69 Organic Chemistry. Substitution Process in the Fatty Series. By ARTHUR MICHAEL [with w. H. GRAVES and w. w. GARNER] (Ber., 1901, 34, 4028--4060).-The process of substitution in the fatty series is dis- cussed, and recognising that the principal factors in tbe replacement of hydrogen by chlorine and bromine are the chemical attraction be- tween the hydrogen atom, which is replaced, and the halogen, on the one hand, and between the halogen and carbon atoms on the other, the author considers that the presence of positive groups (methyl, &c.) renders greater the attraction between the carbon and hydrogen, whilst negative groups (carbethoxy, &c.) loosen this link- i n g ; further, positive groups attract to, and negative groups repel from, their neighbourhood negative substituents.The bromination of hexane in sunlight leads mainly t o the forma- tion of p- and y-hromohexanes, together with a small quantity of a-bromohexane and a dibromohexxne. By conversion of the p- and y-bromohexmes into the corresponding hexanones ( Abstr., 1900, i, 321), it was shown that the quantity of the ,&compound is considerably greater than t h a t of the y-compound. A t its boiling point, ethyl a-bromobutyrate is said to be converted into ethyl P-browobutyrate (Erlenmeyer and Marx). It is found, however, that after many distillations of the pure a-bromo-ester, less than I & per cent. is converted into the P-derivative The boiling point of pure ethyl a-brornohutyrate is 177.5' at 764-6 mm. preshure. a- Brotuoiuohutyric acid is not transformed irito the P-bromo-acid at 100'; the cworrespondiog ester is only transformed to a very swall extent after boiling for 2 hours.a-Bromopropiorric acid can be distilled under the ordinary pressure without undergoiug any change ; when heated for many hours at 120 -130O under pressure, a smail amount of @bromop*opioiiic acid is formed. Er hyl a-bromovalerctte distils unchanged at 193-196' after having been boiled. The chlorides of several fatty acids were chlorinated by a 10 per cent. solution of chlorine in carbon tetrachloride and the resulting pro- ducts fracationated under reduced pres+ure. Propion? 1 chloride yielded mainly (at least 65 per cent.) P-chloroppopionyl chloride, C H,Ci*CH,*COCl, an oil boiliug at 82-82-5" (corr.) under 108 mm. pressure, together with a smaller quantity of the a-chloro compound.It is noticeable that a-chloropropionic acid yields some acrylic acid uuder the action of alkalis, whilst a-bromopropionic acid gives only traces. On ch1orjn:ition of butyryl chloride, P-chlorobut yryl chloride forms 60 per cent, of the product, and the a- and y-c.hloro-dertvatives edch about 20 per cent. ; a t the same time, some ay-dichlorohutyryl clclo~idb CH,Cl-CH,*CHCl*COCl, is produced as an oil boiling a t 98-100 under 42 mm. pressure, and yielding a chlorobutyrolactone when con- VOL. LXXXII. i, 970 ABSTRACTS OF CHEMICAL PAPERS. verted into the corresponding acid and the latter subjected to dry distillation. /3-Chlorobutyranilide, CHMeCI*CH,*CO*NHPh, prepared from aniline and /I-chlorobutyryl chloride, crystallises in thin leaflets melting a t isoButyry1 chloride yields 60-70 per cent.of the a-chloro- and 30-40 per cent, of the /3-chloro-derivative. a-Chlos.oisobutyraniZide, CClMe,*CO*NHPh, crystallises in thin leaflets melting at 69-70', and p-chloroisobutyranilide in leaflets melting a t 104-105'. From isovaleryl chloride, /3-chloroisovaleryl chloride is obtained as the chief product, whilst both the a- and y-chloro-derivatives are formed in smaller quantity. Bromine and isobutyryl chloride give mainly the a-bromo-, together with a little of the /3-bromo-derivative. When bromine and igobutyryl chloride in mol. proportion were exposed to sunlight, bright red crys- tals separated of a substance which melted at 40-42', did not contain chlorine, and in the air readily decomposed, giving bromine aod hydrogen bromide.On being dried in a desiccator over phosphoric oxide, it became white. Two pieces of apparatus are described in the paper, which are especially adapted to the fractionation of the substances dealt with. K. J. P. 0. 8 9-9 0'. Isomerisation of Dimethylcyclopropylcarbinol. By NICOLAI D. ZELINSKY (Ber., 1901, 34, 3887--3889).-0n heating cyclopropyl- dimethylcarbinol (Abstr., 1901, i, 660) with crystallised (hydrated) oxalic acid, a mbstccnce, C6HI20, was obtained as an oil with a pleasant odour, which readily distilled with steam, boiled at 92-93' under 746 mm. pressure, and had asp. gr. 0.835 at 21°/4' and [n]D 1.4063 a t 21'. The same substance was formed when anhydrous oxalic acid was used, It QH,-CH; proves to be a hexylene oxide, CH,.CMe,>O, and is probably formed by addition of the elements of wat& a n i a consequent opening of the methylene ring, followed by elimination OF water with the production of the oxide.K. J. P. 0. Syntheses of Cyclic Tertiary Alcohols by means of Organo- magnesium Compounds. By NICOLAI D. ZELINSKY [and J. GUTT] (Ber., 1901, 34, 3950--3952).-The following compounds have been obtained by Grignard's methods (Abstr., 1900, i, 382). 1 : 3-Dimethyl- cyclopentanoZ-3 (from 1-methylcyclopentanone-3) boils a t 88-5-89' under a pressure of 94 mm., or a t 143-145O under atmospheric pres- sure,not, however, without some decomposition; it has a sp. gr. 0.8935 at 19'/4', n,, 1,4434 a t 19', and a 1.49' when Z -0.25 dcm. When treated with oxalic acid, it yields the uusaturated liydrocarbow, YHMemcH2>C:CH2, which boils a t 93.5' (cow,), has a spa gr.0*'7734 C €12--CH2 at 19'/4'? nD 1.4296 a t 19', [ a l D 57*67', and when oxidised with potassium permangana te yields 1 -methylcyclopentanone-3. 1-Heth yZ- 3-ethyZcyclopentano1-3, boils at 71' under a pressure of 21 mm., and has a sp. gr. 0.8974 a t 19'/4O. R. H, P.ORGANIC CHEMISTRY. 71 Partially Acetylated Polyhydroxylic Compounds. KNOLL & Co. (D.R.-P. 122145).--When completely acetylated hydroxylic compounds are heated with the unaltered substance, a reaction occurs between the two, resulting in the formation of a partially acetylated derivative. When triacetin and glycerol in equal proportion bg weight are heated for several hours a t 200°, the chief product of re- action is monoacetin. Monoacetylresorcinol results from resorcinol (2 parts) and diacetylresorcinol (3 parts) when the mixture is heated at 170'.The monoacetyl derivative of pyrogallol is produced under similar conditions from a mixture of pyrogallol and its triacetyl com- pound. Anthrapurpurin and its triacetyl compound yield the corre- sponding diacetyl derivative. G. T. M. Dihydroxykopropylhypophosphorous Acid. By CH. MARIE (Compt. rend., 1901, 133, 818-820. Compare Abstr., 1901, i, 635).- Dihydrox yiso~opyl~~ypo~~~osphol.ous acid, PO,H,,( C,H,O),, me1 ts a t 185-186' and loses acetone when heated a t 150', or when boiled with strong acids or alkalis. Mercuric chloride does not oxidise the acid in the cold, but when boiled converts it into an acid, PO,H,,C,H,O ; lead oxide similarly gives the lead salt of the last-mentioned acid.The salts of dihydroxyisopropylhypophosphorous acid are all soluble in water, and are easily prepared from the acid and the oxide or carbonate of the metal. The sodium salt, (C,H,0)2,P02H2Na,3H20, forms colourless, efflorescent crystals soluble in alcohol ; the lead salt crystallises with 2H20 ; the silver salt forms anhydrous, delicate needles, sensitive t o light; the lanthanum and ceyium salts are an- hydrous and much less soluble in hot than in cold water. The methyl and ethyl esters are prepared from the silver salt and alkgl iodide and form colourless crystals which melt respectively at 92' and 95'. A diacetyl derivative, (C,H,O),,PO,HAc,, melting at 171" is obtained when the acid is treated with acetic anhydride. The dibenxoyl deriva- tive, (C,H,O),,PO,HBz,, was prepared by dissolving the acid in excess of pyridine and slowly adding an ethereal solution of benzoyl chloride; it melts at 195-196' and is a monobasic acid.The silver salt, ( C,H60)2,P02AgBz,, is an insoluble, crystalline powder. The methyl and ethyl esters were obtained from the silver salt as amorphous masses. The formula PO(CMe2*OH),*OH is suggested for the acid (com- pare Ville, Abstr., 1889, i, 1134). K. J. P. 0. Reactions of Trichloroacetio Acid. By ARTHUR CLERMONT (Compt. rend., 1901, 133, 737--738).-When mol. proportions of tri- chloroacetic acid, alcohol, and sulphuric acid are mixed, heat is developed and the liquid becomes opalescent, On adding water, ethyl trichloro- acetate separates as an oil.Addition of its own volume of ammonia to the oil rapidly converts it into t?vichZoroacetccrnide, which sublimes in plates resembling naphthalene, melts at 135', and boils a t 240'. The ready formation of the ester is suggested, as a means of recog- nising trichloroace tic acid in the presence of other chloro-acids. K. J. P. 0. 9 272 ABSTRACTS OF CHEMICAL PAPERS. Montan Wax. By EDGAR VON BOYEN (Zeit. angew. Chem., 1901, 14, 1110-llll).-Montan wax is a hard, crystalline wax melting a t about 70" and is obtained when bitumen from brown coal is subjected t o steam distillation. It appears to be a mixture of montanic acid, C2,H,,02 (compare Hell, Zed. angew. Chern., 1900, 13, 556), and an alcohol. The alcohol is easily soluble in light petroleum, melts at 60°, and is readily attacked by sulphuric or nitric acid.The original bitumen is probably an ester of the alcohol and acid and is hydrolysed during distillation with steam. Potassium and sodium montunates are readily soluble in hot water, but yield gelatinous precipitates on the addition of much water. The nzccgnesium salt crystullises from alcohol in needles J. J. S. Transformation of Salts of Pyruvic Acid. By A. W. K. DE JONQ (Bec. l'ruv. Chim., 1901, [ii], 20, 365-387. Compare Wolff, Abstr., 1899, i, 483)-Careful analyses of barium parapyruvate (W) (Wolff's salt) agree beet with the formula (C6H,0,Ba,4H,0), ; the salt is decomposed by boiling water t o form the soluble burium nzeta- pyi-uvccte, which, with phenylhydrazine hydrochloride, gives nearly the theoretical quantity of the phenylhydrazone of pyruvic acid.As barium parapyruvate loses exactly 3&H20 when exposed over sulphuric acid, i t is probable that the salt has the molecular composition of the polymerisation of 3 mols. of pyruvic*adid. The metapyruvates The barium parapyruvate, obtained by the action of dilute aqueous potassium cyanide or potassium hydroxide on barium pyruvate accord- ing t o Wolff's method, is always slightly impure, containing barium carbonate and another barium salt ; it does not completely dissolve on boiling with water, although the purer barium parapyruvate, obtained by transforming barium pyruvate by means of a very small quantity of barium hydroxide, readily does so. Finck's so-called basic barium salt, (C,HgOg)2Ba,,Ba(OH)2, is merely a mixture of the impure para- pyruvate with barium carbonate and hydroxide.A large part of the paper deals with the method of purifying barium parapyruvate and the quantitative estimation of pyruvic acid in the form of its phenylhydrazone. are possibly derived from the simpler form, CO,K*CMe<O>CMe*CO,H. 0 W, A. D. Intramolecular Migration of Acyl Groups. By WILHELM WIS- LICENUS and HEINRICH KORBER (Bey., 1901,34, 3768. Compare Abstr., 1901, i, 187).-The conversion of ethyl 0-acetylacetoacetate into ethyl diacetoacetate at high temperatures id best carried out at 240°, but even then the yield is only 1 per cent. of the theoretical, At 260°, the yield is doubled, but a considerable amount of acetylacetone is produced. The two compounds are identified by means of their copper derivatives.G. T, M.ORGANIC CHEMISTRY. 73 Action of certain Acid Chlorides on Methyl and Ethyl Sodioacetoacetate. By A. BONOERT (Conzpt. rend., 1901, 133, 820-821. Compare Abstr., 1901, i, 31 l).-Ethyc! propionylctcetoacetate (C-ester), CMeO*CH(CEtO)*CO,Et, formed together with the 0-ester by the action of propionyl chloride on ethyl sodioacetoacetate, is a colour- less oil boiling at 112-113" under 20 mm. pressure, having a SP. gr. 1-09 1 at 0"/4", and giving a red coloration with ferric chloride ; the copper salt crystallises in blue needles melting at 78". The 0-este~ is separated from the C.ester by means of a saturated solution of sodium carbonate, and is a colourless oil boiling at 121' under 23 mm. pressure and having a sp.gr. 1.061 at 0'/4"; i t gives no color- ation with ferric chloride. The C-ester represents 59 per cent. of the mixed esters. Ethyl C-butyrylacetoacetate, CMeO*CH( CPraO)*CO,Et, is a colourless liquid which boils at 112" under 16 mm. pressure, has a sp. gr. 1.062 at 0°/4",and represents 56 per cent. of the mixed esters; its copper salt forms blue needles melting at 89". The 0-ester boils at 112-113° under 10 mm. pressure and has a sp. gr. 1.033 at 0°/40. With dry ammonia, the C-ester yields acetamide and ethyl butyrylacetate (compare Blake, Abstr., 1901, i, 363), which boils at 101" under 20 mm. pressure and has a sp. gr. 1.007 at 0". Methyl C-isov~leryk~~cetoucetate, CMeO*CH(CH2Pip*CO)*C0,Me, is a colourless oil boiling at 107-108" under 11 mm.pressure and has a sp. gr. 1.069 at 0'/4"; its copper salt crystallises in opalescent, blue needles melting at 137". When heated with water at 140-150O under pressure, the ester decomposes into carbon dioxide, methyl alcohol, and isovalerylacetone, CiXeO*CH,*CO*CH,Prp, which is a colourless liquid with a fruity odour boiling a t 76" under 19 mm. pressure and having a sp. gr. 0.936 at 0"/4"; the copper salt forms small, blue crystals melting at 142'. With dry amirionia, the ester yields acetamide and methyl isovalerylucetate ; tbe latter boils at 95' under 19 mm. pressure and has a sp. gr. 1.006 at 0'/4" ; the copper salt forms small, green crystals melting at 136". The last-mentioned methyl ester givesl with hydrazine, 3-isobutyZpgraxolone, which crystal- lises in white spangles melting at 229".Methyl 0-isovalerylacetoucetate is a colourless oil of disagreeable odour boiling at 113-114' under 11 mm. pressure, and having a sp. gr. 1.039 a t 0°/4". Methyl C-hexoylucetoucelate, CMeO*CIH( CO*[CH,],*CH,Me)*CO,Me, is a colourless liquid boiling at 144" under 21 mm. pressure and having a sp. gr. 1.056 at 0"/4" ; its copper salt crystallises in opalescent blue needles melting at 92'; the corresponding 0-ester boils at 142" under 16 mm. pressure and has a sp. gr. 1.026 at 0"/4". When heated with water at 140-150' under pressure, the C-ester yields carbon dioxide, methyl alcohol, and hexoylacetone, which is a colourless oil with a fruity odour, melting ah - lS0, boilingat 98-100'under 20 mm. pressure, and having a sp.gr. 0.936 at Oo,/4O; it is identical with the diketone obtained by Moureu s a d Delange (Abstr., 1901, i, 1 4 ) ; the copper salt forms small, blue, opalescent crystals melting at 134". With ammonia, methyl C-valerylacetoacetate gives acetamide and nzetlql hexoylacetccte, CH,Me*[CH,],*CO*CH,*CO2Me ; the latter is an74 ABSTRACTS OF CHEMICAL PAPERS. oil boiling a t 118' under 19 mm. pressure and having a sp. gr. 0.991 a t 0°/4' ; with hydrazine, 3-amyl)yraxolone is formed as white plates melting a t 195O. K. J. P. 0. The Red Alkali Chromo-oxalates. By ARTHUR ROSENHEIM and ROBERT COHN (Zeit. anorg. Chem., 1901,28, 337-341. Compare Abstr., 1896, i, 278).