative is obtained which is not as Hollemann thought; a tribromo-derivative of the diacetylene but tribromo-a- phenylnaphthalene CsH,<cph :b Br ; it crystallises in yellow CBr :CBr podules melting a t 151'. When reduced with alcohol and sodium amalgam it is converted into a-phenylnaphthalene C,,H7Ph which boils a t 192-195' under 17 mm. pressure and is oxidised by potassium dichromate and sulphuric acid to o-benzoylbenzoic acid.Reduction of the tribr;.omide with zinc dust and acetic acid yields a dibromo-a-pJienylnccpJ~thccZene C,,H,Br2Ph which forms crystals melting a t 111-111.5°. Diphenyldiacetylene is reduced by boiling in alcoholic solution with zinc dust light being carefully excluded to the labile cis-cis-diphenyl- butadiene 2>C:C*C:C<,h which crystallises in leaflets or four- sided plates melting at 70-70*5'; when exposed t o sunlight this hydrocarbon is transformed into the stable trans- trans-diphenyl- butadiene which melts at 142-145' or when pure at 150-151O. As an intermediate product in the reduction cis-diplhenylbuteninene %>C:C<gCPh is formed ; it is a yellow oil freezing a t about Oo and boiling at 187.5-188O under 12 mm.pressure ; when exposed t o sunlight it is transformed into the stable trccns-diphenylbuteninene (m. p. 97") above described. The cis-diphenylbuteninene forms with bromine a mixture of tetrabromides from which needles melting and decomposing at 205O leaflets melting at 135-136" and prisms melting and decomposing at 160' can be isolated. The two iso- merides with higher melting points are probably identical with the cornpouads obtained from trans-diphenylbuteninene. On treatment HHORGANIC CHEMISTRY. 79 with hydrogen bromide the same compound is obtained from both the cis- and trans-isomerides. cis-trans-Diphenylbutadiene ?>C C C C<Fh is prepared from HH trans-diphenylbuteninene by reduction with zinc copper couple in alcohol solution in the absence of sunlight and crystallises in leaflets melting at 150-151'.It is the most unstable of the diphenyl- butadienes and passes on transitory exposure t o light into the stable trans-trans- f orm. On bromination cis-cis-diphenylbutadiene yields in chloroform solution a mixture of tetrabromides from which two compounds can be isolated one crystallising in leaflets melting at 225' and a second crystallising in prisms melting and decomposing a t 180". trans-Diphen ylbu t eninene yields a tetra bromide CBrPh:CBr*CHBr* CHBrPh when brominated in chloroform solution which crystallises in leaflets melting and decomposing a t 197' ; a t the same time a second tetra- bromide is formed melting and decomposing at 157-158'. Hydrogen bromide converts the trans-diphenylbuteninene into diz~J~e?~?lZbutndiene dibromide Ci6Ki4Br2 which crystallises in needles melting and decomposing a t 142O and a bromodiphenylbutadiene Cl(;HL3Br which crystallises in needles melting a t 11 3.5-1 14' ; the latter monobromo- derivative is not changed by hydrogen bromide and is converted by bromine in to bromodipphenylbutadiene dibrornide C16H13Br3 crystallis- ing in needles melting at 145-147'. All the diphenylbutadiene bromides are reduced by zinc dust or the zinc copper couple to the stable trans-trans-diphenylbutadiene (m.p. 150-1 5 1"). Az-DiphenyZ6utene CH,Ph*CH:CH*CR,Ph prepared from diphenyl- butadiene crystallises in needles melting a t 45-45.5' and yields a dibromide which by heating with quinoline is converted into diphenyl- butadiene.When oxidised with potassium permanganate a t O" ,@y-di%ydroxy-a8-dipJ~enyZbutune CH,Ph-CH(OH).CH(OH)*CH,Ph is obtained as needles melting at 125'. The diphenylbutene can also be prepared by reducing with alcohol and sodium amalgam diphenyl- diacet ylene trans - dip h en yl bu t en inene truns-truns-dip hen yl bu t adiene and cis-cia-diphenylbutadiene. A2-Phenylbutene CH,Ph*CH:CHMe is formed from phenyl- butadiene by reduction with sodium amalgam and alcohol but styrene is not reduced under similar treatment. Phenylacetylene is reduced by zinc dust and alcohol to styrene and diphenylbutadiene ; with zinc dust and acetic acid diphenyldiacetylene yields a number of reduction products. Tolane is not attacked by sodium amalgam and alcohol but by zinc dust and alcohol is converted into isostilbene.When oxidised stilbene yields isohydrobenzoin and isostilbene benzoin. K. J. P. 0. Action of Ethylene Dibromide on p-Nitrosodialkylanilines 11. HENRY A. TORREY (Amer. Chern. J. 1905 34 475-481. Compare Abstr. 1 902 i 755).-Di-p-nitrosodimethylaniline-ethylene,80 ABSTRACTS OF CHEMICAL PAPERS. obtained by the action of ethylene dibromide on p-nitrosodimethyl- aniline is identical with tetramethyldiaminoglyoxime N-phenyl ether described by Pechmann and Schmitz (Abstr. 1898 i 309). When the reaction takes place in alcoholic solution tetramethyldiaminoazoxy- benzene is produced. By the action of dilute nitric acid on tetraethyl- diaminoglyoxime N-phenyl ether tetramethyldiaminoglyoxaldianil is formed which when boiled with an alcoholic solution of salicyl- aldehyde is converted into o-hydroxybenzylidene-p-aminodimethyl- aniline ; whilst by the action of benzoyl chloride benzoyl-p-amino- dimethylaniline is produced.The dianil yields a bronze-coloured picrate gives a blue precipitate with mercuric chloride and a blue coloration with dilute solutions of bromine chlorine hydrochloric acid and acyl chlorides. By the action of ethylene dibromide on p-nitrosodiethylaniline tetraethyldiaminoglyoxime N-phenyl ether (Pechmann and Schmitz Zoc. cit.) and p-nitrosodiethylaniline hydrobromide are produced. E. G. New Derivatives of Pentabasic Phosphoric Acid P( OH)5. PAUL LEMOULT (Compt. rend. 1905 141 1241-1244).-The phos- phorus alkyloxytetra-anilides of the type P(OR1)(NHR) where R1 and R represent alkyl and nryl radicles respectively (compare Abstr. 1904 i 807) condense with acetic or propionic acids to form com- pounds of the type COR1*O*P(NHR) which may be regarded as the acetates or propionates of the base OH*P(NHR),.These compounds form well-defined crystals usually containing acid of cry stallisation which they lose a t 100'; they are readily decomposed by water or alkalis to form the corresponding phosphoryltrianilides PO(NHR) and by hydrochloric acid t o form the corresponding chlorotetra- anilides. The o-tohidine-compound OAc*P(NH*C,H,Me),,AcOH forms beautiful colourless crystals melting a t 221". COEt.O*P(NH*C,H,Me),,EtCO,H forms small crystals melting a t 203'. CH,C1*CO*O*P(NH*CsH4Me) forms a confused crystalline mass. The 1 3 4-xylidine-compound OAc*P(NH*C6H,Me,),,l-5AcOH forms beautiful colourless spangles several millimetres in dimensions melting a t 2 10'.The compounds OAc*P(NHPh) and COEt-0-P(NHPh) obtained by the action of acetic or propionic acid respectively on trianilinephenylphosphimide P(NHPh),iNPh (Abstr. 1903 i 672) crystallise from a mixture of benzene and ether and melt a t 206-207' and 240' respectively. The compound The compownd M. A. W. Partial Reduction of Aromatic Dinitro- and Polynitro- derivatives by Electrolytic Methods. KURT BRAND (Bey. 1905 38 4006-401 5).-m-Nitrophenylhydroxylamine can be easily obtained by the electrolytic reduction of rn-dinitrobenzene in an approximately neutral solution ; the cathode cell consists of a porous pot containing the m-dinitrobenzeae dissolved in aqueaus alcohol with a little aceticORGANIC CHEMISTRY. 81 acid and sodium acetate.The anode liquid used is 20 per cent. sul- phuric acid. The cathode is made of silver gauze and the anode is a perforated lead plate. m-NitrophenyZ?LydroxyZumine NO,*C,H,*NH*OH prepared in this way separates from hot benzene in thick yellow crystals melts at 118-1 19" and is easily oxidised by alcoholic ferric chloride to 9%-nitronitrosobenzene (Bamberger and Hubner Abstr. 1904 i 115) ; when warmed with dilute sulphuric acid m-nitrophenylhydroxylamine is converted into 2-nitro-4-aminophenol. The substance melting at 178" described by Wohl (D.R.-P. 84138) as m-nitrophenylhydroxyl- amine seems to be a transformation product of the latter ; its nature is being investigated. On reducing m-dinitrobenzene in alkaline solution using mercury as the cathode so as to prevent the formation of a solid film on the latter and thus stopping the action m-dinitroazoxybenzene is obtained ; the yield is good and the method can be used for preparing the substance.The reduction of m-dinitrobenzene in strongly acid solution gives m-nitroaniline the yield being good. W. A. D. Hydrogenation Derivatives of Carvacrol. L ~ O N BRUNEL (Compt. Tend. 1905 141 1245-1247. Compare Abstr. 1904 i 158).-When carvacrol is directly hydrogenated in the presence of reduced nickel at 160" a mixture of two isomeric hexahydrocarvacrols (a- and P-carvacro- menthols) is produced ; they are probably the two stereoisomerides formed by the hydrogenation of an intermediate ketone the correspond- ing carvacromenthone (compare Abstr.1905 i 197 363) ; when the hydrogenation is effected at 1 15-120° P-carvacromenthol is the only product. a-Caruucromenthol is a colourless oily liquid with an odour of thyme and boils at 219'. P-Carvncromenthol an oily colourless liquid with an odour of mint boils a t 2 2 2 O does not crystallise at - lo' has a sp. gr. 0.918 a t O' and forms well-defined esters with acids. The formnte HC02*CloH19 obtained by the direct action of formic acid and the alcohol in the cold is a colourless mobile liquid with an agreeable odour like that of camphor boils a t 229O and has a sp. gr. 0.954 at 0'. The acetate OAc'CloH19 prepared by heating acetic acid and the alcohol in sealed tubes at 130° is a colourless mobile liquid with a strong odour which boils at 231.5" does not crystallise at - lo' and has a sp.gr. 0.933 at 0'. The acid succinute CO,H*C,H,* CO2*Cl0Hl9 prepared by heating the alcohol with succinic anhydride at looo crystallises from light petroleum in thin colourless odourless needles melting at 74" and soluble in dilute alkali solutions. C0,H*C,H,-C0,*C,oH,9 crystallises from alcohol in large colourless odourless crystals melting at 136' and soluble in alkali solutions. The m i d phthulate M. A. W. Action of Phosphorus Pentachloride on P-Naphthol. E. BERGER (Compt. Tend. 1905 141 1027-1028).-At temperatures below 1 30° phosphorus pentachloride reacts with P-naphthol to form P-dinaphthyl ether but when the temperature is raised to 135-140' and82 ABSTRACTS OF CHEMICAL PAPERS. the heating continued for twenty-four hours a mixture in the propor- tion 3PC1 SC,,H7*OH yields 30 per cent.of P-chloronaphthalene (compare Cleve Abstr. 1876 ii 81; Rimarenko Abstr. 1876 ii 297) together with small quantities of 1 2- 2 4- 2 6- and 2 8- dichloronaphthalenes PP-dinaphthylene oxide and di-P-nnphthyl hydrogen phosphate melting at 143'. 2 3-Dihydroxyanthracene. KASIMIR LAGODZINSKI (Annalen 1905 342 90-111. Compare this vol. ,i 98).-2 3-Dihydroxy- anthracene which has been prepared in order to procure 2 3-anthra- quinone is obtained from the dimethyl ether of hystazarin which is synthesised from veratrole. 0-3' 4'-Bimethox ybenxo ylbelzxoic acid C,H (OMe) ,*CO*C,H,*CO,H prepared by warming a carbon disulphide solution of veratrole with phthalic anhydride and aluminium chloride crystallises in colourless leaflets melting at 233' and is soluble in concentrated sulphuric acid with a blood-red coloration ; the ammonium salt forms white needles and the silver salt white crystals.The acid does not react with hydroxylamine but with phenylhydrazine yields 2-phenyl-4-veratryl- phthakazone (? o*C6H4>C*C,H,(OMe) which crystallises in yellow needles melting at 189". The dimethyl ether of hystazarin ( 2 3-dimet?~oxyanthrapuinone) M. A. W. NPh-N C,H,<CO>C,H,(OMe) co is formed when dimethoxybenzoylbenzoic acid is warmed with concentrated sulphuric acid and crystallises in golden-yellow needles melting a t 237' ; it yields a blood-red solution in sulphuric acid. Prolonged heating a t 100" with sulphuric acid con- verts the dimethyl ether into the monomethyl ether OH*C,,H,O,*OMe which crystallises in orange-yellow leaflets melting a t 236".The com- plete hydrolysis of the ether to hystazarin is best effected by heating with hydrobromic acid of sp. gr. 1.49 under pressure a t 180'. On reduction with zinc dust and 5 per cent. ammonia the dimethyl ether of hystazarin is converted into 2 3-dimethoxyanthracene C,,H,( OMe) crystallising in colourless leaflets or needles melting a t 204"; the alcoholic solution has a blue fluorescence and the solution in sulphuric acid an orange-yellow coloration ; the picrate is dark brown in colour ; in acetic acid solution it is converted into a polymeride melting a t 314O and in alcoholic solution it is oxidised to the corresponding anthra- quinone. When warmed with hydriodic acid (b.p. 127") the dimethoxy- anthracene yields 2 3-dihydroxyanthracene7 which crystallises in straw- yellow leaflets decomposing at 180-1 92'. 2 3-Diacetoxyanthracem forms pale yellow crystals melting at 155-160'. Attempts to oxidise this dihydroxyanthracene to the corresponding 2 3-dihydroxyanthraquinone were not successful. When dimethoxyanthracene is heated in acetic acid solution with hydriodic acid of sp. gr. 1.70 a compound CsoHzo04 of unknown con- stitution is formed ; it crystallises in yellow leaflets decomposing at about 260". It forms in sulphuric acid an orange-yellow solution which becomes blood-red on heating; its solution in alkali hydroxides is yellow. It can be methylated by methyl sulphate and potassiumORGANIC CHEMISTRY. 83 hydroxide and acetylated by acetic anhydride.With ether it forms the compound C30H2004 20Et2 which crystallises in greenish-yellow plates. K. J. P. 0. Aromatic Sulphine Balses. FRIEDRICH KEHRMANN and A. DUTTEN- HOFER (Ber. 1905 38 4197-41 99).-The pkatiniciiloride of diphenyl- methylsulphine (C,,H,,S),PtCl forms a yellowish-white crystalline precipitate melting a t 169.5' ; the dichromate separates as a yellow flocculent precipitate which rapidly becomes green and decomposes forming a substance crystallising in orange needles and melting at 129". Di-a-naphth ylmeth ylsulphine platinich Zoride ( C,,H,7S)2Pt Cl forms a flesh-coloured powder and melts at 162-163' ; the aurichloride is yellow and the dichromate is orange.Di-P-naphthylmethyls~~p~~ne platinichloride melts a t 136-146'. Behaviour of Esters of Organic Acids when heated with Orthophosphoric Acid. PAUL N. RAIKOW and P. TISCHKOW (Chem. Zeit. 1905,29 1268-1273).-.The combined action of heat and ortho- phosphoric acid on the methyl esters of various organic acids was studied with the object of determining whether or not the ester lost carbon dioxide leaving the methyl group attached to the rest of the molecule. The acid used was first dehydrated by heating 60 C.C. of syrupy phosphoric acid of sp. gr. 1.7 to 200' in a round-bottomed flask of 200 C.C. capacity; after cooling to below loo' a measured quantity of the ester was added and the mixture was then boiled over iron gauzo. The flask was attached to a reflux condenser the upper end of which was connected by an india-rubber tube to one limb of a U-tube containing 50 C.C.of concentrated sulphuric acid ; the other limb was connected to an apparatus for determining the amount of car- bon dioxide evolved by measuring the water which it displaced from a wide-mouthed bottle of 2 litres capacity filled with water. The boiling was continued until the evolution of gas had ceased. The gas remain- ing in the bottle was examined for carbon dioxide and carbon monoxide; the object of the U-tube with strong sulphuric acid was to absorb any dimethyl ether which might be formed. The following compounds were examined in this way. The methyl esters of benzoic 0- rn- and p-toluic 0- m and p-chlorobenzoic p-bromobenzoic o-iodo- benzoic 0- m- and p-aminobenzoic 0- m- and p-nitrobenzoic salicylic m- and p-hydroxybenzoic 2- hydroxy-3-methylbenzoic 2-hydroxy-4-methyl- benzoic 2-hydroxy-5-methylbenzoic 2 4-dihydroxybenzoic gallic anisic vanillic 3-chloro-2-nitrobenzoic 3 5-di-iodo-2-hydroxybenzoic 6-nitro- 2-hydroxybenzoic 4-nitro-Z-hydroxybenzoic phthalic isophthalic tetra- chlorophthalic 0- and p-nitrophthalic a- and /3-naphthoic p-hydroxy- naphthoic phenylacetic hydrocinnamic and cinnamic acids ; also the ethyl esters of propionic and butyric acids the phenyl esters of benzoic and salicylic acids as well as the following two free acids terephthalic and dichlorophthalic.The following conclusions are drawn from the experimental results :-(1) Except in the case of methyl p-chlorobenzoate the methyl of the ester group was never observed to replace the -C02Me group and the method is therefore of no use for the introduction of a methyl group into the benzene nucleus.(2) The methyl group was commonly split off in the form E. F. A.84 ABSTRACTS OF CHEMICAL PAPERS. of dimethyl ether ; in the case of aromatic hydroxy-acids it frequently wandered from the carboxyl group t o the phenolic hydroxyl group in the ortho- or para-position. The ethyl group was split off from the two ethyl esters examined in the form 0-f ethylene. (3) With the exception of the esters of cinnamic and o-nitrocinnamic acids no esters contain- ing the -CO,Me group attached to an aliphatic complex gave off carbon dioxide. (4) The introduction of substituting groups into benzoic acid reduces the stability of the -CO,Me group.(5) The stability of the -CO,Me group is influenced both by the nature of the substituting group and by its position in the ring. (6) The hydroxyl and the amino-groups have the greatest influence. (7) I n naphthoic acids the second benzene ring acts on the-C02Me like a substituting group but exerts a greater influence in the case of the a- than in the case of the P-acid. (8) Unlike all other substituting groups the introduction of a second -CO,Me increases the stability of the C0,Me group. P. H. The Glucoside Structure of Conjugated Glycuronic Acids. HERMANN HILDEBRANDT (Beitr. chem. Physiol. Path. 1905,7 438-454. Compare Abstr. 1901 ii 614; Neuberg and Neimann 1905 i 412).- Emulsin has no action on the glycuronic acid derivative of p-dimethyl- aminobenzoic acid ; the derivative probably has not a glucosidic structure and the following formula is suggested p-Benzobetaine does not couple with glycuronic acid in the mimal system ; the greater part is eliminated unaltered and a small portion is converted into mono- and di-methyl-p-aminobenzoic acids.The glucosides of glycerol and benzyl alcohol (E. Fischer Abstr. 1895 i 6) are hydrolysed by both emulsin and yeast. Glycuronic acid itself is decomposed by yeast or zymase volatile acids are formed and the solution loses its reducing properties. When syringinaldehyde is administered to dogs both free syringic acid and its compound with glycuronic acid are found in the urine. When syringin is injected subcutaneously in dogs Korner's gluco- syringic acid (Abstr.1889 159) and syringaglycuronic acid are found in the urine. When coniferin is administered in the same way no free vanillic acid can be found in the urine but potassium vanillinglycuronste can be isolated. Both acids are hydrolysed by emulain. This is hydrolysed by emulsin. J. J. S. Oxidation of 4Nitro-6-amino-m-xylene. GIORGIO ERRERA and RAFFAELE MALTESE (Gaxxetta 1905 35 ii 370-383).