-Crystals of the red chromo-oxalates, obtained by treating a saturated solution of chromium hydroxide with 3 mols.of oxalic acid and 1 mol. of normal alkali oxalate, lose water a t 110' and change their habit. Further heating at 140' expels no more water, but above this temperature more water is lost. The compounds contain 2 mols. of water of constitution and are dioxalatodiaquochromates, [Cr(C20,),( H2O),]Na,5H,O. Treated with 20 per cent. ammonia (2 mols. NH, : 1 mol. red salt), the crystals liquefy, and if the liquid be warmed until the smell of ammonia disappears, light green crystals of chromamminoxalates separate on cooling. The silver-grey salt prepared by Wyrouboff (Abstr., 1901, i, 579) contains 16 mols. of water (not 13), Cr,(C,0,),,16H20, of which 6 mols. are water of constitution. This may be a hydrate of trioxalatohexaquodi- chromium, [Cr,(C,04),(H,0),],10H20, which would be a non-ionising compound, but since a change in properties takes place on heating, it is possible that the non-ionising compound is the known non-crystal- lising violet chromic oxalate.[Cr(C20,),(H20),]K,3H20, LCr(C,O,),(H,O),]NH,,3H,O ; J. McC. 1-Methylcyclohexane-3-malonic Acid and 1-Methylcyclohexane- By NICOLAI D. ZELINSKY and D. ALEXANDROFF (Ber., 3-acetic Acid, 1901, 34, 3885-3889).-Ethyl l-methylcyclohexane-3-mcdonate, C,H,,Me*CH( CO,Et),, is formed when a mixture of ethyl malonate and 3-bromo-1-methylcyclo- hexane is treated with sodium; it is a colourless oil boiling a t 150-154' under 10-12 mm. pressure, and has [ u],, - 3.94'. The corresponding acid, C10H1604, obtained by boiling the ester with alcoholic potassium hydroxide, forms crystals melting at 143-144' ; at the same time, a second isomeric acid, Cl0HI6O4, is formed, which crystallises in small stars melting and decomposing at 121-122'.From these facts, two stereoisomeric 1 -methylcyclohexane-3-malonic acids appear to exist. On heating the acid with the melting point 143-1 44" a t 160', 1-naetl~?jlcyclohexane-3-acetic acid, CGH,,Me CH;CO,H, is formed as a liquid with the characteristic odour of a fatty acid, boiling a t 144O under 19-20 mm. pressure and having a sp. gr. 0.9827 at 2lo/4O and [nI0 1.4582 at 21'. Ethyl 1 : 1'-di-methylcyclohexanemalonate, (c6HloMe,),C(C0,Et),, is formed together with the ester just described, and is a liquid boiling at 200-205' under 8-10 mm. pressure. K. J. P. 0. Derivatives of /3-Methylpimelic Acid.By ALFRED EINHORN and LUDWIG KLAUES (Ber., 1901, 34, 3793-3798. Compare Abstr., 1897, i, 344).-Ethyl P-methy!pimelate, when heated with sodium,ORGANIC CHEMISTRY. 75 somewhat above loo', yields the sodium salt of ethyl methyl-2-htohexa- methylcnecarbo,-cylte. The ester, obtained from the sodium salt, is a colourless oil, with an odour resembling that of ethyl acetoacetate, and boils at 145-150' under a pressure of 29 mm. ; in alcoholic solution it gives a blue coloration with dry, a deep violet with moist, ethereal ferric chloride, and a red with aqueous ferric chloride. The ester has either the constitution CHMe<CH,.CH, CH2-Co>CH *C02E t or Ethyl n z e t h y l i s o ~ o p y Z - 2 - ~ t o ~ ~ ~ ~ ~ e t h y Z e ~ e c a ~ b * ~ ~ Z ~ t ~ , Cl3HZ2O3, prepared by the action of sodium on a mixture of isopropyl iodide and the ester just mentioned, is a colourless oil boiling a t 165-168' under 20 mm.pressure. When this ester is boiled with excess of concentrated alcoholic potash, a methylisopropylketohexamethylene (b. p. 204-206') is formed, which is probably identical with inactive menthone (Urban and Kremers, Abstr., 1894, i, 468), as it has the same boiling point - - and yields an oxime with the same'melting point (78-80'). I(. J. P. 0. Optical Rotations of Certain Tartrates in Glycerol. By JOHN H. LONG (J. Arner. Chem. Soc., 1901, 23, 813--817).--The rotatory power of a number of tartrates in water and in glycerol at 20° has been determined with the following results : Salt. KNaC,H4O6,4H2O ......... KSbOC,H,O,,QH,O .........K(BO)C,H,O, ............... ( NH,),C,H,06 ............... N H,HC, H,O, .............. NH,(SbO)C,H,06,&H,0 ... NH,(SbO)C,H40,,2~H20.. . [ a ] D for water. 22.1" ~ = 5 t o 30 140-69 c = 2 141.27 c = 5 141.40 c = 6 58.10 c = 5 34.50 c = 5 26.0 ~ = 1 . 5 150.0 c = 5 115.7 C-5 [ a]D for gl yccrol. 28.85" c = 5 28.35 ~ = 1 0 27.87 C-15 27.40 c=20 26.96 ~ = 2 5 139.25 c = 2 141.17 C = 3 143.75 C = 4 30.9 C = 5 43.50 C = 4 27.7 C = 0.75 146.10 C = 3 146.25 C = 4 109.37 C = 4 These determinations show that the simple metallic tartrates ex- amined have a higher specific rotatory power in glycerol than in water. The antimony1 tartrates have nearly the same rotation in water and glycerol, and their behaviour in general suggests a constitu- tion different to that usually assigned t o these salts.Potassium borotartrate has a lower rotatory power in glycerol than in water, probably due to the withdrawal of part or the whole of the borie radicle to form a glycerol compound. Action of Ammonium Pararnolybdate on the Specific Rota- tion of Sodium Hydrogen Tartrate. By PETER KLASON and JOHN KORLER (Bet-., 1901, 34, 3946--3949).-The results of Itzig (Abstr., E. G.76 ABSTRACTS OF CEEMICAL PAPERS. 1901, i, 448) require correction in accordance with the researches of Klason on molybdates (Abstr., 1901, i, 162). The rule formulated by Rosenheim and Itzig (Abstr., 1900, i, 272) is wrong, as the maximum rotation given by sodium hydrogen tartrate depends, not only on the proportion of alkali ions to tartrate ions, but also on the molyhdic acid, the concentration, and the temperature.Complex Derivatives of Uranic Acid. By HRRRMANN ITZIG (Ber., 1902, 34, 3822--3827).--The great increase in the optical rotation of malic and tartaric acids in the presence of uranyl salts is t o be attributed t o the formation of complex urani-organic compounds (Walden, Ahstr., 1898, ii, 149). Peligot's uranyl tartrate (Annalen, 1845, 56, 231, and Dittrich, Abstr., 1899, ii, 629) is not a salt, its molecular weight is normal, its dissociation factor is 0.03 per cent., and its molecular rotation lie.; between +404' and 410'. The constitution suggested is C0,H*CH(OH)*CH(OH)*C~*O*Ur02*OH, uranotartaric acid. It forms a potassium salt which has only been ohtaiued in solution and has a ruolecular robation 500' to 511'; on ex- posure t o light, the solution rapidly turns brown: Potassium, barium, and calcium chlorides do not yield precipitates with these corriplex tartrates. iYranomccZic cccid, CO, H .C H ,*CH (OH)*CO*O*UrO,*OH, has a molrcular rottition -460' to - 467', and yields a sodium salt, CJ4H508UrNa,2H20, with a molecular rotation - 682' to - 686".R. H. P. J. J. S. Methylene Compounds of Hydroxy-acids. By CORNELIS A. LOBRY DE BRUYN and WILLIAM ALBKRDA VAN EKENSTECN (Roc. Trav. Chim., 1901, 20, 331-343).--Most of the facts of this paper have previously been dealt with (Ahstr., 1901, i, 1%)). The cc Impounds previously described are better obtained by heating the hydroxy-acids with dry, powdered trioxymethylene in chloroform solution for several hours ak 150'; in some cases, the addition of anhydrous sodium sulphate is advantageous.The deyivative of Ltartaric acid melts a t the same temperature (1 16-117') as t h a t of the d-acid ; the racemic acid derivative, which could not be obtained formeily, crystallises well and melts at 103'. Lactic, glycollic and glyceric acids yield oily derivatives, and saccharic acid a n oil containing three formal groups and having [a], i- 62' in a 4 per cent. methyl alcoholic solution; the triformal derivative of I-gulonic acid is an oil with [a], - 48'. &Tartaric acid, when heated for 2 hours at 150' with paraldehyde and sodium sulphate in chloroform, yields a small quantity (3 per cent.) of a diacetal derivative, which forms needles, melts at 121', and has [ a ] , about + 82 in a 1 per cent.methyl alcoholic solution. Citric acid yields similarly, at 120°, an acetal derivative melting at 180'. W. A. D. Bismuth Compounds derived from Organic Acids and employed in Pharmacy. By L ~ O N PRUNIER (J. Phccrz. Chim., 1901, [iv], 14, 493-499. Compare Abstr., 1901, i, 593; ii, lOS).- The crystalline compounds of bismuth with organic acids may be divided into two groups. The compounds belongirrg t o the first group0 RG A N IC CHEMISTRY. 77 are true bismuth salts such as bismuth salicylate, lactate, and mslate and normal bismuth citrate. The second group includes those com- pounds which possess acid properties and form salts with potassium, sodium, and ammonium. I n the latter compounds, the bismuth does not play the part of a base but rather that of a n acid, so that they must be regarded a s bismuthic organic acids.To this class belong bis- muthiditartaric acid and the so-called basic bismuth gallate, which is really bismuthigallic acid. H. R. LE S. Reduction-potential of Aldehydes. By E. BAUR (BAT., 1901,34, 3732--3735).-The maximum value of the reduction-potential of form- aldehyde ( 2 C.C. of 40 per cent. formalin with 50 C.C. of N sodium hy- droxide) was found to be - 0.343 volt, that of acetaldehyde (2 C.C. with 50 C.C. of N sodium hydroxide) -0.238 volt; that of benzaldehyde could not be satisfactorily measured owing to the slight solubility of the substance. The aldehydes thus act as powerful depolarisers a t the anode, where they are oxidised to acids; when sodium hydroxide was electrolysed between platinum plates the current was increased more than 100-fold by adding formaldehyde in the anode compartment. The aldehydes are also capable of acting as depolarisers at the cathocie by becoming reduced to alcohols, but this change proceeds only slowly and does not prevent the liberation of hydrogen.T. M. L. Action of Hydrogen Chloride on Aqueous Formaldehyde. By G. H. COOPS (Rec. Tyav. Chim., 1901, 20, 267--289).-Cun- trary t o Losekann's statement (Chem. Zeit., 1890, 14, 1408), the product of this action is not chloromethyl alcohol but a mixture of this with the two substituted ethers, OH*CH,*O*CH,Cl and OH*CH,*O*CH,*O*CH,Cl ; i t is not possible, as formerly stated, to separate t'he chloromethyl ether by simply distilling off the portion boiling below 85' and then washing the residue with water, and the part boiling between 45-85" is not the ether CH,Cl*O*CH,*OH.The unpurified oily product of the action of hydrogen chloride on formaldehyde is decomposed by ao excess of water giving trioxymethyl- ene, formed by elimination of 1 HC1 from OH*CH,*O*CH,-O*CH,Cl; cold aqueous potassium hydroxide yields only formaldehyde but on warming methyl alcohol and formic acid are produced from the latter. The action of alcohol on the original product develops considerable heat and gives a mixture of diethoxymethane boiling at 86-90', and having a sp. gr. 0.840, diethoxydintethyl &?Ley*, (OEt-CH,),O, which boils a t 102-106' and has a sp. gr. 0.864, and the substance, OEt*CH2*O*CH,*O*CH,C1 which has a sp.gr. 1.02 and distils at 47O under 30 mm. pressure, producing considerable quantities of formalde- hyde, The first two substances cannot be isolated by direct fraction- ation of the product of the action of alcohol, but are easily separated by treating this with potassium hydroxide or carbonate until all the chlorine is removed, washing with water, drying, and distilling. The third substance is isolated from the fraction of highest boiling point (b. p. above 47' under 30 mm. pressure) of the distillation of the direct product of the action of alcohol, by allowing as much of it as possible78 ABSTRACTS OF CHEMICAL PAPERS, t o evaporate at the ordinary temperature under a pressure of 7-S mm. ; the residue is the nearly pure ether. A criticism of Litterscheid's results (Abstr., 1901, i, 443) is ap- pended.W. A. D. Aldehyde Derivatives containing Chlorine (Carbonylchloro- aldehydes). FARBENFABRIKEN VORM.. F. BAYER & Co. (D.R.-P. 121223). -aPPP-Teti.achZoroethyl chlorocccrbonate, CCl,*CHCl*O*COCI, resulting from the interaction of carbonyl choride (1 mol.) and chloral (1 mol.) in benzene solution in the presence of dimethylaniline, is a colourless oil having a disagreeable, pungent odour and boiling at 79-80' under 16 mm. pressure. When the reaction occurs between 2 mols. of chloral and 1 mol. of carbonyl chloride or the equivalent amount of trichloro- methyl chloroformate or hexachlorodimethyl carbonate also in the pres- ence of a tertiary base, dichloralchlorocarbonyl [di-aP/3/3-tetrachloroethyl chlorocarbonate], CO(O*CHCl*~Cl,),, is produced and separates as a crystalline mass melting at 64' and boiling a t 170' under 11 mm.pres- sure. This product is almost insoluble in water but readily dissolves in the ordinary organic solvents; it is tasteless, but has a slight odour of chloral. Benzaldehyde reacts with 1 and 2 mols. of carbonyl chloride dissolved in benzene containing quinoline, giving rise to the a-chlorobenxyl chloro- carbonate, CHPhCl*O*COCI, and a-chlorobenzyl cas.bonate, GO( 0. CHPhCl),, respectively ; the former is an oil decomposing, when distilled under 1 mm. pressure, into benzylidene dichloride and carbon dioxide, the latter crystallises from light petroleum in rhombic prisms and melts at 105'. a-Chlorobenxyl aPPP-tetrachloroethyl carbonate, obtained either by condensing chloral with a-chlorobenzyl chlorocar- bonate, or benzaldehyde with a/3&&tetrachloroethyl chlorocarbonate, crystallises from light petroleum in lustrous leaflets and melts at 81.5'; i t is also produced by treating a mixture of chloral and benz- aldehyde with carbonyl chloride or hexachlorodimethyl carbonate in benzene containing quinoline.These condensations all require the presence of a tertiary base, but the bases of the pyridine series are not suitable for the purpose (corn- pare Abstr., 1901, i, 697). Nitrogen Acids. By ANG~LO ANGELI ( A t t i Real. Accad. f i n c e i , 1901, [v], 10, ii, 158-161).