-When oxidised with potassium permanganate 4-nitro-6-diacetylamino-m-xylene yields a mixture of 4-nitro-6-aminoisophthalic acid 4-nitro-6-amino-m-toluic and 6-nitro-4-amino-m-toluic acids and their monoacetyl derivatives. 6 -Nitro- 4- acet ylamino-m-toluic acid C10H1005N2 separates from alcohol or ethyl acetate in sulphur-yellow triclinic crystals [a 6 c = 1.6623 1 1.0340 ; a= 79'40' /3= 64'4' and y = 105'33'1 melts and decomposes at 223-225".and dissolves slightly in water benzene orORGANIC CHEMISTRY. 85 xylene readily in acetic acid. The corresponding potassium salt was prepared and analysed. 4-Nitro-6-acetyZccmino-m-toZuic acid C,,H,,O,N crystallises from alcohol in pale straw-yellow plates melting and decomposing at 254-255" and is less soluble than the acid just described in all solvents except water ; its potccssium salt was analysed. 6-Nitro-4-un~ino-m-toZuic acid C8H8O4N2 separates from alcohol or ethyl acetate in shining red crystals melting and decomposing a t 239-240' and dissolves slightly in water or benzene. 4-Nitro-6-anzino-m-toZuic acid C,H,O,N crystallises from water in golden-yellow needles which on rapid heating in a capillary tube melt a t about 235"; it dissolves readily in alcohol or ethyl acetate and slightly in benzene.On heating the acid or its acetyl derivative with concentrated sulphuric acid it yields 4-nitro-o-toluidine. The methyl ester C9HIOO4N2 separates from methyl alcohol in either needles or hard crystals of a pale yellowish-grey colour and melts at 169'. 4-o-p-BinitroaniZino-6-nitro-m-toZuic m i d C,,H,,0SN4 crystallises from acetic acid in yellow needles which melt after blackening a t 298'; it is only slightly soluble in the ordinary solvents and gives red salts. 1 3 8- Trinitro-7-methyZuccridollze C,,NH,Me(NO,) prepared by heat,ing the preceding acid or its ammonium salt with sulphuric acid and subsequently pouring the mass into water separates from acetic acid in large dark brown crystals or from benzene in orange-brown needles which melt after blackening at 253' ; it dissolves slightly in alcohol and to a greater extent in xylene.T. H. P. [ Claisen's Cinnamic Acid Synthesis.] ARTHUR MICHAEL (Bey. A reply to Storiner and Kippe (Abstr. 1905 38 4137).-Polemical. 1905 i 777). J. J. S. Synthesis of Tyrosine. PETER W. LATHAM (Luncet 1905 ii 1757).-A new method of syn thesising tyrosine from hydrogen cyanide and p-hydroxybenzaldehyde is described. It is pointed out that in the body adenine an isomeride of hydrogen cyanide may take the place of the latter substance in tyrosine formation. W. D. H. Synthesis of Amino-acids of Proteid Origin. LOUIS HUGOUNENQ and ALBERT MOREL (Conzpt.rend. 1906 142 48-49. Compare Abstr. 1905 i 178 264 332).-The symmetrical p-hydrocoumaric acid derivative of carbamide CO~NH~CH(CO,H)-CH,~C,H,*OH] pre- cipitated when a slow stream of carbonyl chloride is passed into an aqueous solution of the sodium salt of tyrosine is very sparingly soluble in water more soluble in alcohol from which solution it is precipitated by water in the form of flakes resembling proteid matter. The dry powder darkens at 150" melts at 240° and gives a red colour with Millon's reagent. The p-hydrocoumaric acid derivative of phenyl- carbamide NHPh*CO*NH*CH(CO,H)*CH,*C,H,*OH prepared by the action of phenylcarbimide on the sodium salt of tyrosine is very86 ABSTRACTS OF CHEMICAL PAPERS. sparingly soluble in water can be crystallised from alcohol melts and decomposes at 194' and reacts with Millon's reagent.31. A. W. Conductivity Measurements with Organic Acids. JOSEF HANS SUSS (Monntsh. 1905 26 1331-1342. Compare Wegscheider Abstr. 1902 i 617 ; and following abstract).-With pZ = 375 nitro- opianic acid has K 0*000291 ; a week-old solution has a 20 per cent. a solution which has been heated on the water-bath for one hour a 5 per cent greater conductivity. 5-Nitro-3-aldehydobenzoic acid has KO.0100 with pz = 378. 3-Nitro- 2-aldehydobenzoic acid has K 0.000130 with px =378. Nitro- hemipinic acid [(CO,H) (OMe) NO = 1 2 3 4 61 has K 2.1 with px = 374 ; at the dilution v = 256 it shows marked dibasic dissocia- tion which is not observed with hernipinic acid a t the dilution v = 1000.The dissociation constant for the second hydrogen atom is s x 106= 208 or 218. Aminoterephthalic acid has K 0.0265 with p-ccr = 377 whilst its 1-methyl ester has K 0.00552 with puy3 =376. Methylaminotere- phthalic acid has K 0.030 with poo = 376 Acetylaminoterephthalic acid has K 0.098 with pa =375. A slightly impure specimen of 1-methyl hydrogen acetylaminoterephthalato had K 0.07 with pa = 374.4. Acetylmethylaminoterephthalic acid has h'= 0.126 with pa = 374.4. Homophthalic acid hzls K 0,0190 with pa = 376.5 ; the a-mono- methyl ester has K0.00434 with pm = 375.3 ; the P-monomethyl ester has K 0.00764 with pa = 375.3. The a-monoethyl ester has K 0.0046 with pa = 374.6 ; the /?-monoethyl ester has K 0.00708 with pa = 3 74.6. 2-Car bamidophenylace tic acid NH2*CO*CGH,*CH2.C0,H has H 0.0050 with pa = 376.has K 0.0089 with pa = 376. Phthalonic acid resembles pyruvic acid in that it is a strong acid the affinity constant of which diminishes rapidly as the dilution increases ; it has K 2.14 at the dilution v== 128 ; K 1.91 a t v = 256 ; K 1.44 at v=512; and K 1-10 at u=1024. Methyl hydrogen phthalonate CO,Me*CO*C,H,*CO,H prepared by partial hydrolysis of the dirnethyl ester as also by the action of methyl alcohol on the acid has KO.015 withpa =375*7. Phenylitaconic acid CHPh:C(C02H)*CH,*C0,H has K 0.0137 with pa = 375; it shows no distinct dibasic dissociation. Phenylacetnmide-o-carboxylic acid NH,.CO*CH,* C,H,* CO,H G. Y. Constitution of o-Aldehydo-acids in Aqueous Solution. RUDOLF WEGSCHEIDER (Monatsh. 1905 26 1231-1234.Compare Wegscheider Abstr. 1902 ii 494 ; 1903 i 562).-The affinity con- stants of o-phthalaldehydic 5-nitro-2-aldehydobenzoic 3-nitro-2-alde- hydobenzoic and nitro-opianic acids are smaller than those of the corresponding acids without the aldehyde group. These aldehydo-acids must exist in aqueous solution to a greater or less extent as the - CH(0H) pseudo-form C6H,<-CO>0 whilst opianic acid the afinity con- stant of which is ten times that calculated for the correspondingORGANIC CHEMISTRY. 87 acid without the aldehyde group must exist in aqueous solution entirely in the normal or carboxylic form. A comparison of the affinity constants of o-phthalaldehydic and opianic acids shows that methoxy-groups in the ortho- and meta-positions prevent the formation of the pseudo-form.The influence of a nitro-group in the rneta- position to the carboxyl-group on the formation of the pseudo-form is only slightly favourable if the nitro- and aldehyde-groups are in the para-position but highly favourable if these groups are in the ortho- position t o one another. G. Y. Action of Diazomethane on Aldehydo-acids and Aldehydes. HANS MEYEE (Monatsh. 1905 26 1295-1301. Compare Abstr. 1905 i 13S).--Diazomethane is estimated by shaking its solution with an equal volume of N/10 aqueous hydrochloric acid whereby it is converted into methyl chloride completely in a few seconds and titrating the excess of acid with N/10 alkali hydroxide. Opianic acid and diazomethane interact energetically to form methyl opia na t e. The action of diazomethane on bromo-opianic acid or of methyl iodide on the silver salt at the laboratory temperature leads to the formation of methyl homo-opianate C11H905Br which crystallises from benzene and melts a t 105-106°.The +-methyl ester formed by the action of thionyl chloride or of boiling methyl alcohol and sulphuric acid on the acid crystallises in needles and melts a t 109-110'. A mixture of equal amounts of the isomeric esters melts at 70" (compare Bietrzycki and Fink Abstr. 1898 i 427). The action of diazomethane on nitro-opianic acid leads to the formation of the normal ester (Wegscheider Kudy von Diibrav and Rugnov Abstr. 1904 i 59). These aldehydo-acids have therefore the normal constitution when anhydrous (compare Wegscheider preceding abstract) but whilst opianic and bromo-opianic acids give an intense blue coloration with congo-red and have therefore the normal constitution in aqueous solution nitro- opianic acid functions in aqueous solution as a $-acid as it is entirely withoiit action on the indicator (compare Lobry de Eruyn Abstr.1899 i S61). Diazomethane does not interact with benzaldehyde or heptoic alde- hyde but evolves nitrogen slowly in contact with the three nitro- benzaldehydes ; o-nitrobenzaldehyde yields a brown oil which distils apparently without change ; sn-nitrobenzddehyde yields a liquid and a solid product ; the latter crystallises in colourless needles melts at 76O forms an orange-yellow hydrazone melting at 127O on oxidation by permanganate gives m-nitrobenzoic acid but is not identical with m-nitroacetophenone as it is odourless and dissolves in boiling aqueous potassium hydroxide forming a reddish-yellow solution ; p-nitro- benzaldehyde yields two poducts melting at 62-65' and at 84" respectively.The more fusible substance C,H70,N dissolves in hot aqueous potassium hydroxide to form a rose-coloured solution changing to yellow and on oxidation yields p-nitrobenzoic acid. Diazomethane and p-chlorobenzaldehyde interact t o form a solid product which melts a t a high temperature. G . Y.88 ABSTRACTS OF CHEMICAL PAPERS. Syntheses by means of the Carboxylic Esters of Cyclic Ketones. Synthesis of Menthone from Metbylhexanone. ARTHUR KOTZ and LUDWIG HESSE (Annalen 1905 342 306-328).- Since the hydroaromatic P-ketocarboxylic acids such as cyclohexanone- o-carboxylic acid CH2<C,2.CH cH2-Co>CH*C0,H would be valuable for synthetical purposes attempts have been made to prepare such acids with readiness.Endeavours t o bring about an internal condensation of esters of dibasic acids in a manner analogous to the formation of ethyl acetoacetate or to condense cyclic ketones with ethyl carbonate led to no result. On the other hand with ethyl oxalate the ketones yielded ethyl keto-o-oxalates. Ethpl l-metluylcyclohexane-3-one-4-oxaZate is prepared from methylhexanlone and ethyl oxalate and sodium wire in the presence of light petroleum; the mixture is treated with water and the aqueous solution acidified and extracted with ether the ketonic ester being finally purified in the form of its copper salt ; it is a colourless liquid boiling at 163' under 12 mm.pressure and has a sp. gr. 1.0903 at 15'. The copper salt C22H300SC~ forms crystals melting at 153'; the semimrbazone melts a t above 245'. 1-Methyl- cyclohexccne- 3-one -4-oxalic mid prepared from the ester by hydrolysis with 10 per cent. sodium hydroxide melts and decomposes at 132'. The semicccrbaxone melts at above 245'. When the ester is warmed ~ H M e * C H * ~ * N P h * ~ O derived from with aniline a compound hexahydroindole is obtained crystallising in needles melting at 162.5'. C:NPh' CH,-CH,*C-- Ethyl l-metl~ylcyclohexune-3-one-4-carboxylate7 CH DI"<CH,- CH2'C co *,>CH-CO,Et prepared by heating the ester j;st described under reduced pressure a t 150-220° is a colourless oil boiling a t 123.5" under 13 mm.and at 165" under 100 mm. pressure and has a sp. gr. 1-05" a t 14'; the copper salt is an olive-green powder melting at 155'. With phenyl- hydrazine the ester gives a compound derived from hexahydro-1 2-benzodiazine which forms crystals melting at 243-245". With ammonia the ester yields ethyl 3-amino-1-methyl- c yclohexane- 4 -curbox ylate C H M e < ~ ~ ~ ~ ' ; ; ' ~ I > C . C O ~ E t which forms crystals melting at 67". ~ H M e . C H * ~ - ~ H CH,-CH,* C CO NPh' Ethyl 1 - dimetlqlc yclohexccne - 3-one- 1 -cccrboqlat e CHMe<CH:-C CH *CH B>CMe C0,Et prepared from ethyl methylcyclohexanonecarboxylate by treatment with sodium ethoxide and methyl iodide is an oil boiling at 120-122' under 12 mm. pressure and has a sp. gr. 1.0189 a t 19'. Zthyl l-methyl-4-isopropylcyclohexune-3-one-4-c~rboxyZate preparedORGANIC CHEMISTRY.89 in analogous manner is an oil boiling at 135-137' under 10 mm. pressure and has a sp. gr. 1.009 a t 14'. The semicarbazone melts at 144-145'. When this ester is hydrolysed by boiling alcoholic potassium hydroxide menthone is obtained melting a t 206-208' and feebly dextrorotatory ; it yields a semicarbazone melting a t 184-1 85". K. J. P. 0. Tautomerism. 111. Apparent Case of Desmotropy. PAUL RABE and DAVJD SPENCE (Awm?en 1905 342 328-355. Compare Abstr. 1901 i 33 and 1904 i 749).-The relation between the "acid " and '' neutral " forms of Hagemann's ester (Absti-. 1893 i 393) which the authors (Xbstr. 1905 i 34s) have shown to be ethyl l-methyl- cycZo-AG-hexene-5-one-2-carboxylate has been investigated.The con- ditions under which the isomerides are prepared do not point to their being tnutomeric and the tautomerism i f it exists cannot be due t o the carbonyl group but rather to the carbethoxyl group. To throw light on these phenomena ethyl phonylniethylcycZohexmonecarboxylate ine t h ylcgclo hexenonecarbox y lat e and dime t h ylcyclohexenonecnrboxylate have been prepared. I c has been found that two desmotropic isomerides do not exist but that the esters can be separated into two fractious which show a gradual difference in chemical and physical properties. The cause of these observations will be discussed later. Ethyl l-methylc~clo-A6-hexene-5-one-2-carboxylate (Zoc. cit.) boils at 157-159" under 19-21 mm. pressure and has a sp. gr. 1-0775-1*0783 a t 20'/4' and a molecnlar refraction hl 48.96-49.02.When shaken with 10 per cent. sodium hydroxide a t a low temperature two fractions are obtained ; the soluble fraction the " acid " ester boils a t 160-163' under 24 mm. pressure and has a sp. gr. 1.0701 at 2Oo/4O and Ms; 49.32 ; an insoluble fraction the " neutral " ester boils at 163' under 24 mm. pressure and has a sp. gr. 1.0856 at 20"/4' and M 4827. Both fractions are soluble in concentrated sodium hydroxide and both give a reaction with ferric chloride. Knoevenaget's ethyl 1 3-dimethylcycZo-A6-hexene-5-one-2-carboxylate behaves iu a similar manner ; the ethyl 4-hydroxy-2 6-dimethylbenzoate obtained from it by Noyes is readily hpdrolysed by alcoholic potassium hydroxide yielding 4-hydroxy-2 6-dirnet?~ylbenxoic cccid which crystal- lises in six-sided prates melting and decomposing a t 185'.Etlyl 1 -naethyZ-3 -phenylc yclo- A6-?~exene-5 -0 ri e- %car.boxylate CO,E t C H<CMe:c CPh*CH Hz>CO prepared by heating ethyl methylphenylcpclohexanolonedicarboxylate with sodium ethoxide in alcoholic solution crystallises in four-sided plates melting a t 55'; it dissolves but sparingly in 10 per cent. sodium hydroxide and only gives a colour with ferric chloride after prolonged boiling. The senaicarbccxone crys tallises in needles melting at 158-161'. K. J. P. 0. Preparation of Chloro-derivatives of Indigotin. BADISCIIE ANILIN- & SODA-FABRIK (D.R.-P. 160817).-When indigotin is chlorinated in absence of water in the dry state or in indifferent solvents the chlorine does not enter the nuclens aqd only unstable VOL.XC. i. h90 ABSTRACTS OF CHEMICAL PAPERS. products are obtained. Stable chloro-derivatives of indigotin are obtained however when indigotin is suspended in phosphorus oxy- chloride or sulphuryl chloride a little iodine being preferably added and chlorine passed through the well-cooled liquid. The product may be poured on to ice or the volatile compound removed by distillation. C. H. D. 6 6’-Dinitroindigotin. JULIUS SCHWARZ (Monatsh. 1905 26 1253-1263. Compare Baeyer Abstr. 1870 937).-5-Nit~ophenyl- ylycine-2-carboxylic acid C,,Hs06N2 is obtained in a yield of 7 0 per cent. of the theoretical by boiling five parts of 4-nitro-2-aminobenzoic acid with 10.5 parts of chloroacetic acid and 13.5 parts of sodium carbonate in aqueous solution in a reflux apparatus for eight hours.It crystallises in long slender yellow needles commences to blacken at 225O melts and decomposes a t 240-242” is readily soluble in alcohol but only moderately so in acetone light petroleum or hot water yields a reddish-brown flocculent precipitate and when heated in a tube sublimes and decomposes par tially. The potassium hydrogen salt C,H706N2K crystallises in microscopic red needles ; the silvw salt C,H,O,N,Ag is obtained as an orange voluminous precipitate. 5-Nits.oanildincetic-2-carboxyZic acid C10H1008N2 is obtained as a by-product in the preparation of 5-nitrophenylglycine-2-carboxylic acid ; it crystsllises from concentrated hydrochloric acid in long slender almost white needles melts and decomposes a t 17’74 and forms a wotassium salt as a vellow DreciDitate.1 .I A 1 3-Diacetyl-6-nitroincloxyl formed by heating 5-nitrophenylglycine-2-carboxylic acid with sodium acetate and acetic anhydride ; it crystsllises from alcohol in large yellow needles melts at 190” is almost insoluble in water but moderately soluble in alcohol ether acetone benzene or light petroleum dissolves in warm aqueous sodium carbonate to form a dark green in concen- trated sulphuric acid to form a dark blue solution and when warmed with concentrated sulphuric acid yields 6 6’-dinitroindiyotin C16H,0,N,. This is obtained in microscopic round dark blue granules is insoluble in water almost insoluble in hydrochloric or acetic acids alcohol ether benzene or light petroleum is slightly soluble in acetone and dissolves in hot aniline t o form a dark green in phenol naphthalene or hot nitrobenzene to form dark blue solutions; when heated in a glass tube it sublimes whilst on platinum foil it evolves violet vapours and detonates slightly. On reduction with zinc and hydro- chloric acid it yields 6 6’-dinitroindigo-white and on further reduction 6 6’-diaminoindigo-white which is oxidised by the atmospheric oxygen to 6 6’-diaminoindigotin.This is distinguished from 6 6’-dinitro- indigotin by its solubility in acetic acid forming a green solution. G. Y. Condensation of Epichlorohydrin with Phthalic Anhydride in Presence of Tertiary Bases. ARTHUR WEINSCHENK (Chem. Zeit. 1905 29 131 l).-When molecular proportions of epichlorohydrin and phthalic anhydride are warmed together over the water-bath in theORGANIC CHEMISTRY.91 presence of a small quantity of dimebhylaniline or dimethyltoluidine the following condensation takes place The resulting <hloromethylglycol phthalate is a iolid below 20° but between 20' and 30' it a=sumes a fatty consistency; it is insoluble i n water dissolves with difficulty in alcohol or ether and is readily soluble in epichlorohydrin. When pyridine is used as the condensing agent the reaction becomes violent and the mixture rapidly darkens. P. H. Butadiene Compounds. XII. Yellow Nitrotriphenylfulgenic Acids and their Red Fulgides. HANS STOBBE and ALBERT KULLENBERG (Ber. 1905 38 4081-4087).-Sodium a-o-nitrophenyt- 66-di;ohe.la~~uZgenate C2tH,,06NNs2 formed by the action of sodiuni ethoxide on o-nitrobenzaldehyde and ethyl yy-diphenylitaconate in absolute alcoholic solution crystallises in glistening leaflets from water or in yellow monoclinic prisms from 50 per cent.alcohol. The acid CPh,:C(CO,H)*C(CO,H):CH.C,H,.NO,,C,H,O crpstallises from alcohol in yellow needles loses C,H,;O at 105' commences to become red a t 180' and melts and evolves gas at 223-224'. The piperidine salt C,,H,70GN,2C,HI,N crystallises in yellow needles and melts and decomposes a t 201-202'. a-o-ilr;tro~?~e~zyZ-66-~ip~en?/lfulgie CPh,:y*Co>() formed N0,-C6H,* CHI C*CO by boiling the acid with acetyl chloride for four hours is obtained on slow evaporation of the solution in large pleochroic nionoclinic crystals; it crystallises from a mixture of chloroform and alcohol in blood-red leaflets from chloroform alone in yellow needles containing chloroform which is lost gradually on exposure t o air the crystals cbanging into an orange-red powder; the three modifications melt a t 207-208'.Its behaviour towards water alkali hydroxides and piperidine is the same as that of dibenzylidenesuccinic anhydride (Stobbe Naofim and Kautzsch Abstr. 1904 i 589); when oxidisetl it yields benzophenone and o-nitrobenzoic acid. a-m-Nitrophesa?/Z-66-~~p~~en~~uZge?zic acid is obtained in the form of its sodium salt C,,H,,O,NNa by digesting m-nitrobenznldehyde and ethyl yy-diphenylitaconate with sodium ethoxide in absolute alcoholic solution ; this crystallises in yellow leaflets. The acid C,,HliO,N crystallises in white leaflets or prisms from ether in yellow leaflet4 from acetic acid and melts aud decomposes a t 221-222'.The piperidine salt C,,H,70,N,2C,H,,N forms yellow needles and melts and decomposes at 177-1 78'. a-m-Nitropl~enyZ-66-dip~~en~f~ut~ide C2,Hl,05N crystallises from a mixture of chloroform and alcohol in orange-red slender needles or from benzene in stellate groups of pleochroic monoclinic prisms and melts a t 194-195'. a-p-Nitrophenyl-88-diphenylficlgenic m i d C,,H170,N from p-nitro- benzaldehyde and ethyl yy-diphenylitaconate crystallises in yellow prisms melts and decomposes at 238' and when oxidised yields benzophenone p-nitrobenzaldehyde and p-nitrobenzoic acid. The h 292 ABSTRACTS OF CHEMICAL PAPERS. sodium salt crystallises in yellow prisms; the pipwridine salt forms nodular aggregates of slender yellow needles and melts and de- composes at 181 -1 82'.a-p-Nitrophenyl-88-diphenylfulgide C,,H,,O,N crystallises in orange pleochroic monoclinic plates melting at 228O or from a mixture of benzene and chloroform in similar crystals melting at 224'. Butadiene Compounds. XIIL Aminotriphenylfulgenic Acid. HANS STOBBE and ALBERT KULLENBERG (Ber. 1905 38 4087-4090).-The a-aminophenyl-68-diphenylfulgenic acids are formed by reducing the corresponding a-nitrophenyl acids with ferrous sulphate in ammoniacal solution and precipitating the product with the calculated quantity of N-hydrochloric acid. a .o- Aminoiuhenyl-66-di~hen ylficlgenic acid G. Y. CPh, C( C0,H) C( C0,H) CH*C,H;NH2 is obtained as a yellow amorphous mass which melts and decomposes at 175-177' and is readily soluble in hydrochloric acid.The piperidine salt C,,H,,O,N 20 H ,N crystallisee in yellow needles melts and decomposes a t 192-193O and on treatment with aqueous silver nitrate forms the siZver salt C2,Hl7O4.NAg2 as a white flocculent precipitate which becomes yellow on drying. a-m- Arninophenyl-6s-dzpheizylfuIgenic acid C24H1904N crystallises in yellow monoclinic prisms melts and decomposes a t 2 2 4 O and when boiled with acetyl chloride forms a-m-acetylami?zophe?zyl-6S-diphenyZ- fulyide >0 which crystallises in slender yellow needles and melts at 215'. forms long dirty-yellow needles and melts and decomposes at a-p- Amino~l~enyZ-68-dipphenylfuIgenic acid is amorphous ; the piperidine salt forms large dark yellow crystals and melts and decomposes a t 182-183'; the copper salt C,,H1704NCu is obtained as a light brown amorphous precipitate.G. Y. Resin Acids from Conifers. V. ALBERT VESTERBERG (Ber. 1905 38 4125-4132. Compare Abstr. 1886 365 1038; 1888 294; 1904 i 151 ; Ducommun Chem. Zeit. 1885 1592).-Although d- and I-pimaric acids yield sparingly soluble crystalline ammonium salts a mixture of either acid with a large quantity of sbietic acid produces a gelatinous salt. When the two acids are in the proportions 1 10 the salt remains gelatinous for weeks but in the proportions 1 5 crystals are often observed in the course of a few days. The separation of the pimaric acid is best accomplished by the following processes (a) fractional cry stallisation of the acids from 85 per cent (vol.) alcohol until an acid is obtained which gives a crystalline ammonium salt ; ( b ) repeated cry stallisation of the sodium salt from water containing a small amount of sodium hydroxide; (c) crystallisation of the acid from alcohol or acetic acid.d-Pimaric acid has been isolated by this method from French colophony and from the resin of Pinus sylvestris. CPh, ?*CO NHAc*C,H,*CH C*CO The piperidine salt C2,H,,04N>2C HIIN 177-1 78'. J. J. S.ORGANIC CHEMISTRY. 93 Positions of the NO and NH Groups in the Mononitro- and Amino-derivatives of Piperonylaldehyde and Piperonylic Acid. EFISIO MARIEL1 ( A t t i 13. Accnd. Lincei 1905 [v] 14 ii 424-432 5 10-518).-The positions of the snbstituent uitrogen chains in the nitro- and amino-derivatives of piperonaldehyde and of the corre- sponding acid have not yet been absolutely proved (compare Abstr.1904 i 668 743 and 1023 ; 1905 i 203 889). The following are the results of the author's investigations on this subject. The oxidation of nitropiperonaldehyde yields the nitropiperonylic acid melting at 172" and already obtained by Jobst and Hesse by the nitration of piperonylic acid (Abstr. 1378 733; 1880 323). This nitro-acid or its calcium salt when decomposed by heat yields nitro- catechol methylene ether which can also be obtained by distilling an alkaline solution of nitropiperonaldehyde in a current of steam '1 he nitro-groups in nitropiperonaldehyde and in nitroca techolmethylene ether must have the same position relatively t o the other substituents as that in nitropiperorivlic acid.Reduction of the last-named com- L L 4 pound gives rise to the y-aminocatechol methylene ether (6-amino- 3 4-methylenecatechol) CH2< o*C*CH:?*NH2 I I already prepared by O-C-CH C H Rupe and von Majewski (Abstr. 1901 i 103) by van Linge (Abstr. 1897 i 618) and by Hesse (Zoc. cit.). The nitro-group in nitro- piperonylic acid must therefore occupy the 6-position with reference t o the carboxyl group the -O*CH,*O- group being in the 3 4-position. Confirmation of this conclusion has been obtained by preparing from nitropiperonylaldehydo and from nitropiperonylic acid the 4-nitro- 1 2-dihydroxy benzene described by various authors. The results given indicate that when piperonaldehyde or piperonylic acid is nitrated directly the first nitro-group introduced enters in the 6-position with respect to the aldehyde or carboxyl group in position 1 and the dioxymethylene complex in the position 3 4 and that further nitration gives rise to symmetrical tetra-substituted derivatives.The above constitution for nitropiperonaldehyde has been confirmed in an indirect manner by the recent work of Herz (Abstr. 1905 i 778). T. K. P. Tetramet*hylphloroglucinolaldehyde. JOSEF HERZIG and FRANZ WENZEL (Honatsh. 1905 26 1359-1389. Compare Abstr. 1904 i 25 1)-[ With PETER Ro~~.]-Dimethylphloroglucino~aldehyde is heated with methyl iodide and potassium hydroxide in methyl-alcoholic solution in a reflux apparatus during one day and after addition of further quantities of potassium hydroxide and methyl iodide again for one day.After distillation of the alcohol the residue is treated with water and ether when there are obtained an aqueous solution of the potassium derivative of tetramethylphloroglucinolaldehyde (1) and an ethereal solution of a condensation product (2). - ~Me,**CO*G*CHO obtained (1) Tetrametl~~~lilorogZ~inoZaZdel~ycSe CO CAIe; C* OH ' on acidification of the alkaline solution crystallisei from ether in large prisms or from methyl alcohol in colourless rectangular plates melts94 ABSTRACTS OF CHEMICAL PAPERS. at 70-71° is readily soluble in benzene but less soluble in methyl or ethyl alcohol and dissolves in aqueous potassium hydroxide to form a colourless solution which remains unchanged on prolonged warming ; it may be titrated with N/lO potassium hydroxide using phenol- phthalein as indicator. The potassium derivative OK*C,O,IsIIe,*COH forms colourless crystals and is not decomposed by carbon dioxide in aqueous solution.The oxime OH*C,O,Me,*CH:NOH crystailises from ethyl acetate in white needles commences to decompose at 189" and melts at 196' to a dark yellow mass. When heated with acetic anhydride and sodium acetate a t 160-lSO0 or when boiled with acetic anhydride only tetrarn et h ylphloroglucinolaldeh yde forms the coumarin CH:(?H which crystallises from methyl alcohol o-co ' derivative C,O,Me,< and melts a t 205-20S0. The methylether OMe*C60,Me;CH0 is formed by the action of diazomethane on tetramethylphloroglucinolaldehyde in ethereal solution ; it crystallises from alcohol and melts a t looo. When oxidised with potassium permanganate in alkaline solution the aldehyde yields a substance which crystallises in glistening scales melts and evolves gas at looo and when heated with alcohol or benzene forms carbon dioxide and the coildonsation product melting a t 2 10-2 1 2 O . [With WILHELM RExsMANN.]- ( 2 ) The condensation product (6-hydroxy-2 2' 4 4' 6'-pentoketo-3 3 3' 3':5 :5 :5':5'-octamztl'~yEtetrcc- Ii,ydrophenyZphenyzyEidenemethane) CO<CMe2*C(oH)~C.~~~C<co'cMe2~ CMe,-CO CO-CMe,' Co' is obtained on evaporation of the ethereal solution and treatment of the residue with benzene ; it is formed also together with formic acid when tetramethy lphloroglucinolaldehyde is dissolved in dilute methyl alcohol or is boiled with water or when its potassium derivative is treated with methyl sulphate.After repeated recrystallisation from a mixture of chloroform and light petroleum it forms nodular aggre- pates of white needles and melts a t 217'; it does not yield an acetyl derivative when boiled with sodium acetate and acetic anhydride. The rnethyE ether C,,H,,O,*OMe formed by the action of diazomethane on the condensation product in ethereal solution separates from alcohol in colourless crystals melts a t 163-164" and when treated with hydroxylamine hydrochloride in presence of sodium hydrogen carbonate or sodium methoxide yields a product which contains nitrogen and melts at 182'. The condensation product dissolves in aqueous potassium hydroxide to form a yellow solution which becomes colourless slowly at the laboratory temperature quickly on evaporation with formation of the potassium derivative of tetrarnethylphloroglucinolaldehyde and tetra- methylphloroglucinol melting a t 198' (m.p. 187-lSSo ; Reisch Abstr. 1899 i 803). The condemation product is again formed when the products of its hydrolysis are boiled with water containing a few drops of hydrochloric acid. The action of methyl-alcoholic potash on the methyl ether of the condensation product leads to the hydrolysis of the methoxy-group,ORGANIC CHEMISTRP. 95 and therefore t o the formation of the same decomposition products as are obtained from the hydroxy-compound. When treated with con- centrated sulphuric acid the methyl ether yields the condensation product. When reduced with zinc dust and aqueous potassium hydroxide the condensation product forms a dil~ydi.o-derivative C21H2sOz which crystallises from benzene in slender needles and melts a t 173 .It is formed also from tetrarnethplphloroglucinol by the action of (a) form- aldehyde and concentrated sulphuric acid a t 40' ; (6) of formaldehyde and potassium hydroxide in warm methyl-alcoholic solution ; or ( c ) of boiling aqueous formaldehyde. The methyl ethel. C,,H,,O,( OXe) formed by the action of diazomethane on the reduction product in ethereal solution crystallises from methyl alcohol in stout needles melts a t &lo and when boiled with hydriodic acid forms an anhydride C21.H2G05 which is formed also by the action of concen- trated sulphuric acid on the reduction product on the water-bath or by boiling this with acetic anhydride and sodium acetate ; it crystallises in needles and melts at 190'.On prolonged action of potassium hydroxide and methyl iodide on dimethylphloroglucinolaldehyde there is formed in addition to tetra- methylphloroglucinolaldehyde and its condensation product a sub- stance C,,H,,O which crystallises in glistening needles and melts at 1'73'. G. Y. Hydroxylamine Derivatives of Ketones of the Type CO(UH:CHR),. GAETANO MINUNNI and RICCARDO CIUSA ( A t t i 12. Accud. Lincei 1905 [v] 14 ii 420-424. Compare Abstr. 1905 i 245).--Attempts to determine the constitution of the base C17H,,N obtained by reducing a-dibenzylideneacetonehydroxylamineoxime (loc. cit.) by preparing its oxidation products have been unsuccessful. The compound C17H,,N,(OH) prepared by reducing disalicylideneacetone- hydroxylamineoxime gives mainly resinous products on oxidation only a small quantity of a crystalline product being obtained by treatment with potassium permanganate and sulphuric acid.~romo-a-cli~r~zz~licle~aencetonehydroxylamineoxime C,7H,,0,N,Br separates from alcohol in white crystals melting and decomposing a t 1 7 2 O and dissolves in methyl alcohol or chloroform and to a slight extent in ethyl acetate. Oxidation of a-dibenzy lideneacetonehydroxylamineoxime by means of amyl nitrite or acid potassium permanganate solution yields a small quantity of a substance C17H140N2 separating from aqueous alcohol in yellow crystals which soften at 165" melt and decompose at 176" and are soluble in almost all the organic solvents.Reduction of P-dibenzylideneacetonehydroxylamineoxime by means of sodium in amyl alcohol solution gives a n oily base the hydrochloride of which melts at 234' and the platinichloricle at 268'; the benzoyl derivative C,7H17N2.Bz of the base crystallises from a mixture of ethyl acetate and alcohol in white needles which blacken at 260° melt at 290° and dissolve readily in methyl or ethyl alcohol and to a less ex tent in carbon tetrachloride. Disa Zic?/lideneacetone?~~drox~la.nzineoxime Ci,H,GO,N,( OH)2 crystal-96 ABSTRACTS OF CHEMICAL PAPERS. lises from alcohol in hard prisms melting and decomposing at 207O and is slightly soluble in ether benzene ethyl acetate or methyl alcohol ; it dissolves in potassium hydroxide solution or in hydrochloric acid and also in sulphuric acid to which it imparts a blood-red coloration.Its tetrchenxoyl derivative C,7H1,0,N2B~4 crystallises from alcohol in hard minute prisms melting a t 1 3 5 O and dissolres readily in methyl alcohol and to a slight extent in ether benzene or ethyl acetate. On reduction with sodium and amyl alcohol it gives a compound C,7H,,N,(OH) which crystallises from alcohol in white leaflets melting and decomposing at 191' and is soluble in ether or benzene with difficulty in ethyl acetate with greater readiness and in acetic hydrochloric or sulphuric acid or potassium hydroxide solution very readily. T. H. P. Reaation between Organic Magnesium Compounds and Unsaturated Compounds. VII. Complex Products from Cinnamic Esters. ELMER P. KOHLER and GERTRUDE HERITAGE (Amer Chenz.J. 1905 34 568-580).-Phenyl a-phenylcinnarnate crystallises in needles melts at 142O is sparingly soluble in alcohol or ether moderately so in acetone or benzene and readily in chloroform. When a solution of the ester in benzene is boiled with excess of magnesium phen yl bromide trip"lenyZpropiop?~enone CHPh,*CHPh*COPh is produced which crystallises in small colourless needles melts at 1 8 2 O is readily soluble in chloroform moderately so in benzene or hot acetone and very slightly in alcohol or ether; it yields neither a hydrazone nor an oxime. When phenyl cinnamate (1 mol.) is added to a well-cooled ethereal solution of magnesium phenyl bromide (3 mols.) and the product is decomposed with cold hydrochloric acid dipbenylpropionic acid and diphenylpropiophenone are produced together with a small quantity of diphenyl.If the solution of the bromide (1 mol.) is slowly added to a cold solution of the ester (1 mol.) a substance CHPh,*CH( C0,Ph) CO*CH,* CHPh is produced which crystallises in long needles melts at 180-189° is readily soluble in chloroform or benzene moderately in ethyl acetate or hot acetone and very slightly in alcohol or ether; it is easily hydrolysed by potassium hydroxide with formation of potassium phenoxide potassium carbons t e and aate-tetraphen ylpentane- y- one CO(CH,*CHPh,) which crystallises in colourless nt edles melts a t 130° is readily soluble in ethyl acetate or chloroform and moderately so in alcohol or acetone does not combine with bromine and is not attacked by potassium permanganate.Tetraphenylpentanone oxime crystallises in needles melts a t 115-116O and when treated with phosphorus pentachloride is converted into the isomeric acid anilide which forms small lustrous prisms melts at 1 5 5 O and if heated in a sealed tube with strong hydrochloric acid yields PP-diphenyl- propionic acid and PP-diphenylethylamine. I n an earlier paper (Abstr. 1905 i 208) the effect of adding methyl cinnarnate to an excess of magnesium phenyl bromide was described.ORGANIC CHEMISTRY. 