-Nitrohydroxylaminic acid, OH*N:NO,H. may be regarded either as an oxidation product of hyponitrous acid, OH*N:N*OH, or as a reduction product of nitrous acid, which, however, only in exceptional cases acts as if it had the bimolecular formula.Besides nitrohydroxylaminic acid, both hydroxylaminesulphonic and benzenesulphonehydroxamic acids are capable of yielding the residue :N*OH, so that i n presence of a n aldehyde they give hydroxamic acids. The action of :NOOH or an aldehyde mag be one of simple addition or the residue may first combine with 1 mol. of water, forming HN(OH),, which with the aldehyde yields the additive product OH*RCH*N(OH),, this then being resolved into the hydroxamic acid CCI,*CHCl*O*CO*O*CHPhCl, G. T. M.ORGANIC CHEMISTRY. 79 and water, In the case of aldehydes, the formation of such inter- mediate additive products has not been established, but in the action of the group :N*OH on nitroso benzene t o form nitrosophenylhydroxyl- amine, it is extremely probable t h a t the product OH*NPh*N(OH), is first formed.The hydrate, NH(OH),, would correspond with hypophosphorous acid which forms well-defined additive products with aldehydes. T. H. P. Researches on the Isomerisation of Pinacone and its Derivatives. By MAURICE DELACRE (Compt. rend., 190 1, 133, 738-740. Compare Abstr., 1896, i, 591, 662).-Neither of the formuls, CMe,*COMe and O<YMe2, proposed for pinacolin (methyl CMe, teskbutyl ketone) appear t o repreient completely the reactions of the compound, The author thinks that free pinacolin is a mixture of the two forms in a state of equilibrium. This view is based on the following reactions, With pinacolin, phosphorus pentnchloride gives a liquid chloride, CMe,*CCl:CH,, and the solid chlorides, ( a ) CMe,*CMeC12, from which a n acetylene hydrocarbon is obtainable ; ( b ) Ch!Ie,*CCl,-CH,Cl, which is formed by the action of phosphorus pentachloride on the liquid chloride ; ( c ) CClMe,-CClMe,(?), which yields, with alcoholic potassium hydroxide, tetramethylethylene. With moist pinacolin, sodium gives symmetrical reduction products. Pinacolyl alcohol yields a bromide which is identical with the compound obtained from hydrogen bromide and tetramethylethylene.The liquid chloride above mentioned yields on reduction a hydrocai*bon, CMe,*CH:CH2, boiling at 44', which, with hydrogen bromide, forms an additive product isomeric with pinacolyl bromide ; it reacts with moist silver oxide, producing mainly a secondary alcohol, CMe,*CH Me*OH, whilst with dilute potassium hydroxide, tetramethylethylene is formed, Pinacolyl bromide, on the other hand, with any moist oxide, gives, at SO-lOOo, mainly tetramethylethylene, together with a small quantity of the secondary alcohol.Oxidation of pinacolin yields 50 t o 60 per cent. of trimethylacetic acid and acetone (?). The hydrocarbon to which Couturier (Abstr., 1893, i, 244) ascribes the formula CMe,*CH:CH,, is regarded by the author as having the formula CMe,*CH*CMe:CH,, as the chloride formed from it and hydrogen chloride is identical with pinacolyl chloride. The formula OH*CMe,*CMe:CH, is given t o the compound formed in the action of potassium hydroxide on the additive product of hypochlorous acid and tetramethylethylene.By OTTO WALLACH (Annalen, 1901, 319, 7 7 7 1 20).-[With AD. GILBERT.]-The base, C,H,,N, produced by treating methylheptenoneoxime with phosphoric oxide (compare Abstr., 1900, i, 46), may contain either a pyridine or a pyrroline nucleus, and accordingly the base, C,H,,N, obtained by reducing this tertiary arnine with sodium and alcohol, is either a trimethylpiperidine, K. J. P. 0. Terpenes aud Ethereal Oils.80 ABSTRACTS O F CHEMICAL PAPERS. C M e , < ~ ~ . ~ ~ ~ ~ > C H , , or C M e , < ~ ~ ~ . ~ ~ > C H , , or a trimethyl- The physical properties of the new base favour the view that i t is a piperidine derivative. It is a colourless oil, having a n odour like t h a t of piperidine and boiling at 166"; the sp. gr. is 0.859 at 19" and n, 1'4596.The hydrochloride is syrupy, the platinichloride crystal- lises in needles melting a t 173', the a u ~ i c h l o d d e melts at 118'. The new base is a secondary amine isomeric with coniine. With nitrous acid, i t yields an oily nitrosoainine boiling a t 134' under 18 mm. pres- sure, and when converted into the cyanamide, c,H,,N.CN, it gives rise to two thiocadamides by the action of ammonium sulphide (com- pare Abstr., 1899, i, 658), one forming plates melting at 171', the other crystallising in woolly needles and melting at 154-155'. When treated with excess of methyl iodide in methyl alcohol, the amine gives rise to two quaternary iodides, C,H,,NMe,I, which are separated by the difference of their solubilities in alcohol. The a-compound is only slightly soluble in alcohol or water, and melts at 238'; the corre- sponding uurichZo?-ide, CsHi6NMe,AuCl4, melts at 105'.The p-corn- pound, produced in larger amount, crystallises in needles and melts at 159-160'; it is readily soluble in water or alcohol; the corresponding aurichloride melts at 99'. These quaternary iodides yield isomeric tertiary bases when their hydroxides are distilled in a vacuum. The tertiary amine, C,H,,:NMe, derived from the a-iodide boils at 167 -169' and yields a quaternary iodide, crystallising in lustrous scales and melting a t 231'. The isomeric tertiary amine produced from the P-iodide boils at 171-173'. The quaternary iodide prepared from this base is not homogeneous, and is obtained as a mixture of plates melting at 217', and needles melting a t 201'.The iodides of the tertiary bases yield hydroxides, which, on dis- tillation in a vacuum, give rise t o a mixture of trimethylamiue and unsaturated hydrocarbon. The Iqdrocurbon, CSHl4, from the @om- pound, boils st 107-110° and is isomeric with conylene. [With A. BLE~B~L.]-~ronzomethy~heptenone, CMe,:CBr*CH,*CH,.COMe, produced by adding bromine to a methyl alcohol solution of methyl- heptenoneoxime and pouring the mixture into a 10 per cent. solution of sodium hydroxide, is isolated in the form of its semicurbaxone, C,H,,Br:N-NH- CO *NH,, a substance crystallising from alcohol in white leaflets and melting at 184'. The ketone itself, obtttined from the semicarbazone by hydrolysis with 50 per cent. sulphuric acid, boils a t 96' under 9 mm.pressure, and has a sp. gr. 1.2715 a t 20' and n, 1.4913. The oxime, C8Hl3Br:NOH, melts a t 58' and boils a t 140' under 9 mm. pressure; i t is exceedingly soluble in the ordinary organic solvents. The benxylidene compound, CsHilOBr:CHPb, formed from its generators, dissolved in alcohol containing a small amount of sodiiim hydroxide, crystallises in lustrous, white leaflets and melts at 155'.ORGANIC CHEMISTRY. 81 The bromo-ketone, when treated with sodium hypobromite, yields y- bromo-8-methyl-y-hexenoic acid, CMe,: CBr C H,. C H,* CO,H, and this substance, on treatment with bromine, gives yys-tribromo-8-methyZhexoic acid, CMe,Br*CBr,*CH,-CH,*CO,H, which separates from alcohol in crystals melting a t 161". The bromo-ketone is reduced t o methylheptenone by sodium and alcohol, whilst the oxime, under these conditions, yields methylheptenyl- amine.Laevulic acid is obtained by oxidising the brorno-ketone, first with potassium permanganate, and then with chromic acid, The semicarbazone, or a solution of its generators, when heated for some time with dilute sulphuric acid, yields a mixture containing two bases, one having the formula C,H,,N, which is identified as 4-amino- 1 : 3-xglene, whilst the other, having the composition expressed by CSHI4N2, is probably a hydrazine derivative ; the latter base boils a t 175' under 15 mm. pressure and evolves ammonia when distilled under the ordinary pressure. These bases are also formed on boiling the bromo- ketone with hydrazine. sulphate. The production of the xylidine base is evidence in favour of the constitution indicated for the bromomethyl- heptenone. [With HEINRICH MEYER and E.MITTELSTENSCHEID.]-T~~ unsatur- ated base, C,H,,N, obtained by adding bromine t o methylheptenyl- amine hydrochloride, evaporating down the aqueous solution of the additive compound and setting free the amine with an alkali hydr- oxide, possesses many exceptional properties. It forms, with benz- aldehyde, an additive compound having the composition C,,H,,ON and melting a t 99-100". The compourbd, C15H2202N, produced by the Schotten-Baumann re- action, is a benzoyl derivative of the unsaturated base, plus the elements of a mol. of water. The base, C,Hl?NMe, obtained in the form of its iodide by mixing to- gether methyl iodide and the unsaturated amine at o", boils at 164-166O and has a sp.gr. 0.852, n, 1.4663 a t 20", mol. refraction 45.21 (calculated 45.08). The iodide crystallises from alcohol and ether in colourless needles melting a t 200-205* ; the picpvate and plntinichloi*ide melt respectively at 84-85" and 194-195". The monomethyl deriva- tive is not acted on by nitrous acid and therefore seems to be a tertiary base. Further methylation of the tertiary amine and treatment of the product with moist silver oxide results in the formation of trimethyl- amine and a ketone, C,H,,O. This ketone, a new naethyll~epterlone, is more readily prepared by treating the unsaturated base, C8H15N, with nitrous acid ; it boils a t 161-162', and has a sp. gr. O*S42 and n, 1.43096 a t 20', the found and calculated values for the mol.refraction being 38.73 and 38.72 respectively. I t s sernicarbazone melts at 93-95', and its oxinte boils at 9 9 O under 12 mm. pressure. Methylheptanol, C8H1,*OH, produced by reducing the new ketone with sodium and moist ether, boils at 166-167'; i t is accompanied by a syrupy product of high boiling point, which is probably a pinacone.82 ABSTRACTS OF' CHEMICAL PAPERS. This alcohol differs from thati obtained from natural methylheptenone in being unaffected by boiling dilute sulphuric acid. Methylheptenylamine, C,H,,*NH,, produced from the preceding oxime, boils at 156-158O ; its oxafute, hydyochloyicle, platinichloride, and carbamide melt a t 153--154O, 207-209', 146-147", and 123' re- spectively. The new methylheptenone, on oxidation with potassium permanganate and chromic acid, yields a mixture of isobutyric and oxalic acids.The following formulae, CMe,:CH*CH,*CH,-CMe:NH, CH,*CH, CH-CK CMe2:C<NH_b.3Me' and CMe2<NH.ClM:>CH21 are discussed in connection with the unsaturated base, C,H15N. A ketone formed from a base having the second formula would have a constitution corresponding with CHMe:CH-CH,*CO*CHMe,, and this substance would, on oxidation, yield isobutyric acid. Further investigations, however, are required in order to explain fully the constitutions of the compounds described in the last section of this communication. G. T. M. Condensation Reactions of Diketones. By THEOUOR POSNER (Rer., 1901, 34, 3973-3986. Compare Abstr., 1901, i, 14and 703).- a-Diketones can react with 2 mols. of hydroxylamine, phenylhydrazine, or semicarbazide, and different substituents do not hinder the condens- ation, as is the case with mercaptans.P-Diketones react with semi- carbazide (1 mol.), yielding pyrazole derivatives. Diacetyldisemicarbaxone, C,Me,(N*NH*CO*NH,),, crystallises from acet,ic acid in small plates melting a t 278-279" and is insoluble in most solvents. Diacet ylphen ylh ydmxone-semicarbaxone, N,HPh:CMe*CMe:N*NH*CO*NH,, crystallises in yellow needles melting at 229-230' and is insoluble in- water or ether. A ce tylpropion y Zdisemicaybct zone, NH,*CO*N,H :CMe*CEt :N,H* CO*NH,, crystallises in needles melting at 251-252' ; attempts to prepare the monosemicarbazone were unsuccessful. The phen ylhydruxone.semicarbaxone, N,HPh: CMe* CEt : N,H* CO*NH,, melts a t 199-200'.Benzil and semicarbazide react only when their alcoholic solution is warmed, and the product is a mixtureof a- benxilmonosemicurbaxone, crystal- lising in yellow needles and melting a t 164-165' with the stereo- isomeric P-compound melting a t 221' ; when the mixture is heated for several hours, the P-isomeride only is formed, but when warmed at 60' for half-an-hour, the a-compound is the chief product. obtained by the action of an aqueous solution of semicarbazide hydro- chloride, and sodium acetate on an alcoholic solution of acetylacetone, It sinters at log', is completely melted a t 111*4-112*4', and dissolves in hot water, alcohol, or ether. On treatment with ammoniacal silverORGANIC CHEMISTRY. 83 nitrate, it yields the silver derivative of 3 : 5-dimethylpyrazole (Rothen- burg, Abstr., 1894, i, 384).3 : 4 : 5-~rimethylpyrccaole-l-carboxylcmide, obtained from methyl- acetylacetone, crystallises in needles melting a t 148-149', and on treatment with ammoniacal silver nitrate yields the silver derivative of 3 : 4 : 5-trimethylpyrazole, Methylacetilacetone and phenylhydr- azine acetate yield 1-phenyl-3 : 4 : 5-ti.imethylpyi*axole, M --Nph>CMe, C Me'CMe in the form of an oil boiling a t 278--280° under 768 mm. pressure; the hydrochloride melts a t 52-53') and the picrate a t 100-103°. 3-Phenyl-5-methylpyrazoZe-l-carboxylamide, obtained from benzoyl- acetone and semicarbazide, crystallises in small needles melting a t 154-1 56'. Benzoylacetophenone and semicarbazide react only slowly and require vigorous boiling in aqueous alcoholic solution for 4 hours.The product is Enorr and Duden's 3 : 5-diphenylpyrazole (Abstr., 1893, i, 231). Benzoylacetophenone and hydroxylamine yield diphenyl- isooxazole (Abstr., 1896, i, 189). Acetonylacetonedisemicarbazone, C,H,( CMe:N,H* CO *N H,),, me1 ts a t 223-224' and is insoluble in most solvents with the exception of boiling water. Dimethylacetonylacetone -phenylhydraxone, CHMa;CO*CH,*CH,*CMe:N,HPh, crystallises in brownish-red needles melting a t 55-57' ; the come- s ponding CHDle, * CO * CH,*CH,-UM e: N,H* CO * NH,, melts at 201'. The diphenylhydrazone and disemicarbazone could not be obtained. J. J. 8. semicarhazone, Carbamide D e r i v a t i v e s of Sugars. 11. By K. SCHOORL (Proc. .K. Akad. Wetensch. Arnaterdam, 1901, 4, 214-217).