97 If on the other hand the magnesium compound is added slowly to a well-cooled solution of methyl cinnamate a nxelkp? ester CHPh,*CH( CO,Me).C'O.CH,* CH Ph corresponding with the plienyl ester obtained from phenyl cinnamute under the sitme conditions is producetl which crystallises in slender needles melts at 2 11-213° is readily soluble in chloroform or benzene moderately in acetone and very slightly so in alcohol or ether; when heated at 200' with concentrated hydrochloric acid i t is decomposed with formation OF 2 rnols.of @/I-cliphenylpropionic acid. P-Ber,xoyl- aa~~-tetrapl~enyZpntane-y-one CHPh,*CHBz.CO*CH,gCHPh which is obtained as a by-product in the preparation of the methyl ester just described and can be prepared by dropping methyl ciunamate into a boiling solution of magnesium phenyl bromide crystallises in nepdles melts at 166O is readily soluble in chloroform or acetone moderately in alcohol and sparingly so in ether. This ketone is hydrolysed by boiling alcoholic potassium hydroxide with formation of tetraphenyl- pentanone and potassium benzoate whilst aqueous potassium hydroxide converts it in to dipheuylpropiophenone and potassium diphenyl- propionate.If ethereal solutions OF methyl cinnamste and maguesium phengl bromide are boiled together for three or four hours arid the product is treated with ice-water a crystalline substcmce CHPh,. CH( CPh,* OH).CO*CH,* CHPh is obtained which melts at 153' is readily soluble in acetone or chloro- form and moderately so in alcohol and when heated alone at 270-30b0 or with concentrated hydrochloric acid at ZOOo is converted into benzophenone and tetraphenylpentanone. E. G. Soluble Preparations of o-Nitrophenyl-P-lactomethylketone. -0-Nitrophenyl-P-lactomethylketone is useful for the production of indigo-blue on the fibre but is very sparingly soluble.It dissolves however in aqueous solutions of the alkali salts of benzylaniline- sulphonic acid CH,Ph*NH.C,H,*SO,H 2 mols. of the ketone requiring at least 1 mol. of the acid for soiution. Salts of benzgl- toluidinesulphonic acids or of chlorobenzylanilinesulphonic acids and hornologues of the ketone show a similar behaviour. Derivatives of Tetrachloro-o-benzoquinone. C. LORING JACKSON and R. D. MAC LAURIN (Ber. 1905 38 4103-4105).- FARBWERKE VORM. MEISTER LUCIUS & BRCNING (D.R.-P. 160783). C. H. D. ~~eleac?~loro-o-quinoccctec~~oZ ether C,,02Cl,<o>C,C14 0 prepared by the action of tetrachlorocatechol on tetrwhloro-o- benzoquinone dissolved i n dilute acetic acid separates from benzene in deep red crystals melts a t 300° and is more soluble than the bromo-compound (Jackson and Koch Abstr.1901 i 597). It is reduced by sodium amalgam t o ILeEacl~Zorodih?/Jroxycatec~~~Z ether C,Cl,(OH),<o>C~C14 0 which crystal- lises from alcohol in colourlesa needles and melts at 290'. When condensed with aniline tetrachloro-o-benzoquinone yields a double compound ccizi~~?ze-dic~~~oro~~c6nili?Lo-o-ben~~qu~noiae C,,02CI,(NHPh),,NH,Ph,98 ABSTRACTS OF CHEMICAL PAPERS. which crystallises from benzene in long thin brown needles and melts and decomposes at 164-165'. crystallises from alcohol In glistening yellow plates and melts at 1 40-1 41'. Bichlorodiccni1ino.o- benzoquinone C,O,Cl,(NHPh) pre- pared by crystallising the aniline compound from a mixture of benzene and light petroleum separates in reddish-purple pointed needles and melts a t 194-1 95'.Chlorodiunilino-p-quinoneanil O:C,HCi(NHPh),:NPh prepared by t h e action of alcohol and aniline on the preceding compound crystallises from benzene and alcohol in broad black glistening needles and melts at 180'. 1 2-Anthraquinone. KASIMIR LAGODZINSKI (Annalen 1905 342 59-89. Compare Abstr. 1904 i 158).-1-Nitroso-2-anthroZ7 which the author regards as being in the tautomeric form O:C,,H8:N*OE can be prepared from 2-anthrol in alcoholic solution by treatment successively with an aqueous solution of zinc chloride and sodium nitrite ; the mixture is slowly heated and the zinc salt of the nitroso- anthrol separates ; it crystallises in orange needles decomposing a t 188' and gives an indigo-blue coloration with concentrated sulphuric acid.The potassium derivative C,,H,O,NK forms green arjd the sodium derivative yellowish-green leaflets. O:C,,H,:N*OEt prepared from the silver salt and ethyl iodide crystallises in golden- yellow leaflets melting at 143'. The methyl ether crystallises in similar forms melting R t 129-1 30'. l-Amino-2-a~zthroZ NH,*C,,H;OH is obtained by reducing either the nitrosomthrol with stannous chloride and hydrochloric acid or with hydrogen sulphide in alkaline solution or benzeneazo-2-anthrol with zinc dust and hydrochloric acid ; it crystallises in yellowish-green leaflets decomposing at 140-150' ; the hydrochloride and the sulphate form greenish-yellow needles; when heated with concentrated sulphuric acid a blood-red coloration is obtained. A trincetyi! derivative NAc,*C,,H,*OAc crystallises in greenish-grey leaflets melting at 165' and dissolves in alcohol solution with a blue fluorescence; on hydro- lysis with dilute alcoholic potassium hydroxide 1-c~etylamino-2- anthrol is obtained as green leaflets decomposing at 200-220°; its alcoholic solution has EL bluish-green fluorescence.1 2-Anthraquinone C,,H,O is formed when the salts of amiro- anthrol are oxidised in the cold with ferric chloride or chromic acid ; it crystallises in orange-yellow needles melting and decomposing at 185-1 go" and dissolves in sulphuric acid with a bluish-violet coloration. It condenses with o-phenylenediamine yielding 1 2- The alcohol compound c,0?c12( NHPh),,C'2H(307 T. M. L. The ethyl ether AT anthraphenmine C,,Hs<Ai >C,H which crystallises in dark yellow N leaflets melting a t 221-222O ; the hydrochloride is cherry-red and the sulphate bluish-green.When oxidised with chromic acid in acetic acid solution triacetylaminoan throl yields 1 -diacetyZamino-2-acetoxy- anthapinone C,H,<CO>C,H,( co OAc) =NAc which crystallises in paleORGANIC CHEMISTRY. 99 yellow needles melting at 1 8 9 O . On hydrolysis it is converted into 1 -amino-2-?~~drox~ar~thrccqzci~one crystdlising in dark red needles melting a t 250-251" and identical with Liebermann's a-alizarinamide. Alizarin is produced by heating the substance last mentioned under pressure with hydrochloric acid a t 250" ; the transformation is not produced by diazotisation. 1 3-Anthraqninol (Zoc. cit.) prepared from the quinone crystallises in greenish-yeilow leufiets melting and decomposing at 131" ; the alkaline solution is a t first cherry-red but soon blackens on oxidation.The diacetyll derivative forins yellow aggregates melting a t 145O and by oxidation with chromic acid is converted into diacstylalizarin. I<. J. P. 0. Chlorination of Mono- and Di-amino-derivatives of Anthra- quinone. BADISCEIE ANILIN- & SODA-FABRIK (D.R.-P. 158951. Compare Wohl this vol. i 9).-The mono- and di-amino-derivatives of anthraquinone are readily chlorinated by means of sulphuryl chloride. Thus P-aminoanthraquinone yields a monochloro-derivative 1 5 4 - aminoanthraquinone yields a tetrachloro-derivative crystallising from nitrobenzene in glistening brown needles and 2 6-diaminoanthra- quinone yields a dichloro-derivative. The solubilities of many such chloro-compounds in sulphuric acid and in organic solvents are described.C. H. D. HUGO VOSWINCKEL (Bey. 1905 38 401 5-4021).-Naphthacenediqiiinone (Gabriel and Leupold Abstr. 1598 i 4S2j dissolved in glacial acetic acid is attacked by chlorine at the ordinary temperature giving the dichloride Studies in the Naphthacene Series. co* yc1* co C,H4<C0 CCl~CO >C,H* which crystallises from nitrobenzene in rhombic crystals and melts at 175" ; with reducing agents i t gives dihydroxynaphthacenequinone (Gabriel and Leupold Zoc. cit.) and on warming with dilute aqueous sodium hydroxide the same substance is also formed but the principal product is an acid C,,H,,O perhaps co - C0,H'C,H4'c0*C~C(OH~. CO>Cf3H4* This crystallises from dilute alcohol containing hydrochloric acid in bright yellow transparent prisms melts a t lS5" and gives rz hydrazone and a red crystallirie silver salt C,,H,O,Ag,,H,O. With bromine in glacial acetic acid naphthacenediquinone gives which separates in well-formed colourless prisms and melts a t '1 98" ; a little dihydroxynaphthacenequinone is also formed.When the bromide is shaken with aqueous sodium hydroxide i t seems to yield the acid C,8Hlo06 described above but the melting point is slightly higher namely 19 go. ,CO*C,-CO,100 ABSTRACTS OF CHEMICAL PAPERS. by leaving powdered naphthacenediquinone with an aqueous suspension of bleaching powder for several days crystallises from benzene i u small orange-coloared needles melts and decomposes at about 240° and is easily reduced t o dihydroxynaphthacenequinone ; with aqueous sodiiim hydroxide the acid C1SH1006 is obtained melting at 199'.W. A. D. Preparation of Bornylenediamine. PAUL DUDEN (D.R.-P. 160 103).-Bornylenediamine (camphanediamine) is prepared by I educiDg amino- isoni troso- or isonitrwamphoroxime by means of sodium and alcohol sodium amalgam or electrolytic hydrogen. BornyEenediamine forms a waxy solid boils a t 246' and dissolves with. extreme readiness in water. The cliacetgl deiivative occurs in two stereoisomeric modifications melting at 246' and 253' respectively. C. H. D. Chemical Investigation of Resin from the Pine (Pinus obies). PETER KLASON and JOHN KOHLER (Arkiv Kern. Min. Geol. 1905 2 i No. 3 1-39).-Resin from the pine contains two isc- morphous acids a- and /3-colophonic acids C2pH309,.The acids have the normal molecular weight in freezing acetic acid and give the acid value 185.4. The separate acids have not been obtained absolutely pure so that the physical constants given below are only approximately correct. a-CoZopJ~oi2ic acid crystallises from alcohol in colourless oblique monoclinic prisms [ a b c = 1.1282 1 0,9716 ; p= 71*24'] melts at 177-182' and has [.ID - 59.41". P-Colophonic acid separates in less well-developed crys tals than the a-acid melts a t 1 68-1;33 and has [ a I + 52.2". The u~~~~~~onzizcna NH 2C20H3002 cuZciuna Ca( C,oH2902)2 and bariu912 Ba(Cl,oH,,0,),2H,0 salts of the mixed at-ids were prepartd. T. H. P. Gutta Percha and Balata. WILLIAM A.CASPARI (J. SOC. Chemz. Ind. 1905 24 1274-1278j.-Analyses of various guttns and balata purified by solution in benzene and precipitation with alcohol thrice repeated confirmed the formula (C5H& Pure gutta is of a leathery consistence and almost destitute of elasticity ; below loo" it becomes soft and can be kneaded whilst caoutchouc becomes sticky and moderately plastic bnt retains some resilience ; at higher tempera- tures the two hydrocarbons tend to approximate in behaviour. When dissolved in dry carbon tetrachloride and treated with chlorine the hydrocarbons of gutta caoutchouc or balatn yielded substances the composition of' which approximated to the formula C,,H3,C1 ; the substances when piirified by precipitation from dilute benzene or chloroform solution by means of alcohol and dried in a vacuum presented white toughish plates.Substances prepared similarly by the action of bromine gave analytical numbers leading to the formula C,,H,,Brlo ; iodine in chloroform solution yielded substances con- taining betneen 12.11 and 13.47 per cent. of iodine. Benzene solutions of gutta o r balata saturated with d i y hydrogen chloride andORGANIC CHEMISTRY. 101 precipitated with alcohol gave substances which when redissolved and again precipitated formed white leathery flakes easily soluble in benzene or in chloroform and had the composition C,oH,,,5HCl ; the behaviour of caoutchouc was found to be somewhat different. A solution of nitrogen peroxide and oxygen in benzene added to a benzene solution of the hydrocarbons produced green gelatinous precipitates of variable composition ; on adding more nitrogen peroxide yellow clots separated which had the composition C,,H,,O,N ; on subjecting these substances to the protracted action of nitrogen peroxide they produced substances which when pure were saffron- yellow powders which dissolved in acetone ethyl acetate alkalis and ammonia with a deep orange colour ; their composition is represented by the formula C,,H,,O,N,. By the action of nitric acid a substance of the formula C,,H2,0,,N was obtained. Benzene solutions of the hydrocarbons on treatment with dry nitric oxide gave substances the composition of which is represented by the formula C,,H,,O,N. The conclusion is drawn from these experiments that the hydrocarbons of gutta percha and of balata are identical whilst as regards gutta and caoutchoucs i t seems as if these were a common molecule differences in the aggregation of which caused differences in mechanical structure.P. H. Butadiene Compounds. XI. Parallel Coloured F u r y l - and Phenyl-fulgides. HANS STOBBE and RICHARD ECKERT (Ber. 1905 38 40'75-4031).-The furyl group has stronger chromophoric properties than has the phenyl group; a number of furyl and the corresponding phenyl compounds are quoted to show that where these have the same colour the former have the deeper shade. This is the case in the fulgide series the three fnryl-fulgides described below being light orange dichromate-red and reddish-brown whilst the corresponding phenyl compounds are light yellow orange-red and lemon-yellow respectively (Abstr.1905 i S57 ; this vol. i 22). a-~~i-yZ-66-di?netJ/~ulgenic (a,furfurylideneteraconic) acid CMe,:C(CO,H)~C(CO,H):CH*C,OH formed by the action of sodium ethoxide on ethyl dimethylitaconatc and furfuraldehyde in absolute alcoholic solution separates from 20 per cent. acetic acid in small slightly yellow rhombic crystals softens at 204' and melts and decomposes a t 218'. When treated with acetyl chloride cooled by a freezing mixture it yields afurpZ-66-di- methyZjidgide C12H1004 which crystallises from light petroleum in small light orange monochic prisms melts at 63' is readily soluble in ether chloroform benzene or carbon disulphide and dissolves in concentrated sulphuric acid to Eorm a yellow solution which becomes greenish-brown and finally reddish-brown changing to yellow on dilution with water.66- Diphenyl -a- furylfulgenic acid CPh, C( CO,H).C(CO,H) C Ha C,0H3 formed from f urf uraldehyde and ethyl diphenylitaconate in alcoholic sodium efhoxide solution crystallises from benzene in shimmering yellow leaflets containing C,H which is lost at 100") becomes dark at 187" and melts and decomposes at 202'. The sodium salt,102 ABSTIcACTS OF CHEMICAL PAPERS. C,,Hi40,Na,2H20,2C2H,0 crystallises from 70 per cent. alcohol in white plates. 88- Diphenyl-a-furylfulgide C22H1404 formed by pouring cold acetyl chloride on to the dicarboxylic acid crystallises from carbon disulphide in dark red prisms which lose CS on exposure to air ;. when free from carbon disulphide it is dichromate-red melts at 156O is easily soluble in chloroform or .benzene and dissolves in concentrated sulphuric acid to form a green solution which becomes brown and on dilution with water deposits a greenish-blue flocculent precipitate.&Dif urylfulgenic acid (dif urfurylidenesuccinic acid) C40H3*CH C(C0,H) *C( C0,H) :CH*C,OH is obtained by treating a mixture of 3 mols. of furfuraldehyde and 1 mol. of ethyl succinate in alcoholic solution with 2 mols. of sodium ethoxide in a yield of 15 per cent. of the theoretical; it melts at 227-228" (217-225' Fichter and Scheoermann Abstr. 1901 i 479 ; 185-187' Titherley and Spencer Trans. 1904 85 190). a8-Difurylf ulgide (dif urfurylidenesuccinic anhydride) forms brown- ish-red rhombic crystals softens at 197' and melts at 204O (187' Wherley and Spencer Zoc. cit.p. 188). Diphenyl-o-phenoxylenedihydroanthracene. FRITZ ULLMANN aud JACOB TSCHERNIAK (Bey. 1905 38 41 10-41 11).-2'-2Zyd~o- Jluorangldipphen ylcartino I O<~~>CH*C6H,*CPh,* OK prepared by the action of bromobenzene and magnesium on methyl hydro- fluoranate (Meyer Abstr. 1895 i 291) O<CFK4>C H*C,H,*CO,Me separates from benzene iu colourless crystals and melts at 196'. By the action of acetic and sulphuric acids it is converted into 10 10-dipphenyl- 1 ; 9-o-p?~enoxylenedihydronnt?waceney which sepa- rates in colourless crystals and melts a t 325'. T. MI. L Salts of the Alkaloid Cinchonamine. BERNARD F. HOWARD and F. PERRY (J. SOC. Chen?,. Ind. 1905 24 1281--1283).-The cinchonamine used in the investigation was obtained from a sample of the crude nitrate which had been precipitated from the alkaloid of the bark of 12emijicc.Puvdeiana. The crude salt was twice recrystallised from water and converted into the hydrochloride jn which form it wcx several times recrystallised ; on precipitating the base and recrystallising it from acetone it was obtained as a perfectly white crydtaliine product. Cinchonamine hydrochloride C,,H,,ON,,HCI crystallises from t h e acid solution in soft almost white glistening laminze. A hot saturated neutral solution of the hydrochloride cooled to 27' deposits cubical crystals of a monohydrated salt. A dihydrochloride could not be obtained. The hydrobromide was prepared in a manner exactly similar t o t h e hydrochloride and was found to be anhydrous ; it is very slightly soluble in cold water. The hydriodide prepared by double decomposition of a salt of cinchonamine with potassium iodide or by boiling the alkaloid with 5 per cent.hydriodic acid crystallises in shining slightly yellow plates; on exposure to dry air it loses hydro- G. Y. C K 6 4 (&H,*FH-y,H CPh,*C,H3 -0ORGANIC CHEMISTRY. 103 gen iodide; it is almost insoluble in cold water but is fairly soluble a t higher temperatures. The platinichloride forms a very insoluble semicrystalline yellow solid. The salicylate prepared by neutralising a warm solution of salicylic acid with cinchonamine forms a resinous mass which crystallises from dilute aqueous solutions in thick colour- less prisms which are very readily soluble in acetone. The sulphate was obtained by neutralising an alcoholic solution of the alkaloid with dilute sulphuric acid a t a temperature just below the boiling point of alcohol; on rendering the neutral solution just acid and cooling it was deposited in small needles ; it is extremely soluble in water and is practically insoluble in absolute alcohol ; it is very soluble in pyridine and crystallises from i t with one molecule of the solvent.The acid sulphate C,,H240N2,H2S04 is best prepared by dissolving the sulphate in a small quantity of water a t the temperature of the boiling water-bath and stirring in a molecular quantity of dilute sulphuric acid ; on slow evaporation in a vacuum the solution deposits large truncated octahedra. The picrate obtained as a yellow amorphous powder by adding a cold aqueous solution of picric acid to the hydrochloride melts at 54' and contains &H20.Solubilit<y curves are given for the haloid salts. P. H. Nicotine and its Specific Rotation. I. FLORIAN RATZ. (Monatsh. 1905 26 1241-1252).-The author has purified two samples of nicotine of different origins by fractional distillation under 20 mm. pressure and obtained two fractions having [.ID - 163.19" and - 166.77' at Z O O respectively. The specific rotation of these fractions was not altered by further fractional distillation but on con- version of each into the zincochloride fractional cry stallisation of this and liberation and fractional distillation of the base two specimens of pure nicotine were obtained. This boils at 246.2' under 719.8 mm. pressure and has the sp.gr. 1.00924-1*00925 at 2Oo/4O and La] - 169.22" to - 169.54" a t 20". Nicotine zincochZoTide C,,H,,N,,2HC'l,ZnC12,H20 is soluble in two parts of water or 4-4.5 parts of 60 per cent. alcohol or in 0.1 or 0.35 part of the boiling solvents respectively. A table is given showing the sp. gr. and the specific rotation of nicotine as found by a number of authors. The different figures obtained previously must be due to the presence in varying amounts of an impurity which is removed only partly by fractional distillation ; the nature of this the author proposes to investigate. G. Y. Scopolamine and Scopoline. ERNST ScHmDT (Arch. Plbarm. 1905,243,559-583. Compare Abstr. 1892,1255 ; 1895 i 158 ; 1898 i 499 ; 1903 i 5l).-Numerous attempts to obtain reactions which would correspond with the presence of ketonic oxygen in scopoline C8H1?02N gave no positive result.Further it was not found possible to reduce scopoline in either acid neutral or alkaline solution ; neither could a compound with hydrocyanic acid be obtained; nor was a benzylidene derivative formed when scopoline and benznldehyde were allowed to remain in acetic acid solution saturated with hydrogen104 ABSTRACTS OF CHEMICAL PAPERS. chloride as happens with substances which contain a CH,*CO group (Willstiitter Abstr. 1898 i 160). By methylating scopoline (Luboldt Abstr. 1898 i 499) a small quantity was obtained of a crystalline methylscopolim which melted a t 69-70"; it was analysed in the form of its awrichloride which melts at 154O. When scopoline is allowed to remain with hydrogen peroxide it yields a product which melts and deconiposes at 122' and forms ft crystalline hydrochloride C8H,,0,N,HC1 ; probably this product is an oxide the NMe group having been converted into NMeO. Scopoline is oxidised but very slowly by a boiling solution of chromic and sulphuric acids ; the products are scopoligenine C,H1102N pyridine methosulphate methylamine and carbon dioxide.[With RUDOLF Gaz~.]-Bromine either in chloroform solution or in the form of vapour converts scopoline partially into scopoligenine ; in the latter case a eniall quantity was also obtained of a substance melt- ing a t 1 10-1 13* .probably a bromo-derivative of scopoline. Scopoligenine yields unsaturated hydrocarbons and pyridine when it is heated with zinc dust in a current of hydrogen gas.When hydrobronioscopoline hydrobromide is boiled with phosphorus tribromide and the product reduced with zinc and dilute sulphuric acid hydroscopolidine is formed; this was analysed in the form of its aurichloride U,H,,N HAuCl which melts at 204-206'. The uuric?doride of hydroscopoline C,H,,U,N HAuCl which is obtained by reducing hydrobromoscopoline (Abstr. 1905 i 51) meIts at 200-201'. New varieties of the platinichloride and anrichloride of scopoline respectively anhydrous and with H,O are described; these melt practi- cally at the same temperature as the salts known already. cgH1s02N HAuC147 Hydriodoscopoline hydriodide melts at 196'. C. F. B. Modern Theories of Double Linkings and the Constitutional Formula of Pyrrole. GIACOMO CIAMICTAN (Guxxetta 1905 35 ii 384-39 S).-The author discusses the various formuh which have been proposed for pyrrole in which as he has already pointed out (Abstr.1893 i 602) two valencies of the nitrogen atom exist in a latent condition. On the basis of Thiele's theory of partial valencies he supposes that in thiophen pyrrole and furan the partial valencies of the group -CH:CH*CH:CH- are more or less satisfied by the latent valencies of the sulphur nitrogen and oxygen respectively the extent of t h i s neutralisation being greatest with sulphur and least with oxygen (see also Abstr. 1905 i SO). T. H. P. Compounds of Copper Salts with Pyridine and Quinoline. PAUL PFEIFFER and V. PIMMER (Zeit. anorg. Chern. 1905,48 98-1 11). -The following additive compounds of copper nitrate and pyridine have been prepared.Cu(N03),,2C,H,N a light blue powder ; Cu(N03),,3C,H,N azure- blue crystals ; CU(NO,)~,~C,H,N violet plates ; Cu(N03),,6C H,N small cobalt-blue crystals. The tetra- pyridine compound is readily formed from its components ; with excess of the base it forms the hexapyridine compound whereas it yields theORGANIC CHEMISTRY. 105 di- and tri-pyridine compounds when heated carefully. The compounds Cu(N0,),,2C5HSN,2H20 and Cu(N0,),,6C,H5N,3H,0 have also been prepared ; the former occurs in light blue plates whilst the latter has a violet-blue colour. Diquinoline cup& nitrate Cu( NO,),,2 C9H7F prepared directly froin its components crystallises in transparent indigo-blue needles. Dippidine cupric bromide CuBr2,2C,H,N prepared from its com- ponents occurs in green needles; with excess of the base it yields hexapyridine cupric bromide CuBr2,6C,H5N as a blue crystalline mass.Ppridinium cupric bromide Cu(C,H,N),Br4 prepared by dissolving the dipyridine additive compound in hydrobromic acid forms lustrous reddish-black prismatic crystals ; the corresponding quinolinium com- pound Cu(C,H,N),Er4,3H,0 prepared by a similar method crystallises in black plates. G. S. Aminoacetals and Aminoaldehydes. 11. ALFRED WOHL (Ber. 1905 38 4154-4157. Compare Abstr. 1901 i 513).-A summary of the results contained in the three following abstracts. Amino- aldehydes and their substitution derivatives are best purified in the form of their platinichlorides ; the free aldehydes very readily undergo condensation and in only a few cases have they been obtained pure by reducing to a minimum the decomposing action of heat alkali and water .c. s. ALFRED WOHL KURT SCHAFER and A. 'J'mEm (Ber. 1905 38 415$-4161).-yy-Amino- bntyraldehyde diethylacetal is conveniently obtained by the interaction of /3-chloropropaldehyde diethylacetal sodium ethoxide and dry hydrogen cyanide in alcoholic solution a t 118-1 22" for two days the product being subsequently reduced with sodium and absolute alcohol. y-A~2ino6ul?/raZde?,?/da NH,*CH,*CH,*CH;CHO obtained by the de- composition of the acetal by a dilute solution of oxalic acid forms a syrup which still contains oxnlic acid. is an unstable crystalline substanc'e. y -.Aminobutyraldehyde and Pyrrolidine. The platinichloride (C,H,ON),,H,Pq y-~o~mylccminobutyru?de7~~de diethylucetal CHO*NH*CH2*CH,*CH,*CH(OEt),~ prepared from ethyl formafe and the acetal base bolls at 170" under 14 mm.pressure and is soluble in water or the usual organic solvents. y- Form~laminobzcI?/rccldeT~yde CRO*KH*CH,*C H,-CH,*CHO is ob- tained in an impure state by the decomposition of the acetal with oxalic acid. The plutinicldoride (C5H,0,N)2,H2PtCl melts and de- composes a t 176". 3 3 obtained by the action of benzenesulphonic chloride on an aqueous- alcoholic solution of y-nminobutyraldehyde diethylacetal and treatment of the oil so protliicetl with a 5 per cent. alcoholic potash is a crystal- line substance which melts a t 76-78" and distils without decomposi- tion. It is insoluble in water but dissoIves in ordinary organic solvents ; i t is reduced to pyrrolidine by sodium and hot amyl alcohol.c. s. VOL. XC. i. i106; ABSTRACTS OF CHEMICAL PAPERS. Hydrogenated Pyridine-aldehydes. ALFRED WOHL FV . HERTZ- BERG and M. S. LOSANITSCH (Ber. 1905 38 4161-4169).-/3-Inrino- dipropaldehyde tebraethylacetal NH[CH,*CH,*CH(O Et)2j2 obtained by heating under preesure P-chloropropaldehyde diethylacetal ( 1 part) with a cold saturated solution of ammonia in alcohol (6 parts) a t 118-120' for not more than nine hours is a colourless viscous liquid inclining t o yellow ; it boils at 157' under 1.5 mm. pressure has a basic odour is somewhat soluble in water dissolves in the ordinary organic solvents and has a sp. gr. 0,9466 at 15'. Dilute oxalic hydrochloric or sulphuric acid hydrolyses it t o the extent of SS per cent.Cold con- centrated hydrochloric acid causes the formation of a syrup which was identified as A"-tetml~?/di.o~?lrid~ne-3-ddeiLyde in the form of the hydro- chloride of i t s nitrop~~en?lEhydraxorLe HC1 rH-UH,-fi.CH N,H- C,H,*N 0 CH,*CH;CH a hygroscopic reddish-yellow substance which sinters at 173.5' and melts with decomposition at 251'. 9 P-Et~~yliminodipropaldehyde tetrnethylucetal NEt[CH,*CH,*CH(OEt),1 obtained from ethylamine jind P-chloropropaldehyde diethylacetnl in benzene solution a t 135-140' is a colourless viscous oil which boils at 159' under 13 mm. pressure; it is sparingly soluble in water and is miscible with the ordinary organic Folvents. The platinicldoride (U H 3504N)2.H,PtCI separates from dilute alcohol in yellow octa- hedral crystals which melt and decompose at 92-93' (corr.).1- Etli~l-~~-tetrah~d~opyridine-3-ulclel~~lde h ydrocldode C,NH,Et BCHO HC1 is obtained from the acetitl by the action of cold concentrated hydro- chloric acid. I t separates from dilute alcohol in long colourless crystals which melt at 208' (corr.) shows reducing properties and gives n reddish-brown coloration with concentrated siilphuric acid and phenol or P-naphthol. The platiniclJoride forms yellow cubes which melt and decompose at 190". The hjdrocltloride of the nitrophenyl- hydrazone separates from dilute alcohol in reddish-yellow hygroscopic needles which melt and decompose at 263'. The hydrochloride of the oxime forms long colourless needles which melt at 248-249' (corr.).The free oxinze which is not produced by mixiog i t s components is obtained from the hydrochloride by the action of potassium carbonate ; it crystallises in white scales and melts at 134' (corr.). The acetate of the oxime obtained by the action of acetic anhydride and sodium acetate on the hydrochloride boils a t 102-105° under 0.1 mm. pressure. Thionyl chloride converts the hydrochloride of the oxime into the IqdroclJokIe of the nitrile C,N H,Et*CN,HCI which separates from dilute alcohol in white needles melting at 265-266" (cow.). prol)arecl I>y the action of 11;drogen clilo~ide on the liydrochloricle of 1 -ethyl-A3-teirahydi~opyriclline-3-aldehyde dissolved in absolute alcohol is a colourless oil which boils a t 79-'80' under 0.05 mm. pressure. I t sOIiG ANIC CHEMISTRY.107 reduction by .?odium and absolute alcohol produces 1 -etlb&ipe?*idi?ze- 3-ccldelqde diethykccetcd which is a colourless oil boiling at 63-65" under 0.04 mm. pressure. c. s. Free Aminoaldehydes. ALFRED WOHL and M. S. LOSANITSCH (Uer. 1905 38 4170-41 72).-l-~th~Z-~~-tetral~~/dropyridirte-3-alde- Ityde obtained from its hydrochloride (see preceding abstract) by the action of solid potassium carbonate is a colourless oily liquid with a basic stupefying odonr ; it boils at 52-44' under 0.06 mm. pressure has an alkaline reaction and reducing properties and is resinified by potassium hydroxide. l-Et?'?lZ~)~~~eridilae-3-aZde?~?lde is obtained in small quantity from the corresponding acetal (Zoc. cit.) by the action of strong hydrochloric acid with subsequent addition of potassium carbonate to the cold diluted solution. It is a colourless oil which boils at 40' under 0.2 mm.pressure ; i t has a burning taste fumes with hydrochloric acid and reduces Fehling's solution. I n contact with air it becomes resinous and insoluble in water. The PZatinicldoride crystallises in octahedra. p- Eth~l~cmi~~zo;u~opciZdehyde diethylacetal NHEt CH,* CH,*CH( OEt) is a by-product in the preparation of the tertiary base (Zoc. cit.). It is a colourless mobile oil with a basic odour and strongly alkaline reaction. It boils at 82*5-83*5' under 13 mm. pressure. When decomposed by strong hydrochloric acid it yields the hydrochloride of the aminoaldehyde C5H,,0N,HC1 which melts at 265-265-5' (corr.) and reduces solutions of silver salts. p- Ethylaminopropddel~yde (NHEt*CH,*CH,*CHO) is obtained from the hydrochloride by the action of potassium carbonate as a slightly yellow oil which reduces solutions of silver salts but not Fehling's solution answers to Schiff's test and forms with hydro- chloric acid a hydrochloride identical with that from which it is pre- pared.The free aldehyde is remarkably stable retaining its properties unchanged after being heated in a vacuum to 180". c. d. Reciprocal Stereochemical Influences. HANS MEYER (Monatsl'. 1905 26 1303-131O).-Two similar or dissimilar groups which influence each other so that they act as if only one group were present the author terms '' conjugated groups." Typical examples of sub- stances containing '' conjugated groups " are the 2- and 4-aminopyr- idines and the 2- and 4-aminoquinolines in which the two basic groups influence each other so that salts are formed with only 1 mol.of hydrochloric acid. On treatment with nitrous acid these bases behave as stable aliphatic amines. In 4-aminonicotinic acid the carboxyl group and in 4-aminolut- idinic acid one of the two carboxyl groups is partially neutralised by the 'i conjugated groups '' j these acids are therefore pseudo-betaines (Abstr. 1904 25 490). On the other hand in the 3-aminopyridines 7-aminoquinoline and 5- and 8-aminoisoquinoline the tertiary nitrogen and the amino-group have no stereochemical influence on each other and these bases form i B10s ABSTRACTS OF CHEMICAL PAPERS. salts with 2 mols. of hydrochloric acid and when diazotised behave as aromatic amines.Similarly whilst the 3-hydroxypyridines react normally the 2- and 4-hydroxypyridines (2- and 4-pyridones) and the 2- and 4-hydroxy- quinolines do not give the typical reactions. Thus the 2- and 4- pyridones do not yield nitroso-derivatives cannot be acetylated do not react normally wiih phenylcarbimide (Goldschmidt and Meissler Abstr. 1890 i 499) and have only feeble salt-forming properties. Claus has shown that on bromination of carbostyril the " conjugated group" exerts no directive influence (Abstr. 1896 i 449). G. Y. Action of Diazomethane on Pyridones and Hydroxy- pyridinecarboxylic Acids. HANS MEYER (Monatsh. 1905? 26 131 1-1329. Compare preceding abstract).-Whilst 2-pyridone is converted into 2-methoxypyridine only slowly and partially by the action of diazornethane this reagent interacts energetically with 3-hydroxypyridine which must be a true hy droxy-compound forming 3-methoxypyridine ; this yields a mercurichloride which crystallises in slender colourless needles and melts at 1 lo' and a platinichloricle which is obtained in yellowish-red crystals and melts at 182'.The action of diazomethane on 4-pyridone leads to the formation of a mixture of 4-methoxypyridine and 1-methyl-4-pyridone. 4-Methoxy- pyridine mercurichloride crystallises in colourless needles and melts at 191'. Carbostyril interacts with diazomethane to form 2-methoxy- quinoline and not the N-methyl derivative. The action of methyl iodide on 6-hydroxynicotinic acid in aqueous alkaline solut,ion leads to the formation of 6-keto-1-methyl-1 2-di- hydropyridine-3-carboxylic acid which melts at 238-239' (compare von Pechmann and Welsh Trans.1885 47 150; Abstr. 1885 174). This differs from all 1 -methylpyridinecarboxylic acids investigated previously as owing to the negative influence of the keto-group on the methylimico-group it does not form the betaine and can be titrated with h'/lO potassium hydroxide. When treated with diazomethane it yields the methyl ester which crystallises in long glistening needles and melts at 1313". The action of diazomethane on 6-hydroxynicotinic acid leads to the formation of a mixture of derivatives consisting of 88.5 per cent. of methyl 6-keto-1-methyl-1 2-dihydropyridine-3-carboxylate and 11.5 per cent. of methyl 6-metlzoxynicotinate OMe*C,NH,*CO,Me which crystallises in soft needles and melts at 122O whereas diazornethane and methyl 6-hydroxynicotinate interact to form methyl 6-keto-1- methyl- 1 2 -dihydropyr.idine-3-car boxylate only.Methyl 2-hydroxycinchonate is formed from the acid by the action of thionyl chloride or sulphuric acid and methyl alcohol or together with methyl 2-methoxycinchonate by the action of diazomethane. It crystallises in glistening colourless needles me1 ts at 242' sublimes at 240-250" and distils apparently without change Jfetlh) 2-methoxy- cinc?~oizate crystallises in needles melts at 120° and has an odour of orange blossoms. When boiled with 2 per cent. aqueous sodium hydroxide propionyliscctin which is formed by boiling isatin with propionic anhydride and melts a t 1 41° yields 2-hy droxy-S-methyl-ORGANIC CHEMISTRY.109 cinchonic acid OH*C,NH,Me*C02H ; this separates from water in colourless crystals melts a t 315-31 7" and when treated with thionyl chloride and methyl alcohol or with diazomethane yields methyl 2-~ydrox~-3-nzeth?/lcinc;cLolzccte which crystallises in long slender needles and melts a t 174-175'. Prolonged treatment with diazo- methane had no further action on the methyl ester. Chelidamic acid interacts energeticdly with diazomethane forming the dimethyl ester OH*G',NH,(CO,Me) which crystallises in long needles melts a t 125" and is only sparingly soluble in ether. The author discusses the constitution of comenamic acid (compare Lapworth and Collie Trans. lS97 71 843 ; Yeratoner Abstr. 1902 i 493) and concludes that it is 4 5-dihpdroxypyridine-2-calk,oxylic acid.It cloes not interact with thionyl chloride (compare Abstr. 1902 i 31) but when treated with diazomethane yields rnet?qZ ~-~~~ldroxy-~-met~~ox~p/pyr~dilze-~-carboxy~c6te melting a t 1 1 8 O . Formation from Furfuraldehyde of Colouring Matters derived from Pyridine. WILHELM KONZG (J. pr. Chew,. 1905 [ii] 72 555-562. Compare Abstr. 1904 i 449 S17; Zincke Heuser and Rloller Abstr. 1904 j 921 ; Zincke and Miihlhausen this vol. i 33).-'L'he hydrobromide of a-hydroxyglutaconaldehyde- dianilide NHPh*CH:CH*CH C( OH) CH (0 H)*NHPh,HBr is formed by heating aniline with furfuraldehyde in alcoholic solution on the water-bath and after cooling adding hydrobromic acid of sp. gr. 1.48 diluted with alcobol. It crystallises from acetic acid in prisms which have a deep blue lustre melts at 164-165O and dyes silk and tannin mordanted cotton-wool deep red or unmordan ted cotton-wool rose-red.When heated with nitrobenzene a t 150" it decomposes into aniline and 3-hy droxy-1-pheny lpyridinium bromide which crystal lises in mhi te needles containing H20 and melts a t 129" (compare Zincke and Muhl- hausen Zoc. cit.). The picrate CI7HIBOSN4 crystallises in slender yellow needles and melts at 219'. The hydrobromide of a-hydroxyglutaconaldehydedi-p-phenetidide C,,H,60,N,,H Br formed from p-phenetidine and furfuraldehyde by the bame method as the dianilide crystallises in glistening blue prisms melts a t 157-15So and dyes silk and unruordanted cotton- wool the rhodamine colour but not fast.The free bc6se is obtained as a yellow oily mass. When heated with nit'robenzene it yields 3-hydroxy- 1 -p-et~~oxyphen?lZpyriin~~nz bromide C,,H,,O,N Br H,O which crystallises in colourless iridescent leaflets and melts a t 167--168O. The picmte forms yellow needles and melts a t 207". Dyes derived from Furfuraldehyde. WALTER DIECKMANN nrid LUDWIG BECK [and in part BRUNO SZELINSKI] (Ber. 1905 38 4122-4135. Compare Zincke and Miihlhausen this vol. i 3 3 ; Kiini g abstract). - H y drox ygl u taconalcle h y ded ian ilid e hydrobromide N HPh*CH:CH*CH:C(OH)*C H:NPh,HBr,H20 pre- pared either by the action of aniline and aniline hydrobromide on furfuraldehyde or by the action of aniline and cyanogen bromide on 3-hydroxypyridine melts and decomposes at 166" and is converted by heating with alcohol and hydrochloric acid into 3-hydroxy-1-phenyl- pyridinium chloride OH*C,NH4PhBr which melts and decomposes a t G.Y. G. Y. preceding110 ABSTRACTS OF CHEMICAL PAPERS. 