-A detailed account of the physical and chemical properties of dextrose-ureide pre- viously described (Abstr., 1901, i, 258).I t has a sp. gr. 1.48 at 25' and the heat of combustion is 8307 R per gram-molecule. The ureide does not reduce a slightly acid solution of copper acet,ate, is only slowly oxidised at the ordinary temperature by hypobromites, but is quickly decomposed by nitrous acid a t 0'. I t s aqueous solution is only slightly hydrolysed by alkalis, but the rotatory power undergoes a rapid change. When acetylated in the presence of zinc chloride, the ureide yields a crystalline pentacetyl derivative melting at 200°, and, when benzoylated, a tetrabenzoyl derivative melting at 117'. The following substituted carbamides have been found to change the rotation of a solution of dextrose in dilute sulphuric acid : methyl-, phenyl-, and benzyl-carbamides, as-dimethylcarbamide, thiocarbamide, biuret, and urethane.The only sugars which condense with carbamide are those which contain an open carbonyl group, such as the aldopentoses and aldo- hexoses and of the bihexoaes, lactose and maltose. R. H. P. O p t i c a l Rotatory P o w e r of Sucrose dissolved i n Pyridine. By GUY MAURICE WILCOX (J. Physical Chem., 1901, 5, 587-599). -The specific rotation of sucrose in pyridine solution at 25" decreases from 86.7 for a 1 per cent. solution to 83.6 for a 6'25 per cent. solu-84 ABSTRACTS OF CHEMICAL PAPERS. tion, the curve being approximately a straight h e . Substitution of water for pyridine causes a considerable decrease in the rotation and a minimum value of 66.0 mas obtained when the percentage of water reached 80, the value in pure water being 66-6.The effect of temper- ature was investigated between - 10' and 105'; the specific rotation decreased from 88.7 to 77.0 between these limits, the rate of increase being slightly greater a t low than a t high temperatures, whilst the temperature coefficient is throughout considerably greater than in aqueous solution, a result probablydue to the greater expansion of the pyridine. The molecular weight as determined by the boiling point gave results lower than the theoretical and increasing with concen- tration. L. M. J. Inversion of Sucrose. By EDMUND 0. VON LIPPMANN (Ber., 1901, 34, 3747-3750). -A criticism of recent theories of sugar inversion (compare Abstr., 1901, ii, 89).By CARL NEUBERO and H. WOLFF (Ber., 1901, 34, 3840-3846).-GZucosamine hyds.0- clJoride p-mitrophenylhydraxone, OH- CH,* [ CH*OH],*CH( NH,,HCl) * CH :N*NH*C6H,*N0,, forms microscopic needles melting and decomposing a t 210' and dis- solves in water, yielding a pale yellow solution which turns deep red on the addition of fixed alkalis. The corresponding hydrobromide begins t o decompose a t 190'. T. M. L. Detection of Chitosamine [Glucosamine]. 4-ITetrcchydroxybutyl-~-p~enyZ~~~~oa~olyZ-2~~ercapta~, N=C(SH) C,HQo, '<(-lH. kp h 9 obtained from glucosamine and phenylthiocarbimide, forms long, colourless prisms melting a t 208' and has [a], + 58'20' ; it yields precipitates with silver nitrate, copper sulphate, or mercuric chloride solution.The corresponding l-azlyl derivative melts at 135'. None of the compounds described above is of use in the identifica- tion of glucosamine, as, although readily obtained from the pure base, they cannot be obtained in a crystalline form from mixtures con- taining other bases. The best method of identification is the con- version into norisosaccharic acid (Fischer and Tiemnnn, Abstr., 1894, i, 167), the alkaloidal salts of which are characteristic. The cinchonilze salt of this acid crystallises in elastic needles containing 2H,O and melting a t 20So, it is soluble in hot water, but only sparingly so in cold, is insoluble in acetone, chloroform, ethyl acetate, or benzene, and has [a]* - 175'. The quinine salt melts a t 207" and has [.ID - 125' and the h u c i n e salt melts at 199'.J. J. S. Ethylenediamine Carbonate. CHEMISCHE FABRIK AUF ACTIEN >GO, YH,*NH,*O (E. SCHERINGI) (D.R.-P. 123 138).-The substance, CH,-NH obtained by passing carbon dioxide into a cooled and stirred solution of ethylenediamine, is a crystalline substance vaporising a t 170" ; it is stable on exposure, its solution has an alkaline reaction and taste, and when evaporated leaves a syrupy residue, G. T. M.ORGANIC CHENISTRP. 85 Discrimination between Basic and Acidic Functions in 801u- tions of Amino-acids by means of Formaldehyde. By HUGO SCHIFF (AnnuZen, 1901, 319,59-76. Compare Abstr., 1899, i, 870).- Glycine is appreciably acid to phenolphthalein, but requires only about half the calculated amount of potassium hydroxide to produce neu- t r a l i t y ; in the presence of formaldehyde, however, it behaves as a monobasic acid, but even in this case the quantity of alkali required diminishes as the solution is diluted.Phenylglycine, owing to the acidic character of the phenyl group, behaves in solution as a mono- basic acid, even without the addition of formaldehyde; the three aminobenzoic acids exhibit a similar behaviour. a- Alanine itself is only feebly acid towards phenolphthalein, and even in a concentrated solution of formaldehyde i t requires less than 1 mol. of potassium hydroxide to give the neutral reaction. MethyZene-a-cLZccnine, a white, amorphous, soluble substance, behaves as a monobasic acid in concentrated solutions; it yields the copper salt, (CH,: N* C2H;CO,),Cu,2H,O.Taurine is slightly acid in concen- trated, and neutral i n dilute, solutions, but behaves as a monobasic acid in the presence of the aldehyde, even when the dilution is considerable. Leucine and tyrosine in strong solutions of the aldehyde behave as monobasic acids, but the action of this reagent is rendered incomplete on dilution. Methyleneasparagine reacts as a monobasic acid, Aspartic acid does not yield a methylene compound nor is its basicity appreciably affected by the aldehyde. Its sodium salt, however, becomes distinctly acid when treated with formaldehyde, the amount of potassium hydroxide required to neutralise the second carboxyl group being 75-80 per cent. of the theoretical; the action of the aldehyde diminishes rapidly as the solution is diluted.Since neutral asparagine is changed into monobasic aspartic acid by the conversion of the radicle -CO*NH, into carboxyl, it follows that the sodium salt is C0,H*CH(NH2)*CH,*C02Na, the acid function of the second carboxyl being neutralised by the adjacent amino-group. Tetraspartic acid itself is tetrabasic, but the fifth carboxyl group is indicated under the influence of the aldehyde, 4.8 mols. of potassium hydroxide being required to neutralise 1 mol. of the acid in the presence of this reagent. These changes in basicity are reversible and are affected by the mass of the reagents, the results obtained varying with the relative propor- tions of formaldehyde and water. On adding formaldehyde to aqueous solutions of ammonium salts, neutral hexamethylenetetramine is produced, and the combined acid set free can be titrated with standard alkali solutions, On the other hand, formaldehyde can be estimated alkalimetrically by adding to its solution excess of ammonium chloride.Boric acid and other weak acids are readily liberated from their ammonium salts by treating these compounds with formaldehyde solution. G. T. 751. Resolution of Racemic Amino acids. V. By EMIL FISCHER and RUDOLF HAGENBACH (Ber., 1901, 34, 3764-3767. Compare Abstr., 1900, i, 172, 646, 647).-l-BenxoyZ-d-amino-n-hcxoic acid, iyor,. LXXXII. i. h86 ABSTRACTS OF CHEMICAL PAPERS. C,,H,,O,N, isolated from the racemic acid by means of the cinchonine salt, crystallises from hot water in long, colourless needles with IH,O, melts at 53O (cow.), and has [aJp - 21.9' in water at 20'.The 1-aminohexoic acid preparedlfrom this has [ u ] D - 22.4' ; Schulze and Likiernik obtained by fermentation an acid which had [a], -26.5' (Abstr., 1893, i, 309). d-BenxoyLa-amino-n-hsxoic acid has [ a],, + 21 *Po. d-Aminohexoic Derivatives of the Alkali Metals and Cyclic Aminoketones. By EMANUEL MEBCK (D.R.-P. 121505. Compare Abstr,, 1901, i, 670). -Tropinone, vinyldiacetoneamine, and triacetoneamine, when dis- solved in dry ether and treated with sodium ethoxide or methoxide, either solid or dissolved in absolute alcohol, yield yellowish-white precipitates consisting of the respective sodium derivatives. The potassium derivatives are produced from potassium ethoxide in a similar manner. G. T. IN. acid has [ a ] D +21'3O.T. M. r,. Formation of Carbamide by the Oxidation of Physiological Nitrogenous Substances by means of Permanganate in Acid Solution. By ADOLF JOLLES (Ber., 1901, 34, 3786--3787).-1n opposition to Falta (Abstr., 1901, i, 795), the author finds that uric acid in a 0.02 per cent. aqueous solution containing 1 per cent. of sulphuric acid gives a quantitative yield of carbamide, but not the slightest trace of ammonia when oxidised with a slight excess of permanganate added gradually to the boiling solution. Crystallography of some Derivatives of Carbamide. By G. NEZ (Zeit. Kryst. Min., 1901, 35, 242-271).-The results are given of detailed determinations of the crystallographic and other physical characters of carbamide and of sixteen of its derivatives. The relations between the angular elements and between the topic axial ratios, depending on the introduction of different radicles, are discussed.L. J. 5. Primary Arsiaes. By ARTHUX W. PALMER and WILLIAM M. DEHN (Ber., 1901, 34, 3594-3599).--iClethyZarsine, AsH,Me, is formed by the reduction of methyldichloroarsine, AsMeCl,, but is best pre- pared by acting on an alcoholic suspension of sodium methylarsenate and amalgamated zinc dust with hydrochloric acid in an atmosphere of dry hydrogen in an apparatus entirely made of glass. The gas evolved is passed through water, dried over soda-lime, and liquefied by solid carbon dioxide. It is a colourless, readily mobile liquid which boils at 2 O under 755 mm. pressure, and at 1 7 O under 1.5 atmospheres pressure. It has the penetrsting, repulsive odour of cacodyl and fumes in the air, but is not spontaneously inflammable.If air has access to the apparatus in which it is prepared, the arsine is oxidised to a lustrous, red substance, the nature of which is not known. When pure, dry oxygen is added to gaseous methylarsine over mercury, equal volumes of the two gases combine, forming water and methylarsine oxide, AsMeO, which then slowly combines with oxygen forming methyl- arsenic acid. G. T. M.ORGANIC CHEMISTRY. 87 On one occasion, the addition of the oxygen was followed by a mild explosion, and the whole of the arsenic was deposited in the free state. The arsine is oxidised by concentrated nitric acid to arsenious acid and monomethylarsinic acid, and when passed into an alcoholic solution of iodine yields arsinmethyl iodide.Monophe.nykursinc, AsH,Ph, is prepared by a similar reaction from calcium monophenylarsenate, although La Coste and Michaelis were un- able to obtain i t in this way (Annulen, 201,203,209). It is a, transparent, strongly refractive oil, which boils at 148', and smells, when concen- trated, like phenylcarbamine, when dilute, like hyacinths. I n the air, it is converted into a yellow substance, which melts at 195-208' and is probably arsenobenzene. Nitric acid converts the arsine into mono- phenylarsinic acid and a yellow oil of unknown nature. Simultaneous Formation of Isomeric Substitution Deriva- tives of Benzene. VI. Nitration of Iodobenzene. By ARNOLD F. HOLLEMAN and B. R. DE BRUYN (Rec. Trav. Chim., 1901, [ii], -20, 352-359. Compare Abstr., 1900, i, 387, 638; 1901, i, 318).-The proportion of 0- and p-iodonitrobenzenes in the product of nitration of iodobenzene was determined by the method of melting points and of sp.gr. (Zoc. cit.). The product obtained by adding gradually 25 grams of iodobenzene to a mixture of 50 C.C. of nitric acid of sp. gr. 1.48 with 10 C.C. of acid of sp. gr. 1.52 consists at -30' of 35.3 per cent. of 0- and 64.7 per cent. of p-iodonitrobenzene, and st 0' of 34.2 per cent. of 0- and 6'7.8 of p-compound. Pure o-iodonitrobenzene, obtained from pure o-nitroaniline, has a sp. gr. 1*8100 at 155'/4' and melts at 54'; it is difficult to purify the o-compound obtained by the nitration of iodobenzene, and Korner, in giving the melting point as 49*4O, had not obtained the pure substance.na- and p-Iodonitrobenzenes have respectively sp. grs. 1.8039 and 1.8090 at 155'/4O. The eutectic point of a mixture of o- and p-iodonitrobenzenes is 45*2O ; the product of nitration a t 30" gave a value for this constant of 43*5O, and a t Oo a value 43.1'. The depression is due to the presence of about 1.1 and 1.3 per cent. of dinitroiodobenzene in the two cases; as the latter is formed only from o-iodonitrobenzene under the given conditions, i t can be expressed as such, and the values just given for the propor- tions of 0- and p-compounds are corrected on this basis. Velocity of Substitution of a Halogen by an Alkoxyl Group in some Aromatic Halogen Nitro-compounds. By P. K. LULOFFS (Rec. Trav. Cluim., 1901, 20,292-327. Compare Steger, Abstr., 1899, i, 745).-The method of procedure adopted was the same as that of Steger (Zoc. cit.), the special points studied being the interaction of I -chloro- and 1-bromo-2 : 4-dinitrobenzenes with sodium methoxide and ethoxide, and of 1-iodo-2 : 4-dinitrobenzene and several other nitro- compounds with sodium ethoxide. The influence of the concentration of the alcoholic solution, the addition of water to the alcohol, the pre- sence of a salt of sodium, and the temperature on the velocity constant, k, of the equation - dc/dt = kc2, was determined ; the results are given in the form of tables and curves, and in the following risumti. The transformation of the monohalogen dinitrobenzenes [X : (NO,), = A. H.W. A. D. h 288 ABSTRACTS OF CHEMICAL PAPERS.1 : 2 : 41 by an alkyloxide takes place in only one direction, the halogen in position 1 being substituted quantitatively by the alkoxyl group; the velocity of replacement by ethoxyl is greater than that by methoxyl, and the substitution of chlorine easier than that of bromine, and much easier than that of iodine. Thus, for sodium ethoxide in an absolute alco- holic solution containing three-fifths of the gaseous concentration of the halogen dinitrobenzene a t 1 5 O , the values of k for chlorine, bromine, andiodine were 3.26, 2.04, and 0.455, and the times in which the re- action was one-half complete, 17.7, 35, and 128 minutes respectively. Iodine is thus much more firmly attached to the aromatic nucleus than bromine, and bromine than chlorine. By comparison with Steger's results,it appears that the replacement of a nitro-group in 0- or p-dinitrobenzene, occurs much more slowly than that of the chlorine atom in chloro-2 : 4-dinitrobenzene.Contrary to Steger's result's, diminishing the concentration increases the velocity constant ; this increase is greater in the case of the chloro- than in that of the bromo-compound, and for absolute ethyl than for absolute methyl alcohol, The effect of changing the concentration is thus the same as in the case of the reaction MeI+NaOEt=MeOEt+NaI (Hecht, Conrad, and Briickner, Abstr., 1890, 1046). When the alcohols employed are diluted with water, there is a definite coefficient for each dilution, even when the quantity of water is as great as 40 per cent. The addition of water diminishes the reaction constant in the case of sodium ethoxide, and initially slightly increases that of sodium methoxide, but in the latter case subsequent diminution occurs.The influence of dilut'ion is most marked with chlorodinitrobenzene and least with iododinitrobenzene (compare Lobry de Bruyn and Stoger, Abstr., 1899, i, 745). The addition of sodium bromide or acetate t o alcoholic sodium ethoxide diminishes the velocity of interaction of the latter with 1-bromo-2 : 4-dinitrobenzene ; the influence of t h e bromide is much the greater, and is especially notable in the cases where the alcohol is diluted with water. The temperature coefficient of the action of sodium ethoxide and l-chloro-2 : 4-dinitrobenzene is 1.28, and for 1-bromo-2 : 4- dinitrobenzene, 1.41.The speed of replacement of chlorine in pnitrobenzyl chloride is greater than in o-nitrobenzyl chloride ; the action of sodium ethoxide and p-nitrobenzonitrile does not give a definite velocity constant because both the nitro- and cyano-group undergo replacement. The action of the ethoxide on p- or m-nitrobenzoyl chloride a t 0' is too rapid for measurement. W. A. D. Molecular Weight of Nitrosoaryls. By EUCAEN BAMBERGER and ADOLF RISING (Ber., 1901, 34,3877-3880).-Nitrosobenzene, 0- and p - bromonitrosobenzene, 0- and p-nitrosotoluene, nitroso-p-xylene, and 1- nitroso-2 : 4-xylene were found to give normal values for the mol. weight, both in freezing benzene and in boiling acetone ; these substances all dissolve with a bluish-green or green colour. Nitrosomesitylene gave M = 180.4 in boiling acetone and M = 233 (mean value) in freezing benzene, the calculated value being M = 149 ; similarly, 1-nitroso-2 : 6- xylene gave M = 188 (mean value) in boiling acetone and M = 237(meanORGANIC CHEMISTRY.89 value) in freezing benzene, the calculated value being M = 135. The indications of polymerisation to a double molecule which are thus afforded correspond closely with observations made on the colour of the solutions ; both substances dissolve in the cold with an exceedingly faint bluish-green colour, which becomes darker on heating, as the colourless polymeride dissociates, and gradually becomes less intense when cooled, the polymerisation taking place only slowly. It is noteworthy t h a t only the diortho-derivatives of nitrosobenzene are polymerised ; for similar observations in the fatty series, compare Piloty (Abstr., 1898, i, 289).The only derivative of nitrosobenzene which appears to be uni- molecular in the solid state is 3 : 4-dimethylnitrosobenzene (Abstr., 1901, i, 529), which forms a clear, bluish-green solid. Diphenyl Derivatives. By FRITZ ULLNANN and W. RUSEEL EORGAN (Ber., 1901, 34, 3802-3805. Compare Abstr., 1901, i, 586). -On adding a solution of o-nitrobenzenediazonium chloride to a cold solution of cuprous chloride, a small quantity (17 per cent.) of o-chloro- nitrobenzene is formed, together with a much larger quantity (68 per cent.) of 2 : 2’-dinitrodiphenyl. By thisimethod, 4 : 4’-dichloro-2 : 2’- dinitrodiphenyl was obtained from 4-chloro-2-nitroaniline (yield 59 per cent.) and 2 : 2’-dinitro-4 : 4’-ditolyl from 3-nitro-ptoluidine (yield 88 per cent.) 5 : 5’-DichZoro-2 : 2‘-dinitrodiphenyl, C,,H,CI,(NO,)~, prepared from 3-chloro-6-nitroaniline, crystallises in pale yellowish-brown needles melting at 170’.Basic Properties of Carbon and the Constitution of the so-called Triphenylmethyl. By FRIEDRICH KEHRMANN and F. WENTZEL (Ber., 1901, 34, 3815-3819. Cornpare Gomberg, Abstr., 1901, i, 77, 319, 638; Norris and Sanders, ibid., i, 198).-Triphenyl- chloromethnne dissolves in cold concentrated sulphuric acid, evolving hydrogen chloride and yielding a golden-yellow solution ; when diluted with water, the solution reuains yellow, but on further dilution be- comes colourless and gives a colourless precipitate of triphenylcarbinol. Similarly, when concentrated hydrochloric acid is added to a colourless ethereal solution of triphenylcnrbinol, the solution first becomes yellow and finally colourless, yielding ordinary tri phenylchloromethane.The authors conclude t h a t triphenylctllorometharle aud similar compounds exist in two forms, namely, CPh,Cl, colourless, and C H C l < ~ ~ $ ~ > C : C P h , , yellow. I t is from the latter t h a t Gomberg’s triphenylmethyl or rather diphenylphenylenemethane is obtained by the loss of HCI. The bivalent carbon atom would thus possess basic properties. p-Rosaniline chloride and dichromate are both anhydrous, and are obtained from the carbinol by the loss of water. The chloride reacts with concentrated sulphuric acid, yielding a golden-yellow solution, which, on diluting with ice and water, becomes paler and finally colour- less.When boiled, i t turns purple, but becomes colourless again on cooling. T. M. L. K. J. P. 0. A yellow compound, CPh3C1,SnC1,, is described. J, J. 8.90 ABSTRACTS OF CHEMICAL PAPERS. Some Relation between Physical C o n s t a n t s and Constit- ution in Benzenoid Amines. By WILLIAM R. HODGKINSON and LEONARD LIMPACH (Chem. News, 1901, 84, 221--222).-The investi- gations on the relationship between melting points and constitution in some amines (Proc., 1893, 41; Trans., 1901, 79, 1080) have been continued and i t is observed that the differences between the melting points of the formyl and acetyl derivatives of bases of the same constitution is constant or nearly so, moreover that this relationship is not disturbed by the replacement of a methyl group by an ethyl or methoxy-group, although, of course, the melting points of the latter compounds differ from those of the methyl compounds.Furthermore, the melting points of the formyl and acetyl derivatives of the tetramethyl bases correspond with the sum of the melting points of two xylidines less the melting point of formanilide. Preparation of Hexahydrobenzylamines. FARBWERKE VORM. MEISTER, LUCIUS, &BRUNING (D.R.-P. 12 1976).--HomocccmphanylaniZine, CH,*$!H-CH* CH,*NHPh I p e 2 I 9 obtained from the corresponding un- CH,*CMe-CH, CH,*yH-CH*CH,*NHPh saturated amine homocum~hernylanili~e, I $!,Me, 1 I 9 CH,*CMe-CH or its additive product with hydrogen chloride by reduction with sodium and ethyl alcohol, is a viscid, colourless oil boiling a t 220' under 20 mm.pressure. D. A. L. 2 : 2 : 4-TrimethyZhexahydrobenzylaniline, CH2-CH, "e2>CH*CH,*NHPh, prepared by reducing 2 : 2 : 4-trimethyltetrahydrobenzylaniline or its additive compound with hydrogen chloride, boils a t 190' under 15 mm. Dressure. L 6 - Chloro - 2 methyl- 5 -isoprop y lhexah y dr o benxy Zdime t h y 1 amine, C H 2 < ~ ~ ~ ? ~ ~ ~ ~ > C H * C H 2 * 3 J M e 2 , produced by the action Gf phosphorus oxychloride on 6-hydroxy-2- methyl-5-isopropylhexahydrobenzyldimethylamine (b. p. 140' under 14 mm. pressure), is a colourless oil, and on reduction with zinc dust and acetic acid containing a little hydrochloric acid it yields 2-methyl-5-iso- popylhexahydrobenzyldimethylamine, this base being a colourless oil having an odour resembling that of coniine and boiling a t 118-120" under 15-16 mm.pressure. 2-MethyL5-isopopylhexahydrobenxylaniZine, 2-methyl-5-isopropylhexa- hydrobenxylamine, and 2-methyl-5-isopopylhexcciLydrobenxyZethyZamine, obtained by reducing the corresponding unsaturated bases or their hydrogen chloride derivatives, are colourless oils boiling respectively at 215" (under 33 mm. pressure), and 226-228" and 135-140' under the ordinary pressure. p-Methyl~~exa?~ydi.obenzyZarniZine is a colourless oil boiling a t 1 9 5 O under 30 mm. pressure. G. T. M.ORGANIC CHEMISTRY. 91 New Bases from Abhydroformaldehydeaniline [Methylene- aniline] and its Homologues. ERNST ERDMANN (D.R.-P. 12 1506).-Isomerides of the anhydroformaldehyde bases are produced by dissolving these substances in glacial acetic acid a t temperatures below 25', and are isolated as amorphous precipitates on diluting the products with water.The compound, (C,H,N),, from methyleneaniline, is a pale yellow powder having no definite melting point ; it yields an ucetyl derivative, (C7H,NAc),, and when reduced with zinc dust yields a mixture of aniline and p-toluidine in approximately equal proportion. The corresponding o-toluidine and p-xylidine compounds form white powders melting a t 150' and 85-90' respectively. The p-toluidine and rn-xylidine derivatives are tarry substances. These compounds dissolve in dilute hydrochloric acid, and with the substantive cotton colouring matters form lakes which are comparatively stable to acids.G. T. M. Preparation of Aromatic Bases [by the aid of Form- aldehyde]. ERNST ERDMANN (D.R.-P. 122474. Compare Troeger, Abstr., 1888, 286). -When 4-m-xylidine, p-toluidine, or p-chloro- aniline is treated with formaldehyde solution in the presence of moderately strong hydrochloric acid, a substance is obtained possess- ing the property of forming lakes with the substantive cotton colour- ing matters, and thereby rendering these less sensitive to dilute acids. The m-xylidine and p-toluidine derivatives are yellow, amorphous sub- stances melting respectively a t 62-65' and a t 65-70'. I n the latter case, the crystalline base described by Troeger is obtained as a bye-product. p-Chloroaniline gives rise to a yellow, crystalline deriva- tive melting a t 188', the hydrochloride of which separates from water in colourless prisms.G. T. M. Mono- and Di-alkyfated Aromatic Amines. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 121683. Compare Abstr., 1901, i, 695 699).- Methylnaphthionic acid (1-methy laminonaphthalene-4-sul- phonic acid), NHMe*C,oH,*SO,H, obtained by heating sodium a-naph- thol-4-sulphonate with a 10 per cent. solution of methylamine sulphite, SO,(NH,Me),, at 150' and acidifying the product, separates from solu- tion in a crystalline form. This operation may be performed in two stages ; the first consists in converting the naphtholsulphonate into its sulphurous ester by means of sodium hydrogen sulphite, and the second in treating this product with methylamine. Sodium P-naphthol-6-sulphonate, when heated for 15 hours at 125' with an aqueous solution of methylamine and methylamine sulphite, readily yields sodium 2-methylaminonaphthalene-6-sulphonate, from which dilute acids liberate the crystalline sulphonic acid.Dimethyl-m- aminophenol is readily produced by treating resorcinol with a solution of dimethylamine and its sulphite at 125' and is isolated from the pro- duct in the form ol its hydrochloride. G. T. M. Preparation of P-Naphthylamine Derivatives. BADISCHE ANILIR- & SODA-FABRIK (D.R.-P. 122570. Compare Abstr., 1901, i, 6 95, 6 9 9 ).-Phenyl-~-nuphthylarnine-6-sulphonic acid, produced by92 ABSTRACTS OF CHEMICAL PAPERS. heating together sodium P-naphthol-6-sulphonate, aniline, and sodium hydrogen sulphite solution, is readily soluble in water and yields a bluis h-viole t azo-compound with diazot ised pnitroaniline .2 : 5-Dihydroxynaphthalene-7-sulphonic acid, when treated in this manner, yields an amino-acid which is probably 2-phenylamino-5-hydr- oxynap?&ialene-7-sulphonic acid. 2-o-ToZylamino-S-hydroxynap?~thulene- 6-sulphonic ucid is obtained from 8-hydroxy-P-naphthylamine-6 -sulphonic acid, o-toluidine, and sodium hydrogen sulphite. 2-o-XylyZanaino-5-?~ydr- oxynaphthalene-~-su~p?~on~c acid is produced from o-xylidine and 5- hydroxy-~-naphthylamine-7-sulphonic acid. Similar substituted p- naphthylamine derivatives are obtained from /3-naphthol-6-sulphonic acid and p-phenylenediamine, and also from 8-hydroxy-P-naphthyl- amine-6-sulphonic acid and p-aminophenol. G. T. M. Naphthalenoid Thiocarbamides containing Hydroxyl Groups.FARBENFABRIKEN VORM. F. RAYER & Co. (D.R.-Y. 122286. Compare D.R.-P. 1 16201 and 11 6 2 0 0 ) . - T ~ ~ i o c a r b o n y l ~ i ~ y ~ ~ o ~ y ~ i n a p ? ~ t ? ~ y l ~ ~ disulphonic acids, CSINH*CloH,(OH)*SO,H],, are obtained by the action of carbon disulphide, sulphur, and sodium carbonate solution on the aminonaphthols and their sulphonic acids in which the amino- and hydroxy-radicles are present in positions other than 1 : 2 or 1 : 8 with respect to each other. G. T. M. Preparation of Tertiary Aromatic Bases from their Alkyl Haloids. By JOHANNES PINNOW (Bey., 1901, 34, 3772).-A claim for priority in the use of the method for converting aromatic quaternary salts into the corresponding tertiary bases by heating with aqueous ammonia (compare Abstr., 1898, i, 184; 1899, i, 588, and Scholtz, Abstr., 1898, i, 567; 1901, i, 749).G. T. M. Derivatives of Phenyl Ether. 11. By ALFRED N. COOK (J. Amer. Chegm. Xoc., 1901, 23, 806-813. Compare Abstr., 1901, i, 144).-o-Nitrophenyl o-tolyl ether, NO,*C,H,-O*C,H,Me, obtained by the action of o-bromonitrobenzene on potassium o-tolyl oxide, is a dark red liquid which boils at 194-196' under 14 mm. and decomposes when heated under atmospheric pressure ; it is not volatile with steam, has a n oily taste, a sp. gr. 1.195 at 20', and is soluble in the usual organic solvents. On reduction with tin and hydrochloric acid, the hydrochloride of o-aminophenyl o-totyl ether is produced as a white, waxy mass ; the base could not be isolated on account of its instability.By the action of sulphuric acid on o-nitrophenyl o-tolyl ether, a sulphonic acid, NO2*C,,H7OMe*S0,H, is produced, which is a reddish- yellow, viscous liquid, soluble in 2.5 parts of water at SO', and readily so in alcohol, benzene, or light petroleum; the barium, strontium, and lead salts are soluble in water to the extent of 0.745, 2, and 8-17 per cent. at loo', and 0.12, 0.68, and 3.5 per cent. at 31' respectively. o-Nitrophenyl in-tolyl etlier is a red, oily liquid which boils a t 223O under 30 mm., but decomposes if heated under atmospheric pressure ; i t is not volatile with steam, has a sp. gr. 1.208 a t 27', and is readily soluble in the usual organic solvents. o-Amirtophsnyl m-tolyl ether hydrochloride is a clear, viscous substance, readily soluble in alcohol orORGANIC CHEMISTRY.93 ether and sparingly so i n water; the base is very unstable and could not be isolated. o-h7itrophenyl -m- to1 yl-ether-sulphonic acid crystallises in short, yellowish-brown needles, and is soluble in water, alcohol or ether ; the barium salt is soluble in water t o the extent of 1.1 per cent. at 82' and 0.61 per cent. at 35'. o-Nitro~~enyZ-p-toZyE-et~er-su~J~orzic acid forms reddish-brown crystals, soluble to the extent of 9.8 per cent. in water nt 31', and readily soluble in alcohol, ether, benzene, or glacial acetic acid ; the burium salt is soluble in water t o the extent of 69.1 per cent. at SO" and 14.7 per cent. at 27'. E. G. Ethoxyisoeugenol (Monoethoxymethylpropenylcatechol Ether). C ~ S A R POMERANZ (D.R.