210° and yields a picrate melting and decomposing at 218-221' and a platinichloride melting and decomposing at 199' ; the identity of the two preparations is thus fully demonstrated. Similar evidence was obtained in the case of the p-chloroaniline derivatives. Hyd~*ox~glutaconaldehydedi-p-chloroaniZide hydrochloride C,H,Cl~?JH~CH:CH*Cl~:C(OH)~CH:N~C,H,Cl,HCl resembles the dianilide hydrochloride and melts' and decomposes a t 167'. 3-Rydroxy- 1 - p - chlorophen y lp yr id inium chloride OH- C 5N H,C1* C,H,Cl cry st all is es from water in long colourless needles and melts and decompo"ses a t 221'.The pZutinichloride crystallises from hot water in orange- yellow needles and melts and decomposes at 217'. T. M. L. Action of o-Nitrobenzaldehyde on Dimethylaniline in Presence of Hydrochloric Acid. THEODOR ZINCKE and WILHELM PRENNTZELL (Ber. 1905 38 41 16-4122).-o-Nitrobenzaldehyde and dimethylaniline which yield a triphenylmethane compound when acted on by zinc chloride give when acted on by concentrated hydrochloric acid at 11 O-115° a compozmd C,,H,,ON,Cl which is formulated as an anthranil derivative but might possibly be an acridone compound C,H,c1<:!>c6H,*NMe ; it crystallises from hot alcohol in yellow needles from acetone in stout reddish-yellow needlw and melts at 162-163° ; its dilute alcoholic and ethereal solutions show a very strong fluorescence similar to that of fluorescein ; concentrated solutions are yellow ; it is stable towards alkali hydroxides and does not lose chlorine but has slight basic properties.The hydrochloride forms colourless flakes the nitrate and sulphate solourless needles; the platirzichloride (C,,€I,,ON2C1),,H,PtC1 crystallises in minute yellow scales is insoluble in water and decomposes above 200" ; the methiodide C,,H,,ON,Cl,BleI crystallises from hot alcohol in glistening scales melts at 184' liberating methyl iodide and fluoresces in alcoholic solution. Reduction by means of zinc and acetic acid gives a compound formulated as 5-ch1?oro-2-umino-4'-dimeth~luminobenxopl~enone NH,*C,H,Cl COO C,H,*NMe which crystallises in minute yellow needles and melts a t 185".The hydrochloride crystallises from dilnte hydrochloric acid in colourless glistening tablets but is decomposed by water or alcohol. The acetyl derivative crystallises from dilute alcohol in yellow glistening needles and melts at 132O. The ketone is reduced by hydrogen iodide and phosphorus a t 19 0-200' to 2 4'-diaminodiphenylmethane (Stadel Abstr. 1895 i 233) which crystallises from ether in transparent tablets melts a t SS-S9O and is readily converted into diphenyl- methane. The hydrochloride crystallises in small colourless needles. The acetyl derivative separates from alcohol in white tabular crystals melting a t 20So or in small glistening needles melting at 218'; only the latter modification is described by Stadel. T. M. L.ORGANIC CHEMISTRY.111 Phenylhydrazine as a Reducing Agent in Organic GIUSEPPE PLANCHER (Gaxxetta 1905 35 ii 460-463). A reply to Odd0 and Puxeddu (Abstr. 1905 i 842). T. 11. P. Chemistry. -Polemical. Phenylethylidenehydrazine. GEORG LOCKEMANN and OTTO LIESCHE (Annulen 1905 342 14-50).-Ptrenylethylidenehydr- azine that is acetaldehydephenylhydrazone was used in the preparation of acmldehyde as a means of recognising acet- aldehyde (Abstr. 1905 i 570). It has been shown by Fischer (hbstr. 1896 i 361) to exist in two or three mutually convertible isomeric forms. A list is given of the phenylhydrazones of aldehydes or ketones or ketonic acids of osazones of diketones and other simi1:tr hydrazones which exhibit isomerism. This isomerism has been variously regarded as a structural or steric isomerism but the explanation given by Hantzseh and based on the latter type of isomerism is regarded as the most adequate.The conditions under which the two forms of the acetaldehyde- phenylhydrazone are stable have been investigated. Fischer (Zoc. cit.) obtained a p-form (m. p. 63-65") which was transformed by alcoholic sodium hydroxide into the a-form melting at 98-101"; the latter then passed slowly into a third variety melting a t 80". It is now found that this substance exists in two modifications; the stable a-variety melts a t 9S-l0lo whilst the labile p-fo?.rn melts a t 57". The P-hydrazone gradually changes into the a-form but the trans- formation is hastened by the action of bases such as sodium hydroxide or ammonia and also by various salts.Crystallisation from alkaline 75 per cent. alcohol is the most efYectual method. The change from the a- into the p-form also takes place in certain solvents but is momentarily effected by treatment with aqueous sulphurous acid. Tho depression of the freezing .point of the a- modification does not appear to be due to cz conversion into a third form but to decomposition oxidation &c. Fischer's isomeride (m. p. 63-65') is probably an amorphous mixture of the a- and P-hydrazones. X cetaldehydephenylhydrazone is prepared by adding molten phenyl- hydrazine to an ice-cold solution of acetaldehyde in light petroleum. The product which is white can only be kept in an atmosphere free from alkaline or acid vapours; i t melts usually a t 51-57' although higher melting points ( 9 P ) have been observed. 011 crystallisation from 75 per cent.alcohol containing a trace of sodium hydroxide prismatic crystals of the a-modification are obtained. The p m( dification is obtained by adding aqueous sulphurous acid either to a 75 per cent. alcoholic solution of the a-hydrazone or by moistenivg the crystals. The use of a stronger acid hydrochloric or nitric brings about the transformation but a t the same time causes some decomposition. Carbon dioxide attacks the a-modification slowly but does not convert it into the p-form. Even in a com- pletely neutral medium such as air the @-modification becomes coloured and the melting point rises. Indifferent solvents cause the transformation of either form into the other but in no case can a complete transformation be effected by simple112 ABSTRACTS OF CHEMICAL PAPERS.recrystallisation. The melting point of the p-form may be somewhat raised by recrystallisation or that of the a-form somewhat lowered. Both isomerides show the same behaviour towards benzoyl chloride. Dibenzoylphenylhydrazine (m. p. 177-1 78') is formed when an aqueous suspension of the hydrazone is treated with benzoy 1 chloride and sodium hydroxide ; a t the same time tribenxoylphenyl~ydraxilze C27H2,0,N2 is formed; it can be prepared by repeated treatment oE phenylhydrazine with benzoyl chloride in ethereal solution in the presence of sodium hydroxide and crystallises in rhombic plates melting at 200-201°. Both the a- and /3-hydrazones yield the same p- benxoyl-P-phenyl- a-ethylidenehpdraxine CHMe N *NPhBz when the benzoylation is carried out in pyridine solution; it crystallises in rectangular plates or cubes melting at 89-90° and is reduced by zinc dust and acetic acid to benzanilide. I t does not condense under the action of phosphoric oxide or zinc chloride to a diphenylpyrazole.It is thought that the isomerism of acetaldehydephenylhydrazone is not explicable from a stereochemical standpoint but rather is better accounted for as a case of tautomerism. Diphenylhydraeine Hydrazobenzene and Beneylaniline and Miscibility of the last two with Azobeneene Stilbene and Dibenzyl in the Solid State. F. M. JAEGER (Proc. K. Akad. N'etenach. Amsterdam 1905 8 466-474).-The following crystallographic constants were determined as-diphenylhydrazine triclinic [a b c = 0.7698 1 0,5986 ; hydrazo- benzene rhombic [a b c = 0.9787 1 1.24971 ; benzylaniline mono- clinic [u b c = 2.1076 1 1.6423 ; p = 76'36.5'1.Bruni and Gorni (Abstr. 1899 ii 407 732) and Garelli and Calzolari (Abstr. 1899 ii 732 ; 1900 ii 65) have concluded from freezing-point observations that mixed crystals are formed bet ween dibenzyl stilbene tolane and azobenzene the groups -CH,*CH,_ -CH:CH- -CiC and -N:N- being capable of mutual replacement in an isomorphous series a conclusion which has been confirmed by the crystallographic measurements of Boeris (Atti Soc. ItaZ. Sci. MiZano 1900 39 111-123). It has therefore been suggested that if two aromatic substances can form mixed crystals their hydro-products can do the same.This conclusion is contradicted by the marked contrast between hy drazobenzene (rhombic) and azo benzene (monoclinic) which are not isomorphous do not form mixed crystals and give the normal V-shaped melting-point curve ; the group -NH *NH- must therefore be excluded from the above series. Benzylaniline containing the mixed group -CH,*NH- might be expected to fall in with the rest of the series ; actually although not isomorphous with azobenzene a rearrangement of the indices gives very similar values for a b and for p but different values for c b ; the ielatiouship is therefore morphotropic but not isomorphous. Action of Nessler's Solution on Antipyrine Pyramidone Antifebrin and Exalgin. PAUL N. RAIKOW and CHB. KULUMOW (Chem. CeiLtr. 1905 ii 1595; from Oesterr. CILenL.Zeit. [ii] 8 445-448. Compare Schuyten Abstr. 1898 i 452 ; Ville and Astre Abstr. 1900 i 363 4ll).-The author has succeeded in preparing K. J. P. 0. a = 89'24' p = 137'28.5'. y = 90O4.5'1 ; T. M. L.ORGANIC CHEMISTRY. 113 mercuric iodide compounds of antipyrine pyramidone antifebrin and exalgin by using alkaline solutions of mercuric iodide. " Antipyine oil" forms a bright yellow somewhat viscous liquid and has a sp. gr. 1.3518 a t 19" ; it is readily soluble in alcohol or acetone less so in water and insoluble in ether carbon disulphide chloroform or alkalis. The aqueous solution is alkaline. The com- pomd is decomposed when treated with water which has not been distilled or by boiling the solntion in distilled water a white precipitate being formed in each case ; hydrochloric and sulphuric acids also give precipitates.Antipyrine oil is not volatile and is decomposed when strongly heated. With concentrated sulphuric acid i t gives a red coloiation and on warming the mixture small red crystals are forrued and iodine liberated. By the action of hydrogen sulphide silver nitrate and a n excess of silver nitrate on a solution of the oil in acetone mercuric sulphide mercuric iodide and silver iodide are formed respectively ; when heated with acetic acid a compound Hg[N(I)<ggIXE] 1 is formed which crystallises in pale yellow prismatic crystals mhts a t 133" and is decomposed by repeated crystallisation from glacial acetic acid. It is soluble in acetone chlotoform or glacial acetic acid but insoluble in cold water ether or carbon disulphide.When heated with water i t becomes deep yellow but regains its original colour on cooling ; the warm aqueous solution is neutral. 9 The compound H g 1 * ~ ~ [ 2 ~ ~ > C * N H l l l e I (?) formed by the action of Nessler's reagent on dimethylaminoantipyrine ( pyramidone) crystallises from acetic acid in sulphur-yellow ueedles and melts a t 170-172°; i t is readily soluble in acetone or hot acetic acid sparingly so in water arid insoluble in ether chloroform or benzene. The aqueous solution is neutral to litmus. Acetanilide (antifebrin) is only partially attacked by Nessler's reagent a yellow mercuric iodide compound being formed which is insoluble in ether chloroform or alcohol and is decomposed by water with liberation of mercuric iodide.The yellow oil " exalgin oil," HgI*NPhMeI*COMe or Hg,(NPhlMe*COMe),,BHI obtained by the action of Nessler's reagent on ruethylacetanilicle (exalgin) gradually becomes darker ; i t is mihcible with a small quantity of water. By the action of a large quantity of water on the oil yellow mercuric iodide is formed m d the liquid becomes opaque; after a time however red mercuric iodide separates out and the liquid regains its transparency and becomes almost colourless. When water or' ether is added to a solution of the oil in acetic acid red mercuric iodide is formed. The oil is insoluble in carbon disulphide and is partially decomposed by light petroleum regenerating its components ; by the action of concentiated sulphuric Pyrimidines ; 2 5-Diamino-6-oxypyrimidine.XII. TREAT L;. JOHNSON and CARL 0. JOHNS (Anaer. Chem. J. 1905 34 554-56S).- or nitric acid exalgin and iodine are formed. E. w. w. 5 -,\.itw-B-cunaino- 6-oxypyrimidine NH<Co.C(No2)>CH C(NH,) :N- obtained by114 ABSTRACTS OF CHEMICAL PAPERS. the nitration of 2-amino-6-oxypyrimidine (isocytosine) (Wheeler and Johnson Abstr. 1903 i 526) crystallises in groups of yellow micro- scopic prisms becomes brown at about 280" does not decompose below 300° and is insoluble in the usual organic solvents; when heated for four hours at 190-200° with dilute sulphuric acid i t is converted into nitrouracil. When 5-uitro-9-amino-6-oxypyrimidirie is reduced with aluminium amalgam in preseiice of ammonia 3 5-diusnino-6-oxypyim- idine NH<Co. C(NH C(KGp)>CH,H,O )-N is produced which crystallises in large radiating prisms is very soluble in water and is probably identical with the diamino-oxypyrimidine obtained by Kutscher (Abstr.1903 i 668) from the nucleic acid of yeast. The anhydrous base decomposes a t about 2 4 5 O aod has no definite melting point. The picrate hydrochloride nitrute and siclphate are described. When 2 5-diamioo-6-oxypyrimidine is heated with 20 per cent. sulphuric acid for three hours a t 130-140° in a sealed tube it is partially con- verted into 2-umino-5 6-dioxypyrimicline which crystallises from water in groups of microscopic prisms and does not decompose below 300'; its picrate is described. 2 5-Diamino-6-oxypyrimidine may also be prepared by heating 5-bromo-2-amino-6-oxypyrimidine with concentrated solution of ammonia or by the action of alcoholic ammonia on 5.amino-6-oxy- 2-ethylthiolpyrimidine.When an aqueous solution of guanidine is heated with ethyl sodioformylhippurate 2-arnino-6-oxy-5-benzo~lumi?zo- - _ _ pprimidine hydrochloride N H < ~ & ~ ~ d & B ~ > C H H C l is produced which crystallises from hot water in microscopic needles and decom- poses at about 275O. By the action of benzaldehyde on 3-amino-6-oxy- pyrimidine 6-oxy-2-benxylidenec6m~nopyr~m~dine C(N:CHPh) :N is obtained which forms yellow crystals decomposes a t 238 -242O and is very stable towards nitric acid. When a solution of 2-amino-6-oxy- pyrimidine in acetic acid is treated with sodium nitrite a substance is formed which crystallises in microscopic prisms is very soluble in water turns brown a t about 280° does not melt below 300° and is probably an acetate of 2-amino-6-oxypyrimidine. NH<CO-CH>CH E.G. New General Method of Syn thesising Pyrazole Derivatives. GAETANO MINUNNI [in part with G. VASSALLO RICCARDO CIUSA and GUIDO LAZZARINI] (Atti R. Accad. i%zcei 1905 [v] 14 ii 414-420). -On heating a mixture of equal quantities of bonzaldehydephenyl- hydrazone and ethyl acetoacetate at 195-205O a substunce C21H,602N2 is obtained which crystallises from alcohol ir white nacreous laminae melting a t 140-140.5° and is soluble in ether light petroleum or amyl alcohol and very readily so in ethyl acetate benzene or chloroform. It dissolves in cold concentrn ted sulphuric acid imparting t o it a n inteose red coloration and when boiled with concentrated potassium hydroxide solution is converted into a substance which separates from alcohol in white crystals melting a t 11 2 -1 13".With bromine in chloroform solution it gives a compound which crystallisesORGANIC CHEMISTRY 115 from alcohol in long white needles melting a t 160° and contains 20.5 per cent. of bromine. Later attempts to prepare the substance C,,K,,O,N from other samples of ethyl acetoacetate have proved fruitless and its constitution has not been determined. The condensation of benzaldehydephenylhydrazone and ethyl aceto- acetate in presence of zinc chloride yields ethyl 1 3-diphenyl-5- methylpyrazole-4-carboxylate ( I h o r r and Blank Abstr. 1885 810). Similarly the condensation of sixlicylaldehydephenylhy drazone with ethyl acetoacetate in presence of ziuc chloride leads first t o the formation of ethyl 1-phenyl-3-hydroxyphenyl-5-methylpyrazole-4- carboxylnte which loses one mol.of ethyl alcohol giving the lactone of 1 -phenyl-3-hydroxyphenyl-5-methylpyrazole-4-carboxylic acid N=-Y*C,H By alcoholic potassium hydroxide solution this lactone is transformed into the acid which is readily reconverted into the lactone by heating or by the action of acid chlorides. The phenylhydrazone of m-(or p - ) - nitrobenzaldehyde when condensed with ethyl acetoacetate in presence of zinc chloride yields ethyl l-phenyl-3-~n-(or p-)nitrophenyl-5- met h ylp yrazole- 4-carbox yla t e. endoIminotriazoles. 11. MAX BUSCH and GUSTAV MEHRTENS (Bey. 1905 38 4049-406s. Compare Abstr. 1905 i 307).-The action of aldehydes on triarylsminoguanidines leads to the formation of aminodihydrotriazoles >C*NHR which are decomposed by mineral acids and on oxidation yield endoiminotriazoles which are formed also by the action of acetic and benzoic acids on triarylamino- gFanidines in presence of phosphorus pentachloride but not of the acids alone ; they form sparingly soluble nitrates.With alkyl haloids the endoiminotriazoles form additive compounds NPh<C~e:C-cO>O' T. H. P. P;;IR-N CHR-ER N=y- I TR ?NRyA.lkX which yield csrbinol bases NR* C EL-/ YR-N OH*CR*NR >C*NR*Alk and when heated with potassium hydroxide are decomposed with rupture of the cyclic nucIeus. 3-Anilino-1 4-diphenyl-4 5-dihydro-1 2 4-triuxoZe C,N,H,Ph,*NHPh formed by the action of formaldehyde on triphenylaminoguanidine in boiling alcoholic solution crystallises in stout white glistening needles melts at 128" is easily soluble in chloroform ether benzene or hot alcohol and yields formaldehyde when heated with dilute sulphuric acid.When oxidised with alcoholic ferric chloride or sodium nitrite in alcoholic-acetic acid solution i t yields 1 4-diphenyl- 3 5-endoanilodihydrotriazole which the author terms '' nitron." This forms a picrate C,,H,,07N7 which crystallises in sheaves of small needles and melts at 257--258' and a diddoride C2,H,,N,,2HCl which cryst,alliees in glistening white leaflets and commences t o116 ABSTRACTS OF CHEMICAL PAPERS. N=C- N€'h-CH-/ decompose at 160'. The methiodide I (?Ph 'NPk,Mel formed by heating nitron with an excess of methyl iodide in a reflux apparatus fitted with a mercury valve crystallises from alcohol in yellow plates or from water in glistening needles melts a t 31 1-2 13" and has the conductivity p272 = 85 a t 25".The aqueous solution of the methiodide becomes neutral immediately on addition of sodium hydroxide but in dilute alcoholic solution the isomeric change from the strongly alkaline ammonium base first formed into the carbinol base takes place more slowly and is represented by the gradually diminishing alkalinity of the solution. The action of sodium hydroxide leads further t o the hydrolysis of the carbinol base and formation of a red axo-compound which on reduction with hydrogen sulphide yields anilinodiphenyZmet?