-P.122701. Compare Abstr., 1892, 9 7 2 ).-Etll,oxyisoeugenoZ (2-monoet J~oxymethyZ-4-propenylcatecJ~oZ ether), OEt*CH,*O*C,H,(OH)*CH:CHMe, results from the action of alcoholic potassium hydroxide solution on safrole at 140-150"; it is a colour- less, almost odourless oil boiling a t 173" under 22 mm. pressure. G. T. M. GoChavibetol. CZSAR POMERANZ (D.R.-P. 123051. Compare Abstr., 1901, i, 699).-The condensation products of the alcohols with isosafrole having the general formula OR-C H2*O*U,H,( OH)*CH: CH He yield isochnvibetol when treated with dilute alcoholic solutions of the mineral acids. G. T. M. Substituted Thiocyanates of the o-p-Dinitrohydroxy- diphenylamines. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 122569).-1 : 3-Dithiocyano-4 : 6-dinitrobenzene, obtained by adding powdered potassium thiocyanate or the corresponding salt of another metal t o an acetone solution of 1 : 3-dichloro-4 : 6-dinitrobenzene, crystallises from alcohol in pale yellow leaflets and decomposes at 185'.When this compound is treated with a mixture of sodium acetate, alcohol, and a n aminophenol for 8 hours at 65', one of the thiocyano-groups is removed and a diphenylamine derivative is produced. o-p-Dinitro-m-thiocyano-p-h.ydroxydiphenyZamine, SCN*C,H,( NO,),*NH*C,H,*OH, obtained fromp-aminophenol, separates from acetone, alcohol, or glacial acetic acid in red crystals melting at 227-228"; the corresponding compound from o-aminophenol melts at 255'. SCN*C,H,( N0,),*NH.C6 H,( OH) *SO,Na, of the p-aminophenol-o-sulphonic acid derzvative crystallises in reddish- brown needles ; the aminosalicylic acid compound is a yellowish-brown powder ; these substances decompose without melting.The sodium salt, G. T. M. Preparation of Chlorides and Anhydrides of the Carboxy- acids. CEIEMISCHE FABRIK VON HEYDEN (D.K.-P. 123052).-When 1 mol. of a n aromatic sulphonic chloride is heated with 1 mol. of the anhydrous salt of a carboxylic acid, the corresponding acid chloride is formed in accordance with the following equation : Ph*SO,Cl+ R-C0,Na = Ph*SO,Na + R-COCl. If 2 mols. of the anhydrous salt are employed, t h e corresponding anhydride is produced. Acetyl chloride and acetic94 ABSTRACTS OF CHEMICAL PAPERS. Chloronitrobenzoic ............ 3 , ............ 9 , 9 , ........... ........... Bromonitrobenzoic ............9 9 ,¶ 9 9 ............ ........... ............ anhydride are obtained by the action of y-toluenesulphonic chloride on 1 and 2 mols. of sodium acetate respectively. Propionic and benzoic anhydrides and salicylyl chloride may also be prepared by this process. G. T. M. Phenylglycine-o-carboxylic Acid. DANIEL VORLANDER and RUDOLF VON SCHILLING (D.R.-P. 12 1287).-Nitroso-o-tolylglycine, C,H,Me*N(NO)*CH,*CO,H, an oil obtained by treating o-tolylglycine with sodium nitrite and dilute sulphuric acid, yields nitrosophenyl- glycine-o-carboxylic acid (m. p. 1 20°) on treatment with potassium permanganate solution ; the oxidation product when reduced with zinc dust and sodium hydroxide or sulphurous acid, or when boiled with alcoholic hydrogen chloride, gives rise to phenylglycine-o-carboxylic acid (compare Abstr., 1900, i, 295, and 1901, i, 462, 463).G, T. M. 1 : 2 : 5 1 : 3 : 3 1 : 3 :6 1:3:2 1 : 2 : 5 1 : 2 : 3 1 :3 : 6 1 : 3 : 2 Electric Conductivity of Chloro- and Bromo-nitrobenzoic Acids. By ARROLD F. HOLLEMAN and B. R. DE BRUYN (Rec. Truv. Chim., 1901, [ii], 20, 360-364).-The following table gives a com- parison of the afinity constants, k, of chloro- and bromo-nitrobenzoic acids as determined with carefully purified material and as calculated by Ostwald and Bethmann's method : Acid. Structure. CO,H : X : NO,. k cnlc. 0.75 0.75 1-60 1-60 0 -83 0.83 1-41 1'41 Found PCm * 356 356 366 356 353 353 355 353 k found. 0 '62 0.87 1-42 0'44 0.91 1-16 1'55 0 -34 There is a satisfactory agreement between observed and calculated values except in the case of the 1 : 3 : 2-acids. I n the original paper, a table is given showing a similar comparison of a large number of other disubstituted benzoic acids, and here again satisfactory agree- ment is visible except in the case of a-nitrophthalic acid (calc. 12.4, found 1-22), P-resorcylic acid (calc.1.73, found 5.0) and o-nitrosalinylic acid (CRIC. 0.58, found 1.57). I n all cases where a divergence occurs, the position of the groups is adjacent. It is true that o-chloro- and 0- bromo-m-nitrobenzoic acids and hydroxysalicylic acid [CO,H : (OH), 7 1 : 2 : 31 give a good agreement, but here the halogen or hydroxyl is in the ortho-position relatively to the carboxyl ; when a great diver- gence occurs it is the nitro-group which is in this position.W. A. D. Anthranil. By OTTO BUHLMANN and ALFRED EINHORN (Bey., 1901, 34, 3788--3793).-The substance obtained by Einhorn and BullORGANIC CHEMISTRY. 95 (Abstr., 1837, i, 345) by the action of hydroxylamine hydrochloride on ant.hrani1 in alcoholic solution is. shown to be the oxime of o-amino- benzaldehyde, and not the oxime of anthranil ; the hydroxylamine has acted as a reducing agent. Free hydroxylamine and anthranil yield a compound, C7H802N2, which crystallises from benzene in white, prismatic needles melting a t 114-115', and is not the oxime of anthranil, but probably o-hydroxyl- aminobenzaldehyde; it dissolves in dilute alkalis and acids, and is quantitatively converted by the latter into anthranil. With benzalde- hyde, i t gives a condensation product, C1,H,,02N2, which crystallises in pale yellow, prismatic needles melting and decomposing at 164'.Hydrazine hydrate and anthranil react in the presence of alcohol a t 100' to form a compound, C7H,0N,, which crystallises in pale-yellow, transparent, prismatic leaflets melting and decomposing a t 120' ; dilute acids immediately decompose it into authranil and a hydrazine salt, From phenylhydrazine and anthranil a compound, Cl,H130N3, is obtained as yellow, prismatic needles, which darken at 140°, and melt and decompose at 155'; when boiled with acetic acid, or heated alone, i t is converted into the phenylhydrazone of o-aminobenzaldehyde. Other compounds, besides anthranil, which contain the group *CO*NH*, are able to combine with hydrazines without elimination of water ; thus when benzamide and phenylhydrazine are heated at 100' in acetic acid solution, acetyZbenxnmidephenylIhgdraxone hydyate, NHPh*NK*CPh(NH,)*O*COMe, is formed, and crystallises from benzene in white, silky needles melting at 105O; acids decompose it into phenylhydrazine, acetic acid, and benzamide.By EUGEN BAMBERGER and ED. DE- MUTH (Ber., 1901,34, 4015-4028. Compare Buhlmann and Einhorn, preceding abstract).-When anthranil (1 mol.) and hydroxylamine, (3 mols). are heated together in solution in absolute alcohol, 0-hydroxyZ- aminobenxaldoxirne, OH*NH*C,H,*CH:N*OH, is formed ; this substance can also be obtained by reduction of o-nitrobenzaldoxime with zinc dust ; it crystallises in long, white, silky needles melting at 120-121°, is soluble in alkalis with a lemon-yellow colour, and reduces silver nitrate and Fehling's solution.I n dilute acids, it dissolves, and is then con- verted into an$hranil and hydroxylamine. With aldehydes, it condenses; thus with benzaldehyde, a benxylidene compound, CHPh b >N*C,H,*CH:N*OH, is formed which crystallises in lustrous needles melting a t 172-172.5O ; the p-nitroberwylidene compound crystalhes in small, silky needles ; both substances dissolve in alkali hydroxides with an intense red coloration, Molecular proportions of anthranil and hydroxylamine, dissolved in dilute alcohol, ..gave mainly o-axoxybenxacldoxime, ON,(C,H,* CHXOH),, which crystallises in needles melting at 210*5-211° ; this azoxy-corn- pound was also prepared from o-azoxybenzaldehyde and hydroxylamine. When 2 mols.of hydroxylamine interact with 1 mol. of anthranil, besides o-azoxybenxaldoxime,o-triazobenzaldoxime,o-aminobenzaldoxime, and benzaldoxime are formed. Prolonged action of a still greater K. J. P. 0. Constitution of Anthranil.96 ABSTRACTS OF CHEMICAL PAPERS. excess of hydroxylamine on anthranil produces mainly o-aminobenzald- oxime together with the other substances just mentioned. In the presence of potassium hydroxide, hydroxylamine and anthranil yield o-ni tro- and o-amino-benzaldoxime. The view is expressed that the first action of hydroxylamine on anthr- . From N-- NH*OH a d is one of hydration, C,H4<b ,>o + H,O C,H,<CHO the hydroxylaminobenzaldehyde, o-aminobenzaldehyde, o-nitrobenzalde- hyde, and o-azoxybenzaldehyde would be produced respectively by oxidation or reduction.It is suggested that the o-triazobenzaldehyde is produced by union of the group @HO*C6H,*N: (formed from anthr- anil) and molecular nitrogen, which arises by oxidation of the hydroxyl- amine (compare this vol., i, 25). I n the presence of excess of hydroxyl- amine, these aldehydes would be converted into oximes. K. J. P. 0. Methyl Methylanthranilate. SCHIMMEL & Co. (D.R.-P. 122568)- Methyl methylanthranilate, NHMe*C6H4*C02Me, prepared either by treating methylanthranilic acid with methyl alcohol and concentrated hydrochloric or sulphuric acid, or by heating sodium or potassium anthranilate with potassium hydroxide and methyl iodide under pres- sure, boils a t 130-131" under 13 mm. pressure, and has a sp.gr. 1.120 at 15"; its solution has a blue fluorescence. This ester has the char- acteristic odour of mandarin oil, and is contained in this essence to the extent of 1.5 per cent. Preparation of o-Benzoicsulphimide (" Saccharin ") and other Aromatic Sulphonamides. BASLER CHEMISCHE FABRIK (D. R.-P. 122567). -Benzene- and o-toluene-sulphinic acids, dissolved in a mix- ture of alcohol and excess of aqueous ammonia and treated with chlor- ine at 35-40', yield the corresponding amides. o-Benzoicsulphimide (" saccharin ") is obtained by this process in one operation, and from monomethyl o-carboxybenzenesulphinate, 8O2H*C,H4*CO2Me (m, p. 98-99"), the latter substance being produced from diazotised methyl anthranilate by the action of alcoholic sulphurous acid and copper sulphate.G. T. M. Stable Carbonyl Derivatives of Indigo-white. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 121 866).--The normal carbonic ester of indigo-white is produced on treating a mixture of indigo- white, acetone, and sodium hydroxide solution with carbonyl chloride ; it decomposes without melting, yielding indigotin, and is hydrolysed by warming with dilute solutions of the alkali hydroxides. The product of the action of methyl or ethyl chlorocarbonate on indigo-white in the presence of alkali hydroxides, when extracted with alcohol, yields a n insoluble ester crystallising from acetone in felted needles and melting at 257-259" ; the alcoholic extract contains a second ester separating in needles and melting at 110-1 12". These esters are also obtained along with the infusible product by treating indigo-white with car- bony1 chloride in aqueous sodium hydroxide solution. Phenanthrene Derivatives.By ROBERT PSCHORR ( B ~ Y . , 1901, 34, 3998-4007).-[ Wit h C. SEYDPL .]-The hitherto unknown G. T. M. G. T. M.ORGANIC CHEMISTRY. 97 2-methoxyphenanthrene was synthesised by condensing 6-nitro- 3-methoxybenzaldehyde with sodium phenylacetate in the presence of acetic anhydride at 100'; the a-phenyl-~-6-nitro-3-methoxycinnamic acid, N02*C,H,(OMe)*CH:CPh*C02H, thus obtained crystallises in pale yellow leaflets melting at 165-166", and yields sparingly soluble silver, lead, and calcium salts, which all crystallise in needles. a-Phenyl-P-3-methoxy-6-aminocinnamic mid, N H,*C,Ha(OMe)*CH:CPh*C02H, obtained by reducing the corresponding nitro-compound with ferrous sul phate in presence of ammonia, crystallises in greyish-violet leaflets having a silvery lustre, which become coloured at 182-187' and melt at 227-228' ; this substance' forms well-crystallised salts both with acids and bases.a-P?LenyZ-P- 6-diazo-3-methoxycinnumic acid was obtained in the form of the sulphate from the last-mentioned substance ; the sulphate crystallises in yellow prisms which explode a t 140-150'. On boiling the aqueous solution of the sulphate and gradually adding sodium car- bonate, 2-metAoxyphenanthrene-9-carboxyZic acidis obtained; i t crystallises in lustrous prisms or needles melting at 2%', and exhibits in solutior, a blue fluorescence ; the ammonium, silver, ferric, cupric, and lead salts are crystalline and sparingly soluble.z-A~ethoxyp?~enanthrena is pre- pared from the acid by distilling it under 100 mm. pressure; i t crystallises in lustrous leaflets melting at 99', and, in solution, exhibits a faint blue fluorescence ; the picrate crystallises in orange needles melting at 124". [With AUGUST KLEIN.]-F~o~ the sulphonic acids obtained from phenanthrene, two were isolated by fractional crystallisation of the lead salts, which crystallise respectively with 2 and 3 H,O. From the sulphonic acid, which corresponds with the lead salt, crystallising with 2H,O, a phenanthrol was prepared by fusion with 50 per cent. potass- ium hydroxide ; it crystallises in lustrous leaflets melting at 168'; its acetyl derivative crystnllises in needles melting at 141' ; i t s methyl ether is identical with the 2-methoxyphenanthrene just described.The hydroxyl group is therefore in position 2. This phenanthrol is iden- tical with thecompound obtained by Werner and Kunz (Abstr., 1901, i, 696) from phenanthrylamine, the constitution of which is therefore confirmed. 2-Methoxyphenanthrene, unlike the 3- and 4-derivatives, yields only a monobromo-derivative, which crystallises i n needles melting at 176'. On oxidising 2-acetoxyphenanthrene with chromic acid, a quinone, CIBHloO,, is formed as yellowish-red crystals melting at 222'. r h e lead phenanthrenesulphonate crystallising with 3H,O yields 3-phenanthrol (Abstr., 1900, i, 487), which was recognised by pre- paration of the acetyl derivative and methyl ether (Bbstr., 1900, i, 233).The latter gives a dibromo-derivative which crystallises in pale red needles melting at 150'. 3-Acetoxyphenanthrene, on oxidation, yields a quinone, C16H1004, which forms yellow leaflets melting at 206O ; from the latter, on hydrolysis, is obtained 3yhenanthrol~uinone, C14H803, crystallising in yellowish-red needles which begin to decom- pose at 315' and finally melt at 330". The temperatures quoted are corrected. K. J. P. 0.98 ABSTRACTS OF CHEAIICAL PAPERS. The Mononitrophthalic Acids. By MARSTON T. BOGERT and LEOPOLD BOROSCHEK (J. Amer. Chem. ~ o c . , 1901, 23, 740-761).- 3-Nitrophthalic acid, when heated in a closed tube, melts at 222', but in an open tube it decomposes a t about 207" with formation of the anhydride, The aniline salt (Graebe and Buenzod, Abstr., 1899, i, 762) crystallises in colourless needles and melts a t 185-187".The acid o-toluidine salt, NO,*C,H,(CO,H),,NH,*C,H,Me, forms slender, white needles, melts a t 181', and at a slightly higher temperature de- composes into water and the o-tolil. NO,=C,H,(CO,H)*CO,Et, is a white, crystalline substance melting at 157". The anhydride, obtained by heating the acid a t 235-240' for 6-8 hours, crys- tallises in colourless needles and melts a t 163'. The imide, prepared by the action of heat on tho ammonium hydrogen salt, crystallises in pale yellow, lustrous needles, melts a t 215-216", and furnishes a white, crystalline potccssiunz salt. The arnide melts and decomposes at 200-201° with formation of the imide. NO,* C,H,( CO,H)*CO *NH,, obtained by heating the imide with baryta water a t SO", melts at 156" with production of the imide.The ethylimide crystallises in long, yellow needles and melts at 105'. The anil melts at 137'. The anilic mid, NO,*C,H,(CO,H)*CO*KHPh, forms pale yellow needles and melts a t 180° with formation of the anil. The 0-, m- and p-nifroanils melt a t 3 67", 219", and 249' and the 0-, m- and p-tolils a t 145', CO'YH - or 139", and 154' respectively. CO*NH The monoethyl ester, 3-Nitrophthalamic acid, The hydruxide, NO,-U,H,< N0,*C,H3<CO>N co *NH,, forms pale yellow, microscopic crystals and melts and decomposes a t about 320'. When 3-nitrophthalic anhydride is heated with phosphorus pentachloride, 3-chlorophthalic anhydride is produced, which on boiling with dilute hydrochloric acid yields the corresponding acid melting at 186".3-Chlorophthalimide crystallises in white needles; when heated in an open tube, it sublimes, but in a closed tube i t melts a t 118-120'. 4-Nitrophthalic acid is best prepared by the oxidation of p-nitro- phthalide with alkaline potassium permanganate. When an alcoholic solution of 4-nitrophthalic anhydride is hoiled for 8 hours, an ethyl ester, N02*C,H,(C0,H)*C0,Et~, is produced which melts at 141-150°, and ap ears to be an isomeride of the ester (m. p. 127-128°) obtained by Milyer (Abstr., 1882, 404) by the action of hydrogen chloride on an alcoholic solution of the acid. The imide crystallises in pale yellowish- brown flakes, melts a t 197", and yields a potassium salt. The arnide melts a t 200' with Pormation of the imide. The ethylimide forms pale yellow scales and melts a t 111-112'.The anilic mid forms pale yellow crystals, and melts at 181' with pro- duction of the anil. The 0-, m- and p-nitroanils melt a t 233', 243O, and 251-253', and the 0-, m- and p-tolils a t 160°, 197', and 165O re- spectively. The p-tolilic acid crystallises in white needles, and melts at 172" with formation of the p-tolil. The hydvaxide forms small yellow crystals, gives a white sublimate at 270', darkens at 280°, and remains unmelted at 300". 4 : 4'-Axophthalic m i d , obtained by reduc- The anil melts at 194'.ORGANlC CHEMISTRY. 99 ing 4-nitrophthalic acid with sodium amalgam, forms a salmon-coloured, crystalline powder, does not melt at 360°, and furnishes a red, crystal- line silver salt which is insoluble in hot water; if, however, the azophthalic acid is prepared by the oxidation of 5 : 5'-azophthalide with potassium permanganate, it melts and decomposes at 285-300°, and yields a silver salt soluble in hot water.5 : 5'-Axophthalide, obtained by the reduction of p-nitrophthalide with sodium amalgam, forms small, red crystals and melts and decomposes at 260-280'. Derivatives of the Two Nitrophthalic Acids. By PAUL E. G. ONNERTZ (Ber., 1 9 0 1, 34, 3 7 35 -3 74~).-P-Ethoxyphthalylace~ic acid, OEt.7 H >C:CH*CO,H, prepared by heating ethoxy phthalic an- co hydride with acetic anhydride and sodium acetate, forms small, yellow needles, melts a t 246-248' and does not dissolve in water. Beneyl- idene-P-ethoxypiithalide, O E t * C 6 H 3 ~ C O > 0 , prepared from ethoxyphthalic anhydride and phenylacetic acid, forms prismatic crystals and melts a t 133-134'.When warmed with potassium hydroxide, it is converted into 4-(or 5-)ethoxydeoxybenxoin-2-carboxylic acid, C02H*C6H3(OEt).CO*CH2Ph, which crystallises from a large bulk of hot water in minute, white prisms and melts at 95-96'; with alcoholic potassium hydroxide or sodium ethoxide, on the other hand, 6-ethosy-2 -phenyl- 1 : 3-diket ohydrindene, OEt*c6H3<EE>CHPh, is obtained, which crystallises from boiling alcohol in yellow plates and melts at 172' ; with alcoholic ammonia, &(or 5-)ethoxydeoxybenxoin-2- carboxykumide is formed, which crystallises from aqueous alcohol in well-formed, rhombic prisms, melts at 149-151°, and is converted by acetyl chloride into benxylidene-p.ethoxyphthalimidine, C( * CHPh) C( 'CHPh) 0Et*c6H3<L(!O>0 ; this separates from dilute acetic acid in yellow flakes and melts at With hydroxylamine, ethoxydeoxybenzoincarboxylic acid gives the oxirnino-lactone of benxyL4-(or 5-)ethoxyphenylketoxirne-2-carboxylic acid, OEt*C6H3<C0 o, which crysfallises from alcohol in long, transparent, prismatic tablets and melts at 1120. With phenyl- hydrazine, it gives 6-(or 'I-)ethoxy-l -benxyl-3-phenyZphthalaxone, OEt* C,H,<$Tg:l>N, which crys tallises from hot alcohol in pale yellow needles and melts at 126-127'.With sodium amalgam, the first product is a-hydroxy - 4 -(or 5 -)ethoxydibenx y I- 2 -car boxy lic acid, OEt*C,H,(CO,H)*CH(OH)*CH,Ph, which readily, passes by loss of a molecular proportion of water, into benql-P-ethoxyphthalide, 160-1 62'.C(CH P h ) : r CH(CH,Ph) 0 E t* c, q<-- (70-0 ; this crystallises from alcohol in microscopic prisms and melts at 87-88'. 4-( or 5 -)EthoxystiZbene-2-carboxylic acid, OEt C,H,( CO,K)*CH: CHPb, isomeric with the preceding compound, is formed wheu the hydroxy-100 ABSTRACTS OF CHEMICAL PAPERS. acid is heated with potassium hydroxide at 213O; i t crystallises from alcohol in small needles and melts a t 172". 4- (or 5-) Ethoxydibenxyl-2- cavboxylic acid, OEt*C,H3(C0,H)*CH,*CH2Ph, prepared by reducing ethoxystilbenecarboxylic acid with sodium amalgam, separates from alcohol in long, silky needles and melts at 117". 4-Bromo-6-(or 7-) ethoxy - 3-phenytdih ydroisocoumarin, OE t *C6H:3<co CHBr*(?HPh, -o prepared by the action of bromine on ethoxystilbenecarboxylic acid, crystallises from absolute alcohol in colourless needles anb melts at 103'., prepared CH:yPh co-0 6- (or ?-)Ethozy-3-phenylisocoumarin, OEt *C,H,< by distilling the preceding compound, separates from alcohol in large, flat crystals and melts at 144-145'. 4'- (or 5'-)E~l~oxydeoxybeizxoira- 2'-ca~boxylic acid, OEt*C,H,( CO,H)*CH,*COPh, prepared by the action of potassium hydroxide on the preceding compound, crys- tallises from dilute alcohol in long, silky needles and melts at 172--173" ; with hydroxylamine, i t gives the oximic acid, OEt*C,H,( CO,H) CH,*CPh:NOH, which separates from dilute alcohol in small, pale rose-colorired, pointed crystals, and melts and intumesces a t 174" ; when this is allowed to cool after fusion and crystallised from CH-fiPh is obtained in CO.0.N ' acetic acid, the oximinokcctone, oEt*C,H,< clear, rhombic tablets melting at 164.5-166".The phenylhydraxone, CO,H*C,H,*CH,*CPh:N,H?h, preparod by the action of ghenyl- hvdrazine on the ketonic acid. separates from alcohol in white, felted flikes and melts at 187". 6-(or ~--)Ethox~-3-~henyldihydroisocoum~rin, , prepared by reducing the ketonic acid with CH,*yHPh OEt *C6H3<~o-() sodium amalgam, crystallises from dilute alcohol in microscopic tablets and melts at 83-84'; by heating the crude alkaline solution obtained on reduction, the isomeric P-ethoxystilbenecarboxylic acid is formed, as in the case of the isomeride described above. 6-(or 'i-)Ethoxy-3- ,,CH: C P h phenylisocarbostyril, OEt 'C6H3\CO-&H , prepared by the action of ammonia on ethoxyphenylisocoumarin, forms minute, pointed crystals and melts at 16 1'.l-ChZo~o-6-(or 7-)etl~ox~-3-p?~enyliso~z~inoline, OEt-C6Hs<CCl:k , prepared by the action of phosphorus oxy- chloride on ethoxgphenylisocarbostyril, crystallises from hot alcohol in pointed prisms and melts a t 113-114'. l-Iodo-6-(or 7)-hydvoxy-3- phenylisopuinoline, OH*C,H,< CH:?Ph, prepared by the action of hydriodic acid and phosphorus on the preceding compound, forms yellowish, pointed crystals and melts at 141-143'; by the further action of hydriodic acid and phosphorus, the hydriodide of 6-(or 7-) hydroxy-3-phenyZisopuinoline, OH*C,H,< cH:qph, is obtained in yellow, microscopic needles which darken at 180', become deep brown- red a t 190', sinter at 196", and melt and decompose at 203-204' ; CH:CPh CI=N CH:NORGANIC CHEMISTRY. 101 the 6ase crystallises from a mixture of alcohol and light petroleum in microscopic, felted prisms, which sinter at 190-191O and melt a t 196-197' to a yellowish-brown liquid ; the hydrochloride forms long, silky prisms ; the platinichlovide separates from alcohol in golden-yellow needles, sinters at 253', and melts at 267-269O ; the picrate crystallises in long, yellow needles and melts a t 211-212'.a-Aminophthalic m i d , NH2:C,H,(C02H)?, is a yellow, crystalline powder, dissolves readily in acids and alkalis, darkens at 174', sinters a t 179-181°, and melts a t 184-186O with liberation of carbm dioxide ; the copper salt crystallises in small, green, sparingly soluble tablets.Methyl a-methoxyphthalute, OMe-C H (C02Me)2, crystallises from hot water in small needles and melts at7f'. Ethereal Carbonyldiphenylglycinates. BADISCHE ANILIN; & SODA-FABRIK (D. R.-P. 12 11 98).--EthyZ car6onyZdipAenylgZycinate, CO(NPh*CH,*CO,Et),, prepared by passing carbonyl chloride through melted ethyl phenylglycinate, is,separated from the soluble hydrochloride of the unaltered ester by treatment with water ; it melts at 57'. The corresponding methyl ester is obtained in a similar manner. These substances are readily converted into indigotin (compare Abstr., 1901, i, 714). G. T. M. By MARTIN FREUND and LUDWIG MAI (Ber., 1901,34, 3717-371 9).-As a lactone, artemisin dissolves in dilute aqueous barium hydroxide, and on adding silver nitrate to a solution of the soluble barium salt so formed, the silver salt, C,,H,,O,Ag,BH,O, is precipitated ; the derived methyl ester, C16H2205, crystallises from alcohol and melts and decomposes at 180'.On distilling artemisin with zinc dust, a dimeth?/lnaphthalene boiling a t 264' is formed, which is not identical with that obtainer! by Cannizzaro from santonin, as its picrate melts at 119O, not a t 139' ; it is perhaps identical with the P-dimethyl- naphthalene of Ernmert and Reingruber jb. p. 264", picrate m. p. 118O, Abstr., 1882, 733). So-called Basic Bismuth Gallate of the Codex. By PAUL THIBAULT (J. €'harm. Chim, 1901, [vi], 14, 487-493. Compare Abhtr., 1893, i, 643 ; 1901, ii, 106).-An excess of crystallised gallic acid is added to pure hydrated bismuth oxide (the anhydrons oxide has no action) previously mixed with water, and the mixture is well stirred.The action is complete a t the end of 24 hours, and the product, after being washed and dried, is amorphous and opaque, and has the composition C,H,O,Bi. If the mixture is left fora fortilight, the bismuth compound appears in the form of small, yellow, micaceous crystals, which have the same composition as the amorphous compound. Sulphuric acid diluted to a fifth disholves this compound in the cold, but when diluted to a tenth only dissolves i t when heated. It dissolves in a solution of potassium hydroxide, and the residue left after evnpor- ation and removal of the excess of potassium hydroxide is of definite composition and corresponds with the formula K,BiC7H70,,2H20.From a consideration of the properties of this potassium salt, the so- called basic bismuth gallate must be regarded, not as a bismuth salt, but as a bismuthigallic acid. The action of sodium hydroxide is similar to that of potassium hydroxide. T. AT. L. Artemiain. W. A. I). H. R. LE S. VOL. LXXXII. i. i102 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Hydrogenised Cyclic Aldehydes. FARBWERKE VORM. MEISTER, LUCIUS & BR~NXNG (D.R.-P. 121975. Compare Abstr., 1900, i, 69 1, 692).-Z't+nethyltetrahydrobenxcclclehyde, produced by oxidising trimethyltetrih ydrobenzylaniline with chromic acid mixture in boiling aqueous solution, is a colourless oil volatile in steam and boiling a t 90-91' under 18 mm.pressure; it is isomeric with cyclocitral ; its odour when concentrated resembles that of cedar Wood, but when diluted recalls that of violets. 3 : 2 : 4-Z'rz'meth~~ZhexahydrobenxaldeJ~~de, prepared in a similar manner fro& trirr;ethylhexahydrobe3laylaniline, is a colourless, pungent oil. 2-MethyL5-isopropylhexah~dro6e~zaZdehyde, derived either from methylz'sopropylhexahydrobenzylethylamine or methylisopropylhexa- hydrobenzylaniline, is a colourless, pungent oil, which, when diluted, has the odour of geranium oil. obtained from 2-methyl-5-isop~pyltetrahydrobenzylideneaniline, is a colourless oil boiling a t 98' under 15 mm. pressure and has an odour of orange oil. CH,*YH-C*CHO CH,*CMe-CH , prcjduced from the correspond- ing amine, CIGH,,*NHPh, is a colourless pungent oil boiling a t 104-105O under 15 mm.pressure. Acetates derived from the Aromatic Aldehydes. FARBENFABRIHEN VORM. F. BAYER & Co. (D.R.-P. 12 1788).-Aromatic compounds containing methyl groups are oxidised to aldehydes by chromic acid or it,s salts in the presence of acetic anhydride, the pro- ducts being shielded from further oxidation by conversion into the corresponding acetyl esters. p-Nitrobenxylidene diacetate, N0,*C6H4.CH(OAc)2, results from the action of chromic acid on a cold solution of p.nitrotoluene, sulphuric acid, acetic anhydride, and acetic acid ; it crystallises from alcohol in truncated prisms and melts at 125'. The corresponding diacetate from o-nitrotoluene melts a t 87-88', The tetra-acetate, C,H,[CH(OAC)~]~, derived from isophthalaldehyde and produced by the oxidation of m-xylene by the preceding method, separates in needles melting at 101'. The tetra-acetates derived from 0- and p-xylene melt reRpectively a t 126-127' and 164-165'.These acetates on hydrolysis yield the corresponding aldehydes, New Aromatic Aldehyde occurring in Eucalyptus Oils. By HENRY G. SMITH (J. Roy. SOC. N.S. Wales, 1900, 286--295).-The crude oil of Eucalyptus hemiphloia was distilled; after the con- I YMe2 I1 CamphenaldeJhyde, G. T. M. G. T. M.ORGANIC CHEMISTRY. 