~?lZguanidine NHPh*NH*C(NPh)*NMePh ; this crystallises in sheaves of needles melts a t 96-97" is readily soluble in benzene or ether and is oxiclised in alcoholic solution by the air becoming red.The cccrbinol base (5-~~ydroxy-3-rnet?~~ZccniZi~zo-l ; 4-diphenyl-4 ; 5- N>C*NMe€'h is prepared by dihydro-l ; 2 4-triaxole) treating the methiodide with aqueous ammonia; it forms a yellow powder melts a t 65O is readily soluble in alcohol ether or benzene and on treatment with nitric acid in dilute acetic acid solution forms the rnethonitl.de C2,H1,N4*N0 which crystallises in glistening clear flat needles and melts a t 1 60°. "'l'he rrzethopicrcnte Cz1H19N4,CGH207N formed by the action of picric acid on the carbinol base in dilute acetic acid solution or on the methiodide in alcoholic solution crystallises in long glistening needles and melts a t 193".YPh- CH(OH)*NPh The additive compound of nitron and benzyl chloride C27H23N4C1,H20 crystallises in clear thick tetragonal plates sinters slightly a t 1 80° melts at 210° is readily soluble in alcohol or warm water forming neutral solutions has the conductivity plo = 60 a t 25" and exhibits the same behaviour as the methiodide on treatment with alkali hydroxides. The hydrochloride C,7Hz3N,Cl,HCI crystallises in colour- lees needles softens a t 150° and melts and decomposes a t 160'; the nitrate C27H,303N5 crystallises in white needles sinters a t 209O and decomposes hucldenly a t a few degrees higher. The cavbinol base (5-hydroxy-3-henxylanilino-1 ; 4-diphenyl-4 ; 5-ditqdro-l 2 ; 4-triaxole) Cz7Hz4ON4 formed by the action of aqueous ammonia on the chloride crystallises in glistening transparent short tetragonal prisms melts at 153q is only sparingly soluble in alcohol ether o r benzene and on treatment with alcoholic hydrogen chloride is converted into a mixture of the benzyl chloride additive compound and its hydrochloride.N HPh* N H- C (NPh)-NPh* CH2Ph formed by the action of sodium hydroxide on the benzyl chloride additive compound crystallises in nodular aggregates of needles melts Amilinodipheny Zbenxylguanidine,ORGANIC CHEMISTRY. 117 at 153" and is oxidised on expmure t o the air with formation of the red axo-compound. 3-Anilino-1 4-diz3?~en?/l-5-nzetl~yl-4 5-dihydro-1 2 4-t?iuzoZe C,N,HMePh;NHPh formed from triphenylaminoguanidine and acetaldehyde crystallises from alcohol in glistening white leaflets melts at 131° is readily soluble in chloroform ether or benzene and on oxidation yields 1 4- diz3l~en?/Z-5-?izetl~~l-~ 5-endoanilo-4 5-dihydro-1 2 4-triazole 1 $Ph 'NPh.which is formed also by boiling triphenylaminoguanidine with acetyl cliloride in a retlux apparatus. It crystallises in moss-like aggregates of yellow needles melts at 245-346O is moderately soluble in methyl alcohol acetone or chloroform forms e a d y soluble salts and is decomposed by alcoholic alkali hydroxides forming acetic acid and triphenylaminoguanidine. The pZatinichZoride (C,lH,,N,),,H,PtCI, forms microcrystdine leaflets and melts at 180-1 S lo. 1 4-Dip?~enyZ-5-etl~yZ-3 5-endoani/o-4 5-dihydro-I. 2 4-triuxoZe formed by heating triphenylaminoguanidine with propic nic chloride at 120' and finally at 140" crystallises from dilute alco 101 in long brown rectangular plates melts at 229-230° i s moder ttely soluble in boiling benzene or chloroform and readily so in dilute siilphuric or acetic acids.N=C- BlPh*CMe- / C@?"N4 3-Adino-1 4 5-triplLeizyZ-4 5-dilqdro-l 3 4-triaxoZe C,N,HPh,*NHPh formed from triphenylaminoguanidine and benzaldehyde crystallises from alcohol in colourless needles melts at 165" is readily soluble in chloroform etlizr or benzene yields an odour of benzalclehyde and when oxidised with sodium nitrite i n acetic acid solution yields 1 4 5- triphenyl-3 5-endoanilo-4 5-dihydro-1 2 4-triazole \ X=C- I I k p h ,NPh NPh-bPh- which is forrn ecl also by heating triphenylaminoguanidine with benzoic chloride a t 130' or by boiling the gnanidine with benzoic acid and phosphorus pentachloride.It crystallises from alcohol in glistening dark yellow flat needles melts at 231-2.32° and forms a n additive compound with benzoic chloride C,,H,,ON,Cl which crystallises from ether in colourless needles melts and decomposes with forma- tion of benzoic chloride at about 262" and when dissolved in alcohol yields triphcnyle~ado,znilodihydrotriazole hydrochloride and ethyl benzoate or benzainide when trentc d with nlcoholic ammonia. The nit?*ate C2GH20N4 Hilu'O. cryst:~llihes froiii boiling water in colourless needles aiicl inelts nbovc 270" ; the Iiydrochloride forms dieeves of colourleqs flat needleq and melts at 270'. The nzethiodide C2,H2,N,,MeT crystallises from its ethereal-alcoholic solu- tion in colourless needles melts at 231" and is readily soluble i n alcohol or chloroform.118 ABSTRACTS OF CHEMICAL PAPERS.5-Hydroxy-3-methylanilino-1 4 ; 5-t~iphenyl-4 5-dil~ydro-1 ; 2 4-tri- axole OH*C,NgPh,*NMePh formed by the action of potassium hydroxide on the methiodide in ice-cooled absolute alcoholic solution cry stallises from a mixture of light petroleum and chloroform in yellow hexagonal leaflets melts a t 1 5 8 O is readily soluble in chloroform and when treated with dilute hydrochloric acid yields the methochloride C,7H,,N,CI which crystallises in spherical aggregates of white needles and melts above 265'. Anilinophenyl-p-tolylguanidine NHPh*NH.C(NPh)*NH.C7H7 formed from phenylhydrazine and carbodiphenylimide crystallises in spherical aggregates of needles melts a t 184-1 85O and condenses with formaldehyde t o form 3-anilino-2-~~~enyZ-4-p-tol?/l-4 ; 5-dihydro-1 ; 2 4- triazole C H20N4 which crystallises in colourless needles and melts at 148O.On oxidation with sodium nitrite i t yields a l-phen?/l-$-p- tolyl-3 ; 5-endoanilo-4 ; 5-dihydro-l 2 4-t&xoZe 1 $Ph N*C7H7 NPh*C H-/ mbich crystallises from a mixture of chloroform and light petroleum in dark yellow needles and melts a t 210O. C,,H,,N formed from formaldehyde and p - toluidinodipheoylguanidine crystal- lises from alcohol in glistening leaflets melts a t 123O is easily soluble in benzene 01- chloroform and on oxidation with nitrous acid yields 4- pl~enyl-1-p-tobyl-3 5-endoanilo-4 ; 5-dihydro-l ; 3 ; 4-triaxoZe "==C \ N = C- 3-Anilino-4-pl~e~zl/l-l -p-tolyl-4 5-Jihydro-l 2 d-t~iaxole I -\ I T P h )NPh N (C,H,)* C H - which crystallises in matted; glistening light yellow needles and melts a t 222'.3-Tolzcidino-I-phen?/l-4-p-toly1-4 ; 5-dihydro-l 2 4-tricmole C,,H,,N formed from formaldehyde and anilinoditolylguanidine crystallises in matted long white needles melts at 132O and on oxidation yields 1- phenyl-4-p- tolyl-3 5-endotohido-4 ?-di?tydro-l 2 4-triccxole (-12aH,,N which forms glistening yellow needles melts a t 170° and is readily soluble in chloroform. It has been found that as a test for nitrates nitron is even more delicate than was stated previously (Abstr. 1905 ii 28%). G. Y. Synthetical Bases from 4-Aminoantipyrine.MAX LUFT (Bey. Compare Knorr and Stolz Abstr. lS97 i 1905 38 4044-4049. 1 12).-Dinntip~lryEethyZelzediamine formed when 2 mols. of 4-nminonntipyrino arc heated with 1 mol. of ethylene dibromide i n alcoholic solution on the water-bath and 20 per cent. aqueous sodium hydroxide is added until the mixture is alkaline. It separates from a mixture of chloroform and ether as a colourless flocculent powder melts a t 54O is extremely hygroscopic absorbsORGANIC CHEMISTRY. 119 carbon dioxide from the atmosphere and is precipitated unchanged on addition of alkali hydroxides to its acid solutions. The platinichloride C,,H,80,N,H,,PtCl forms orange needles and decomposes at 20G-208'; the picrate crystallises in yellow needles and melts at 182' ; the mei.curic?Zoridee is insoluble in water and decomposes at 70 -72".Biantipyn$d iet?ylenediamine ( 1 4-diant ipyryZpiperaxine) Ph-C0 CH,*CH CO-YP1-1 NMw CMe ~c"<C€I"*Ca >N*cGCMe.NMe' formed by the act'ion of an excessYof ediylene dibromide on antipyrine or on diantipyrylethylenediamine at l20-13O0 crystallises from alcohol in colourless nacreous rhombic plates or needles me1)us at 2 6 2 O is only sparingly soluble or is inqoluble in all solvents and is very stable towards alkali hydroxides. crystallises in colourless needles and melts at 24s' ; the hydrobromide melts a t 237' ; the pZntinicMoride C~,H300,",,H,PtCI forms yellow needles becomes grey at loo" and decomposes at about 145"; the mercuricldoride melts a t 2 3 1 O . The hydroclJoride C ~ H ~ O @ N ~ ~ H C ~ rPh-CO C H,*CH NMe-C Me " 0 1 -Antippyllpiperidine >'"<(JH .CH >CH formed O O by heatiug 4-aminoantipyrine with a€-dibromopentane at loo" crystal- lises from ether in colourless needles has an odour of piperidine melts a t 144" is soluble in alcohol ether benzene or dilute acids and is stable towards alkali hydroxides.The hydrocldoride is deliquescent ; the hydriodide Cl,H210N3,HI crystallises in glistening yellow needles and decomposes with evolution of a gas at 215"; the picrate forms glistening yellow prisms and melts and decomposes a t 198'; the pkatinichloride C3,H,,0,N,,H,PtC1 forms plates and melts and decomposes at 208-2 10" ; the mercurichZoi*ide crystallises in white rhombic plates and melts and decomposes at 204"; the methiodide is obtained as a brown oil which solidifies t o a yellow mass; it melts a t 206" and decomposes when warmed with water.1 - Antipyrp Ztetrahydro- 1 4-oxaxine (antipyrykn2.orphoZi92e) >OY YPh-CO UH,*CH NNe CMe 9 C €3 r) is obtaiaed by digestion of 4-aminoantipyrine with ethylene oxide or ethylene bromohydrin in aqueous solution in R sealed tube for two days at the laboratory temperature and then for fourteeti hours a t 60° and heating the yellow oily product with 50 per cent. sulphuric acid at 125-135" under pressure. The intermediately formed hy droxy ethyl- and d i h y droxj e th yl-aminoan t ipyrine could not be isoliited. The morpholine derivative crystallises in rosettes of long colourless needles has an aromatic odour melts at 157" and is soluble in alcohol ether benzene or dilute acids. crystallises i n yellow plates and iiielts a t l i 2 O ; the while crystalline wercurich,Zoride me1 t s and decorriposes at 201' ; thc msthiodide C,,H,90,N,,MeI crystallises in colourless needles melts at 134" and decouiposes when warmed with water.'The picrate C1,T3190,N3 c(j'3307N3 G. Y.120 ABSTRACTS OF CHEMICAL PAPERS. Action of Sulphur Dioxide on nt-Toluenediazonium Chloride and Benzenediazonium Sulphate. JULIUS TROGER W. H ILLE and P. VASTERLING (J. pr. Chem. 1905 [ii] 72 511-535. Compare Abstr. 1904 i llS).-The red sulphonic acid formed by the action of sulphur dioxide on diazotised m-toluidine is considered now to have the constitution C,H,*N,*C,H,*NH*NH.SO,H. It yields sulphuric acid when hydrolysed with aqueous hydrochloric acid and potassium sulphite with dilute potassium hydroxide whilst reduction with stannous chloride and hydrochloric acid leads to the formation of sulphuric acid ammonia m-toluidine and a tolylenediamine.The potassium salt is oxidi$ed by mercuric oxide in aqueous solution with formation of the potassium salt C7H,*N,*C,H,*N,*S0,K which does not give a red coloration on acidification and is reduced to the original sulphonate by ammonium sulphide. The colourless sulphonic acid Cl4HI4O3N4S forms stable silver barium and calcium salts whereas the red sulphonic acid reduces warm ammoniacxl silver solutions . The action of nitrous acid on the red sulphonic acid leads to the formation of a derivative C,H,*N,*C,H,-N (P) which forms short dark red prisms or small orange-red crystals and melts at 65'.The sulphonic acid condenses with salicylaldeh yde in presence of sulphuric acid to form the sulphate OH*C6H4*CH(C7H,*N2 C7H,-NH*NH,),,H2S0 which is obtained in microscopic needles having a green sheen and dissolves in water to form a violet-blue solution. The hydroc?doride C,,H,,ON,,HCl and the nitrute C3,H,,0N,,HN0 formed by con- densation of the sulphonic acid with salicylaldehyde in presence of hydrochloric and nitric acids respectively have similar properties. The action of ammonia on the salts of the condensation product leads to the formation of an orange-red crystalline substance ~H'NH*C6H4>CH*C7H,."N.NH,. which melts a t 130" and forms dark-coloured crystalline salts with strong acids. The red sulphonic acid forms similar condensation products with other fatty and aromatic aJdehydes and with ketones.When a current of sulphur dioxide is passed through a cooled aqueous solution of benzenediazonium sulphate for one day the sulphonic cccid N,Ph*C,H,.NH*NH*SC),H is formed as a voluminous red mass (compare Koeaigs Abstr. 1878 219). It crystallises in micro- scopic dark red needles decomposes when dried a t looo and when re- duced with stannous chloride and hydrochloric acid yields sulphuric acid ammonia aniline and p-phen ylenediamine. When treated with sulphuric acid and sodium nitrite in alcoholic solution i t forms the substance N,Ph*C H *N3 which crystallises in small bronze leaflets and melts a t 9029ib. The potassium salt C,2H,,0.3N,SK forms reddish- yellow crystals dissolves in water forming a yellow solution which becomes red on addition of mineral acids tmt not of carbon dioxide or hydrogen sulphide and when oxidisetl with mercuric oxide yields the potassium salt N,Ph*C,H,*N,*SO,K from which it is again formed by reduction with ammonium sulphide.The colourless sulphonic acid C,,H1,O,N,S forms stable barium calcium and silver salts. 7H(j*N,* C7H6 G. Y.ORGANIC CHEMISTRY. 121 Azo-dye from 3 4-Dichloroaniline. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 1607SS).-The diazonium compound of 3 4- dichloroaniline combines with sodium P-naphthol-3 6-disulphonate to yield a red azo-dye which forms sparingly soluble metallic lakes remarkably stable towards light. The lakes of the corresponding azo- compounds from 3 4- and 2 5-dichloroanilines are so unstable towards light as to be practically useless.C. H. D. Yellow Disazo-dyes. FARBENFABRIKEN VORM. FRIEDR. BAYER C!G Co. (D.R.-P. 160674 and 160675).-Tbe tetra-azotised solutionsof benziciine- 2 2’-disulphonic and 3 3’-tolidine-2 2’-disulphonic acids combine with 2 mols. of l-phenyl-3-methyl-5-pyrazolone to form yellow disuzo- compounds which dye wool. Similar dyes are obtained when the same tetrazo-compounds are combined with 2 mols. of methylindole or with 1 mol. of methylindole and 1 mol. of l-phenyl-3-methyl-5- pyrazolone. C. H. D. o-Hydroxyazo-dyes. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 160536. Compare hbstr. 1905 i 250).-The formation of diazosulphonates in the treatment of diazotised a- and P-naphthyl- arninedi- or poly-sulphonic acids with alkali acetates or carbonates is avoided by adding chlorine or alkali hypochlorites as well as the salt used to fix the acid thus destroying any sulphites formed.Thus a diazotised solution of P-naphthylamine-1 5-disulphonate is neutralised with sodium carbonate and an alkaline solution of sodium hypochlorite added. The temperature may rise to 35’. Combination with P-naphthol then takes place in the usual manner. C. H. D. Hydrolysis of Egg-albumin. A. ADENSAMEH. and PH. HOERNES (Monutsh. 1905 26 1217-1230. Compare Skraup Abstr. 1904 i 954).-Using Skraup’s method the authors have isolated from the products of the hydrolysis of egg-albumin d-alanine leucine amino- valeric acid and a mixture of substances which crystallises in micro- scopic plates or needles melts in a sealed capillary tube at 280° has [ alD + 30.1 96O and contains probably aminovaleric acid and isoleucine ; it forms a copper salt which is readily soluble in methyl alcohol.The copper salts obtained from the filtrate from the phosphotung- states were fractionally crys tallised and made alkaline. The liberated ammonia was removed by distillation in a vacuum and the residue shaken with naphthalene-P-sulphonic chloride when the only product obtained was naphthalene-6-sulphonainide. No glycine pyrrolicline-2-carboxylic caseanic or caseic acids could be detected amongst the products of hydrolysis and if present they must be so only in extremely small quantities. G . Y. Colloidal Solutions. The Globulins. WILLIAM I;. HARDY (J. Physiol. 1905 33 25 1-337.Compare Abstr. 1903 ii 469).-This paper deals with the behaviour of globulins to acids alkalis and salts and the properties of the solutions considered as cases of colloidal solution. Globulins are amphoteric electrolytes ; the globulin salts iouise in solution therefore in an electric field the entire mass of proteicl VOL. XC. i. k122 ABSTRACTS OF CHEMICAL PAPERS. moves. A method for the direct measurement of the specific velocity of globulin ions is described. Among the many other points raised for which the original paper must be consulted the complete absence of “ionic ” globulin from blood serum is noted. It is probable that the globulin is formed in serum by the decomposition of a more com- plex proteid. W. D. H. Globulins. J. MELLANBY (J. Plzysiol. 1905 33 335-373).- Solution of globulin by a neutral salt is due to forces exerted by its free ions.Ions with equal valencies whether positive or negative are equally efficient and the efficiencies of ions of different valencies are directly proportional to the squares of their valencies. The amount of globulin dissolved by a given percentage of neutral salt is directly proportional to the strength of the original globulin suspension. The precipitation of globulin by neutral salts depends on a molecular combination between the salt and globulin the compound so formed being stable only in excess of the combining salt. Precipitation by salts of the heavy metals depends on the formation of a stable com- pound. Solution of globulin by acids or alkalis is of the nature of chemical combination.The relative solvent efficiencies of acids or alkalis are of the same order as their chemical avidities. W. D. H. The Group of Organic Acids containing Nitrogen and Sulphur which is present in Normal Human Urine. STANIS- LAUS BONDZY~SKI ST. DOMBROWSKI and KAZIMIERZ PANEK (Zeit. physiol. Chein. 1905 46 83-124. Compare Abstr. 1898 i 501; 1902 i 847).-nZZo0xyproteic acid is precipitated by the addition of lead acetate and the excess of lead removed by means of sodium carbonate. The addition of mercuric acetate and acetic acid precipitates a new acid antioxypoteic acid in the form of its mercuric salt and when the filtrate from this is neutmlised with sodium carbonate a precipitate of‘ the mercury salt of oxyproteic acid is obtained.The 6cwiurn and silver salts of the new acid have been analysed and the values calculs~ted therefrom for the acid are C 43.21 H 4.91 N 24.4 S 0.61 and 0 26-33 per cent. It gives a precipitate with phosphotungstic acid which is soluble in an excess or in water and from this precipitate the barium salt may be obtained without precipitation with mercuric wetate. The sodium and potassium salts dissolve readily in water and yield emulsions with alcohol. The alkali-earth salts also dissolve readily in water but are precipitated as white powders on the addition of alcohol. It gives neither the biuret nor the Millon reaction but gives both Ehrlich’s and Prieclenwald’s diazo-reactions. To obtain a good yield of oxyproteic acid it is advisable to remove the acetic acid and acetates before precipitating antioxy- and oxy-proteic acids with mercuric acetate ; if however the pure antioxyproteic acid is required the removal of the acetates is not recommended as when these are absent a considerable quantity of the oxyproteic acid is pre- cipitated with the antioxy-acid.Oxyproteic acid has the composition C 39.62 H 5-66 N 18.08 S 1.12 and 0 35.54 per cent. The acid is dextrorotatory.ORGANIC CHEMISTRY. 123 The acid previously described as dlooxyproteic acid was not pure as acids free from sulphur and nitrogen are removed when the colourless mercuric salt is decomposed with hydrogen sulphide and extracted with ether. The composition of the pure allo-acid is C 41.33 H 5.70 N 13.55 S 2.19 and 0 37.23 per cent. The salts are less soluble in alcohol than those of the other oxyproteic acids.These salts are often coloured by a substance which is comparatively rich in sulphur and appears to be identical with urochrome. Thiele’s uroferric acid (Abstr. 1904 i 452) closely resembles but does not appear to bc identical with cdlooxyproteic acid J. J. S. Action of Lactic Acid on Casein and Paracasein. 0. LAXA (kIiZchw. Zentr 1905 1 538-547).-Casein combines with lactic acid t o form a number of lactates. The latter are soluble in water except those which contain less than 1 per cent. of lactic acid. By dialysis a lactate containing from 1.4 to 1.9 per cent. of lactic acid is produced whilst by ‘‘ salting out ” a solution of casein in lactic acid :t lactate with 7.5 per cent. of acid is obtained. To term the insoluble litctates ‘‘ mono-lactates ” and the solable lactates “ cli-lactates ” is therefore inconclusive.The casein lxctates contain a proportionately small percentage of phosphorus from 0.45 to 0.48 per cent. The lactic acid produced by bacteria in the milk converts the phosphates present into acid phosphates and a t the same time combines with the casein forming soluble and insoluble lactates. The soluble lactates however are precipitated subsequently by the mineral salts present and the whole milk curdles. Impregnation of casein with calcium lactate renders the former exceedingly plastic. Paracasein is very probably a coinpound of casein with calcium phosphates. Acids con vert i t into casein and it yields the same lactates as casein. w. P. s. Amount of Glycine and Alanine from Casein.ZDENICO H. SKRAUP (Monatsh. 1905 26 1343-1349. Conipare Abst,r. 1905 i 619).-Details are given of the method by which d-slanine and glycine have been obtained from casein. I t is considered that the composition of casein varies and that the appearance of glycine amongst the products of the hydrolysis of commercial casein purified by Hammarsten’s method is not due to the presence of an impurity. G. Y. Kyrines. ZDENHO H. SKRAUP and RUDOLF ZWERGER (Xonatsl~. 1905 26 1403-1414. Compare Skraup Abstr. 1905 i 398; Siegfried Abstr. 1903 i 586 ; 1905 i 104).-When casein is heated on the water-bath for one hour with an equal weigbt of concentrated hydrochloric acid the mixture dissolves completely in an equal volume of water and if the resulting solution is further heated its lm-0- rotatory power changes to clextro-rotatory becoming constant in about forty-eight hours; a t the same time the behaviour of the solution t o phosphotungstic acid changes the precipitates formed a t first are resinous but those obtained after about forty-two hours’ heating on the water-bath consist of short prisms and contain nitrogen124 ABSTRACTS OF CHEMICAL PAPERS.and carbon in the atomic proportion 1 2.6 which was found by Siegfried for his caseinokyrine. The basic syrup obtained on treatment of the crystalline phosphotungstate with bnryta forms a double salt with cadmium iodide containing nitrogen and carbon in the atomic proportion 1 2.6 a double salt with potassium iodide containing nitrogen and carbon in the atomic proportion 1 2-4 and a derivative with naphthalene-P-sulphonic chloride in which the proportion is 1 2.2.The basic syrup (30 grams) yields 21 grams of lysine picrate 0.5 gram of arginine nitrate and 1.5 grams of crude histidine from which 0.2 gram of the crystalline hydrochloride is obtained. G. Y. Gelatin. 11. ZDENKO H. SKRAUP and F. HECKEL (ikfonutsh. 1905 26 1351-135s. Compare Abstr. 1905 i 398 619).-Gelatin was hydrolysed by heating with hydrcchloric acid and the product evaporated in a vacuum and esterified by treatment with absolute alcohol and hydrogen chloride. After removal of ethyl aminoacetate hydrochloride the filtrate was extracted with ether and the residual solution precipitated with phosphotungstic acid in three fractions. The final filtrate after removal of the phosphotungstic acid yielded a small amount of glutamic acid.The second phospho tungstate precipitate yielded lysine and arginine. The third precipitate mas crystallised from water when three fractions were obtained ; the least soluble part yielded an uncrystallisable syrup ; the moderately soluble fraction yielded a mixture of d-alanine and glycine whilst the most soluble part yielded almost pure glycine. d-Alanine and glycine are separated by repeated fractional crystal- lisation alternately of the copper salts and of the acids. G. Y. Jecorin. J. MEINERTZ (Zed physioE. Chern. 1905,46,376-382),- Manasse states that Drechsel’s jecorin yields on decomposition the same products as lecithin with dextrose in addition. Ring regards it as a mixture of various compounds of lecithin of which lecithin-dextrose is an abundant one.I n the present research jecorin was prepared from liver by Drechsel’s method treated with dilute hydrochloric acid and dialysed ; the dialysable substances are the reducing substance a nitrogenous material and inorganic matter containing calcium and phosphoric acid ; the residue was without reducing action and showed all the properties of lecithin. W. D. H. The Chromogen of the so-called Scatole-red contained in Normal Human Urine. J. PII. STAAL (Zeit. physiol. Chern. 1905 46 236-263).-Normal human urine when mixed with hydrochloric acid and a few drops of potassium nitrite solution yields in addition t o indigo-red a dye which is insoluble in chloroform and diEers spectro- scopically from indigo-red.A close examination of this dye proves i t to be identical with Pl’encki and Sieber’s urorosein (Abstr. 1883 101). The chromogen which gives rise to this dye may be extracted by Stokvis’ method (Ned. lrijdsch. Gem 1901 i 961). The ethyl acetate extract may be freed from indican by shaking with water and when mixed with magnesium carbonate yields a rnugnesiurn derivative which may be isolated by removing the ethyl acetate and extracting theORGANIC CHEMISTRY. 125 residue with 90 per cent. alcohol. It is a brownish-yellow amorphous powder soluble in wa,ter alcohol acids or alkalis but insoluble in ether chloroform or acetone. With hydrochloric acid and a few drops of potassium nitrite solution it yields the stable red dye which may be extracted with nmyl alcohol.The composition of the magnesium compound is Mg 10.26 C 46.59 €1 4.98 and N 3.35 per cent. It is not a “coupled” sulphnric or glycuronic acid and is not a scatole derivative as this base is not formed when the compound is reduced distilled o r fermented by bacteria. When heated with sulphuric acid,!it yields acetic and hippuric acids. J. J. S. Preparation and Analysis of Nucleic Acids. XI. Nucleic Acid from the Mammary Glands of the Cow. *JOHN A. MANDEL and PHOEBUS A. LEVENE (Zeit. plqsiol. Chem. 1905 46 155-158. Compare Abstr. 1900 i 572 ; 1‘301 i 299 623 ; 1902 i 668 779 ; 1904 i 126 ; 1905 i 105 847).--The copper salt of the nncleic acid gave the following analytical data C = 31.34 H = 4.07 N = 14-65 P=S-48 Cu=7*00 per cent.When hydrolysed with 2 per cent. sulphuric acid 100 grams yield guanine 1.05 and adenine picrate 4.56 grams. With 25 per cent. sulphuric acid thymine 5 grams and cytosine picrate 10 grams are obtained. When distilled with hydrochloric acid the acid yields furf uraldehyde and with concentrated sulphuric acid I~evulic acid. J. J. S. Nucleic Acids of the Thymus. 111. HERMANN STEUDEL (Zeit. physiol. Chein. 1905 46 332-336. Compare Abstr. 1904 i S37).- When hydrolysed with acids nucleic acid yields both purine and pyrimidine bases among other substances. The relationship between these is doubtful. If a reducing agent is added to the acid ased in hydrolysis much of the purine bases is destroyed but there is no cor- responding increase in the pyrimidine bases If the hydrolysis is carried out with sulphuric acid so energetically as to destroy all the purine bases the same negative result regarding pjrimidine bases is obtained.Cytosine and thymine are present but in smaller amount than in experiiiients where the hydrolysis was not carried so far. W. D. H. Catalysis and Enzyme Action. C. HUGH NEILSON (Anzer. J. Pl~ysiol. 1906 15 148--158).-Further evidence is adduced which shows the similarity between the action of enzymes and that of nietallic catalysts. Platiniim black and manganese dioxide act in the same way on salicin and amygdalin as emulsin does. W. D. H. Physico-chemical Nature and Activity of Enzymes. LUIGI MARINO and G. SEBICANO (Guxxettcc 1905 35 ii 407-417).-The authors have prepared carefully purified specimens of emulsin and msltase which were white a,nd dissolved in water giving solutions having a faint reddish-yellow or brownish-red colour according to the concentration.If a drop of a very concentrated solution of ernulsin126 ABSTRACTS OF CHEMICAL PAPERS. is added to a very large quantity of water the latter becomes milky but as more emulsin is added the amount remaining in solution gradually increases. The authors compare this phenomenon with that observed with readily hydrolysable inorganic salts. The deposited emulsin has the same composition as that in solution and exhibits similar behaviour. A t temperatures above about 30° the emulsin solutions remain clear however great the quantity of added water may be. Maltase exhibits similar comportment but the temperature above which its solutions remain clear on dilution with water is lower than with emulsin.Rmulsin has the following percentage composition carbon 43.68 ; hydrogen 7.62 ; and nitrogen 13.64 that of mnltase being carbon 43.48 ; hydrogen 6.87 ; and nitrogen 6.80. On exposing an 18-20 per cent. emulsin solution to the action of sunlight in absence of oxygen it was found that the activity of the enzyme decreased and increased in a periodic manner. The following are the relative amounts of salicin decomposed by a constant quantity of the emulsin solution after exposure to sunlight for different periods at first 93.6 ; after six days 70.2; after eleven days 15.1 ; after sixteen days 28.0 ; after twenty-one days 35-0 ; after twenty-six days 38.5 ; and after sixty days less than 10.6.After such exposure to sunlight the emulsin has the same chemical composition and the same physical properties as the original enzyme. Emulsin solutions exposed to only the heat rays or only the light rays of the sunlight underwent no change. The weak sunlight of the end of October exerts no influence on the activity of emulsin solutions. Maltase exhibits the same behaviour as emulsin when its solutions are acted on by sunlight. Solutions of emulsin and maltase of equal concentration have the same refractive index specific rotatory power and specific conductivity. Studies on Enzyme Action. Lipase. HENRY E. ARMSTRONG (Proc. Koy. Xoc. 1905 B 76 606-60S).-In the experiments on castor oil ground castor oil seed was employed; in the experiments on other esters the oil was first removed by means of ether.The observations of Connstein and his co- workers that ricinus lipase is effective only in presence of acid and that it acts preferentially on the natural fats are confirmed. Ethyl mandelate is not much affected by ricinus lipase whereas it is readily attacked by animal lipase (compare Dakin Abstr. 1904 i 10'71). Attempts to prepare an extract containing an enzyme were un- successful. U7hen the material free from fat is digested with the amount of sulphuric acid in presence of which hydrolysis of fatty oil is rapidly effected the enzyme is destroyed. Nuclease. FRITZ SACHS (Zed. plqsiol. C'hem. 1905 46 337-353). -The experiments recorded support the theory that ferments exist which are capable of cleaving nuclein with the liberation of nuclein bases.Such ferments are found in the extracts of many tissues but especial attention is directed in the present research to the iiuclease of the pancreatic juice; this is not identical with trypsin but is destroyed by tryptic action. T. H. P. G. S . W. U. H.ORGANIC CHEMISTRY. 127 Papain-digestion. FRIEDRICH KUTSCHER and LOHMANN (Zeit. physiol. Chew,. 1905 46 383-386).-Contrary to Mendel's statement (Abstr. 1901 i 355) it is found that abundant quantities of crystal- line cleavage products are obtained by the action of papain on proteids. They resemble those obtained by the use of trypsin. Tetra- and penta-methylenediamines which are characteristic of the prolonged action of pepsin could not be prepared. W. D. H. Action of Rennin.I. H. REICHEL and KARL SPIRO (Beitr. chem. Physiol. Path. 1905 '7 485-507).-The experiments relate mainly to reaction velocity and show that within quite wide limits the amount of enzyme and the time of curdling are inversely proportional. The influence of calcium salts follows an equally simple law. The effect of other snbstances was also studied. W. D. H. Ferment Action and Ferment Loss. 11. H. REICHEL and KARL SPIRO (Beitr. chem. Physiol. Path. 1905 7 479-484. Compare Abstr. 1904 i 1071).-In milk the loss of the enzyme rennin is related to the amount of calcium salts present. I n specimens con- taining such salts the loss increases and in those in which the calcium percentage is kept constant the amount lost rises with higher con- centrations of rennin and is relatively greater than in those poor in calcium salts.Magnesium chloride acts in a similar way but not so markedly. Potassium thiocyanate increases the loss slightly ; glycerol and urea increase i t greatly but possibly in some cases an injurious effect on the ferment has here to be dealt with and not merely a division of the amount of ferment between curd and whey. W. D. H. Studies on Enzyme Action. VII. The Synthetic Action of Acids contrasted with that of Enzymes. Synthesis of Maltose and isoMaltose. E. FRANKLAND ARMSTRONG (Proc. Roy. Soc. 1905 B 76 592-599. Compare Trans. 1903,83 1305 ; Abstr. 1904 i 956-958 1070 ; 1905 i 746).-When dextrose is condensed by means of hydrochloric acid (compare Fischer Abstr. 1891 412; 1896 119) both maltose aud its isomeride isomaltose are produced. To detecb isomaltose the acid was removed by means of lead carbonate and the filtered solution fermented with Xucclmrontpes intermedians to get rid of unaltered dextrose; from the resulting solution an osazone was obtained which behaved in all respects like the osazone of isomaltose obtained by E. Fischer. I n testing for maltose the dextrose was removed from another portion of the solution by fermenting with S. Mu~*x&anu which contains no maltase and the maltose confirmed by observing the rotatory power of the solution by preparation of the osazone and by its behaviour towards maltase. I n the former case isomaltose was produced but the solution was not tested for maltose; with emulsin maltose was formed but probably not isomaltose. The theory of condensation by acids and enzymes is discussed. Dextrose was also condensed by means of maltase and emulsin. The investigation of these points is being continued.128 ABSTRACTS OF CHEMICAL PAPERS. With acids both isomerides are t o be expected since the condensation is '' uncontrolled," but with enzymes owing to their selective action the process is probably controlled. Experiment shows as in the above examples that a n enzyme favours the production of a sugar isomeric with that which it can hydrolyse; the question as to how the control of the enzyme is exerted so as to produce this result is considered. G. S. Studies on Enzyme Action. VIII. The Mechanism of Fermentation. E. FRANKLAND ARMSTHONG (Proc. Roy. Soc. 1905 B 76 600-605. Compare preceding abstract).-The action of twenty typical pure yeasts prepared by Hansen's methods on dextrose mannose lwulose and galactose has been investigated. Whereas the three first-mentioned sugars were fermented apparently with equal readiness by all the yeasts about half of the latter had no action on galactose a result which is in accordance with previous observations. This inability to ferment galactose has nothing to do with the absence of hydrolysing enzymes since i t was observed with yeasts contain- ing invertase maltase and lactase respectively. Further dextrose mannose and lzevulose were readily fermented by yeasts which do not contain any enzyme capable of inducing the hydrolysis of bioses. Prom these results it is clear that the processes of enzymo-hydrolysis and of fermentation differ in some essential respects although for reasons given in a previous paper (Abstr. 1904 i 957) i t is probable that they are cognate phenomena. It is pointed out that the three hexoses which behave alike have a common enolic form and the change to this is probably the initial stage in fermentation. The mechanism of the fermentation of galactose seems to be different from that of the other three sugars. G. S. Diphenylsilicone and Benzylsilicon Compounds. WALTHER DILTHEY [and FRITZ EDUARDOFF] (Bey. 1905 38 4132-4136. Com- pare Abstr. 1904 i 132 464).-The gelatinous diphenylsilicone (diphenyl silicoketoue) becomes crystalline when rubbed with a few drops of acetic anhydride. It separates from chloroform and light petroleum in clear flat prisms melting a t 188' and readily soluble in ether benzene or chloroform. Both the gelatinous and the crystalline compounds are trimolecular probably O<siph5.0 Si Dibenx?/ZsiZicoZ Si(CH,Ph),(OH) crystal1i;es from a mixture of benzene and light petroleum melts at 76O and dissolves readily in ether benzene or chloroform. The yield is small. FribenzyZsiZicoZ Si(CH,Ph),*OH is obtained when a larger quantity of magnesium benzyl chloride is used ; it crystallises from alcohol in long colourless needles and melts a t 106". SiPh - 0 ~ Ph,. J. J. S.