103 stituents boiling below 190" had been removed, the residue, on treatment with sodium hydrogen sulphite, yielded a crystalline mass which, when decomposed with sodium carbonate, furnished an aldehyde. This aldehyde (arornadendval), C,,H,,O, boils a t 2 1 O", has a yellowish colour, a sp.gr. 0.9477 at 15'/15", and [ u ] ~ - 49.19; it can also be obtained from the higher boiling fractions of the oils of E. cneroifolia, E. albens, and E. Woolsiana. Its oxime forms colourless crystals and melts at 84". The phenylhydraxone melts and decomposes at 105". The 6-naphthacinchonic acid melts and decomposes at 247". When the aldehyde is oxidised with potassium dichromate, crystals of aromadelzdric acid, C,H,,*CO,H, are obtained ; it melts a t llOo, is soluble in alcohol, ether, or hot water, and furnishes ammonium, silver, and copper salts. If the aldehyde is oxidised with potassium permanganate, eucalypt01 is produced, together with an acid which is easily soluble in alcohol or ether, melts a t 259-260", and is thereby converted into the anhydride.This anhydride melts a t l52", sublimes readily, and is very soluble in alcohol, ether, or boiling water. Dialdehydes resulting from Aldehydes and Aromatic Hydroxyaldehydes. I. Action of Benzaldehyde on Vanillin. By M. ROGOFF (Ber., 1901, 34, 3881-3884).-Benzylidenedivanill~n, CHPh [C,H,( OMe) (OH) *CHO],,- prepared by condensing benzaldehyde with vanillin in presence of zinc chloride, forms white, microscopic needles, melts at 22 1.E;-222*5° (corr.) to a reddish-brown liquid, reduces ammoniacal silver solution in the cold and Fehling's solution on warming, dissolves in sodium hydroxide, ammonia, and sodium carbonate, but not in sodium hydrogen carbonate, and is readily soluble in most organic solvents, but only sparingly so in benzene or ether, and not at all in light petroleum. The hexa-acetate, C,,H,,OI4, prepared by the action of acetic anhydride and sulphuric acid on the preceding compound, crystallises from 60 per cent.alcohol, melts at 159.5-162.5O (corr.), and is not hydrolysed by heating for 10 minutes with 15 per cent. sodium hydroxide. [Oxidation of Mesityl Methyl Ketone and +-Cumyl Methyl Ketone]. By L. VAN SCHERPENZEEL (I2ec. (rrav. Chim., 1901, [ ii], 20, 328-330).-1n a previous paper (Abstr., 1901, i, 32S), the author made no mention of the isolation by Meyer and Molz (Abstr., 1897, i, 474) of mesitylglycollic acid during the oxidation of mesityl methyl ketone. q-Cumyl methyl ketone, which melts a t 11' and boils at 245-250", gives, on oxidation with potassium permanganate at 154 according t o Claus' method (Abstr., 1890,981), +-cumyiglyoxylic acid without any $-cumylglycollic acid; the acid obtained melted a t 61-62' and the melting point could not be raised to 75", that given by other authors.Two Stereoisomeric Benzylidenedeoxybenzoins. By HANS STOBBE and KARL NIEDENZU (Ber., 1901, 34, 3897--3913).-When a mixture of deoxybenzoin and benzaldehyde in mol. proportion is satur- ated with hydrogen chloride, according t o Klages and Knoevenagel's method (Abstr., 1893, i, 350, 353), besides chlorobenzyldeoxybenzoin E. G. T. M. L. W. .A. D. i 2104 ABSTRACTS OF CHEMICAL PAPERS. (which melts at 172-172.5' and not at 182-185'), benzamarone (m. p. 215-216') and a ketone, isobenzylidenedeoxybenzoin (phenyl a-phenylcinnamyl ketone), CHPh:CPh*COPh (m.p. 88-89'), are formed. The latter is stereoisomeric with benzylidenedeoxybenzoin, formed by the action of concentrated alkali hydroxides on the chloro-com- pound just mentioned (compare Klages and Knoevenagel) and identical with the ketone, /3-C21H1S0, obtained by distilling benzamarone (Klinge- mann, Abstr., 1893, i, 353); i t is formed to the extent of 60-70 per cent. when hydrogen chloride is passed into a mixture of deoxybenzoin (2 mols.) and benzaldehyde (1 mol.) at a temperature of 75-80', and crystallises in yellow prisms or white needles. It is distinguished from its isomeride by the fact that i t dissolves in sulphuric acid with a purple-red colour, which in a few seconds becomes violet, and, later, dark green ; addition of water produces a n orange-red coloration ; benzyl- idenedeoxybenzoin, on the other hand, dissolves in sulphuric acid with a n orange-red coloration which does not change; on addition of water, the solution becomes colourless.After prolonged heating with phenyl- hydrazine, the is0 compound yields the phenylhydrazons of benzylidene- deoxybenzoin (m. p. 163-164'). On oxidation with nitric acid, both substances yield benzoic acid and benzil (or their nitro-derivatives). By heating either of the ketones alone at 160°, or by boiling or by expos- ing to light a solution of either in benzene in the presence of iodine, a mixture of the two ketones is always obtained, partial transformation of the one into the other having taken place. With bromine, isobenzyl- idenedeoxybenzoin gives the same dibromo-compound (m.p. 134-135") as does benzylidenedeoxybeozoin. With deoxybenzoin, the normal reacts far more readily than the iso-compound to form benzamarone. On treating the normal ketone in benzene solution with hydrogen chloride, chlorobenzyldeoxybenzoin ( m. p. 172') and the isoketoue are formed; similar!y, the isoketone yields, but more slowly, the same chloro-compound, together with a certain amount of the normal ketone. The chloro-compound (m. p. 135') obtained by Klingemann (Zoc. cit.) was not found. From these facts, the conclusion is drawn that under the action of hydrogen chloride, benzaldehyde and deoxy benzoin first form isobenzyl- idenedeoxybenzoin, which is transformed into the normal ketone ; the latter then combines with hydrogen chloride, forming chlorobenzylde- oxybenzoin.K. J. P. 0. Constitution of Piceol. By ERNEST CHARON and DSMBTRIUS ZAMANOS (Compt. rend., 1901,133,741-743. Compare Tanret, Abstr , 1894, i, 616).-It is shown that piceol (obtained from a glucoside, picein, occurring in the leaves of Pinus picea) is p-hydroxyacetophenone. From piceol and synthetical p-hydroxyacetophenone, the same oxime, phenyl- hydrazone, and semicarbazone, were obtained. OH* C,H,* CMe:N %OH, crystallises in colourless needles melting at 143' ; the phenylhydrazone melts at 148" ; the sernicarbazone crystallises in colourless needles and melts at 1'39'. The authors have prepared p-hydroxyacetophenone from anisole ; this is first converted into p-methoxyacetophenone by the action of acetyl The oxime,ORGANIC CHEMISTRY. 105 chloride and aluminium chloride, and the methoxy-group in the latter is then converted into hydroxyl by passing hydrogen bromide into hot water containing the p-methoxyacetophenone in suspension.K. J. P. 0. a-Hydroxybenzylideneacetophenone. By %. J. POND, H. J. PORK, and B. L MOORE (J. Anter. Chem. Xoc., 1901, 23, 789-796. Compare Abstr., 1900, i, 102).-When bromine is added to an ethereal solution of benzglideneacetophenone, a dibromide separates which melts a t 157" (Wislicenus, Abstr., 1900, i, 37) ; bp evaporating the filtrate, a second (or p-) clibromide is obtained, which crystallises in small, slender needles and melts at 108-109°. If the a-dibromide (1 mol.) is heated with sodium methoxide (2 mols.), the methyl ether of a-hydroxybenzyl- ideneacetophenone is produced as an oil which boils at 206--310° under 12 mm.pressure, and is readily hydrolysed by hydrochloric acid with formation of the a-hydroxy-compound. The ethyl ether may be pre- pared in a similar manner, The a-hydroxybenzylideneacetophenone, obtained as above, is identical with that described by Wislicenus (Zoc. cit.), but the isomeric dibenzoylmethane is not produced under these conditions. The copper and iron salts are described. E. G. By STANISLAUS VON KOSTANECKI and A. R ~ ~ Y C K I (Ber., 1901, 34, 3719-3721. Compare Kostanecki and Lloyd, Abstr., 1901, i, 735).-2 : 4 : 6 : 3'-Tetramethoxy-4'-ethoxybenzoylscetophenone (Diller and Kostanecki, Abstr., 1901, i, 476) interacts with ethyl iodide in boiling alcoholic potassium hydroxide solution to form 3'-met?~oxy-4'-et?~olcybenxoyl-2 : 4 : 6 -tvirnethoxgeth ylacetophenone, C, H2(0Me),* CO-CHE t*CO*C,H,( OMe)* OEt ; this crystallises from alcohol in white leatiets, melts at 138-133', and when boiled with concentrated hvdriodic acid yields a-ethvlluteolin, a-Ethylluteolin.which crystnllises from dilute alcohol in pale yellow needles, melts at 286-287", and yields a tetra-acetyl derivative crystallising in white needles and melting a t 129-130'. 3 : 3' : 4'-Trihydroxyflavone. By STANISLAUS TON KOSTANECKI and A. R~ZYCKI (Ber., 1901,34, 3721-3727). -Previous attempts to pre- pare this substance have failed (Emilewickz and Kostanecki, Abstr., 1899, i, 368, and Kostanecki and Rhiycki, ibid., i, 911), but the follow- ing method gave the desired result.W. A. D. 3'-Methoxy-4'-ethoxt~benxoyL2 : 4-diethoxyacetophenone, CoH,(OEt),* CO*CH,- CO*C,H,( OMe) *OEt, which is obtained by heating ethyl ethylvanillate with resacetophenone diethyl ether in presence of sodium, crystallises from alcohol in yellow needles, melts a t 134-135", and with boiling hydriodic acid yields o--I;;~,H;(oH), 3 : 3' : 4'-tri?tyd~oxyJ~vone, OH*C6H3<Co,CH ; the latter crystallises from very dilute alcohol in slightly yellow needles, melts at 326--327O, and yields a triacetyl derivative crystallising in white needles and melting at 209-210".106 ABSTRACTS OF CHEMICAL PAPERS. Benxoyl-2 : 4-diethoxyacetophenone, C,H,(OEt),* CO*CH2Bz, obtained by condensing ethyl benzoate and resacetophenone diethyl ether with sodium, crystallises from alcohol in yellow needles, melts a t 120-121°, and is converted by boiling hydriodic acid into 3-ethoxyflavone. W.A. D. Addition of Alcohols to Quinone. By EMIL KNOEVENAGEL and CARL BUCKEL (Ber., 1901, 34, 3993-3998).-When ethyl alcohol is heated with quinone in the presence of zinc chloride, an interaction takes place in which p-diethoxyquinone (compare Nietzki and Rech- berg, Abstr., 1890, i, 967) and quinol are formed quantitatively. Other primary alcohols (ethyl alcohol, kc.) behave in an analogous manner. I n the absence of zinc chloride, no such reaction takes place ; other metallic chlorides cannot be substituted for zinc chloride. 2 : 5-Bi6enxoyloxyquinone, C,H,O,{OBz),, prepared by heating with benzoyl chloride the p-dihy droxyquinone obtained from diethoxyquinone, crystallises in yellow leaflets melting a t 174".2 : 5-DipropyZoxyquinone, C6H202(0Pra)2, crystallises in golden-yellow leaflets melting a t 187". 2 : 5-DipopyZoxyquinoZ, C,H,(OH),(OPra),, prepared by reducing with stannous chloride the corresponding quinone, crystallises in flattened needles melting at 95". K. J. P. 0. Attempted Synthesis of the Camphor Ring as a Contribu- tion to th6 Tension Theory. By NICOLAI D. ZELINSKY (Bcr., 1901, 34, 3798-3801).-The author has attempted to convert the cistmns- form of hexahydroterephthalic acid into a dicyclic ketone, that is, a compound containing the camphor ring. On heating the barium salt of the acid with calcium carbonate, hydrogen is evolved and benzene obtained, together with a small quantity of a substance of a ketonic nature.This substance yielded a sernicarbaxone, C,H,,ON,, which crystallised in white scales melting a t 209-210" and is probably the derivative of a dicyclic heptanone. K. J. P. 0. Action of Cyanogen Chloride on Sodium Camphor. By H. DUVAL (Bull. Xoc. Chim., 1901, [iii], 25, 953-955).-By the action of cyanogen chloride on sodium camphor, a compound, C1,H1,02N2, was obtained ; this crystallises from hot water (which dissolves about 9 grams per litre) in colourless needles, melts a t 168', and has acid properties. camphor, C,H,,< C(CN)2 I -+ UsHI,<Co2H C W W , . It is regarded as a product of hydrolysis of dicyano- T. M. L. co Transformation and Oxidation of Fenc honeimine by Atmo- spheric Oxidation. By FRIEDRICH MAHLA (Ber., 1901, 34, 3777-3785.Compare Abstr., 1897, i, 85).--Fenchoneimine, CH,*QH-CHMe I ?Me, I , obtained by treating fenchonenitrimine with 25 per CH2* CH-C:NH cent. ammonia, boils a t 83' under 15 mm. pressure, has [.ID '76.30' at 19.5", a sp. gr. 0.9322 at 11.5", and n, 1.47809 at 17"; the experi-ORGANIC CHEMISTRY, 107 mental and calculated values for the molecular refraction are 45.857 and 45.78 respectively, The anhydrous base is stable and remains unchanged even when heated a t 200'. The picrata, C16H2007N4, melts at 202' ; nzethylfeencho~.leimine iodide, CI~l~,,,N I, is a crystalline product formed From methyl iodide and fenchonelmine dissolved in anhydrous ether. When a stream of dry air is passed through fenchoneimine heated at 105O, the base is partly transformed into dihydrofenchonitrile, yH,*CMe, >CH* CHMe.CN, and partly oxidised to hydroxydihydro- CH,-CH, fenchonitrile, >CH-CHMe.CN ; the former compound is an oil boiling at 98-104' and having a pungent odour recalling that of fenchvnitrile ; i t has aD 25'at 19' i n a 100 rum.tube, a sp. gr. 0.8951 at 16*5', and nD 1.44743 a t 17.5'; the experimental mol. refraction is 45*15', the calculated value being 45.09. This nitrile, when hydrolysed with boiling 30 per cent, alcoholic potassium hydroxide solution, is only partially decomposed, yielding a mixture of dihydrofencholeneamide and dihydrofencholenic acid, CH2* CMe2>CH*CHMe*C0,H, the latter in the form of its potassium salt. The amide melts at 130.5' and sublimes slowly a t 107'; it is only incompletely hydrolysed by alcoholic potass- ium hydroxide solution, but when heated at 200' with concentrated hydrochloric acid yields the corresponding carboxy-acid in theoretical quantities.The acid boils a t 145-146' under 13 mm. pressure, and has a sp. gr. 0,9816 a t 15' and [ u ] ~ 4.3' at 15.5'. The silvev salt crystallises from hot water, the ammonium salt is unstable and hygroscopic. Hydroxydihydrofenchonitrile, which remains in the residue after distilling the oxidation product of fenchimine in a current of steam, is an oil boiling a t 153-154' under 23 mm. pressure; it has a sp. gr. 0.9792 at 15', [ a ] D - 8' a t 18", nD 1.46464 a t 1 8 O , and mol. refraction 47.11, the calculated value of the last constant being 47.30. C)H,-CH, OH* CH*CMe, CH,--CH, - ?H2-cr-r2>C K* CHMe* CO NH,, 0 H CH C Me, Hydroxydih ydrofenc?mleneamide, obtained by hydrolysing the preceding nitrile Gith alcoholic potassium hydroxide solution, crystallises from ethyl acetate and melts a t 78'.CH,*yH--QHMe CH; CH-NH Dihydrofencholenic lactam, I ?Me, 70 , is produced together with a non-basic, oily substance by dissolving the preceding amide in warm dilute hydrochloric acid; i t separates from aqueoiis solu- tions in lustrous, highly refractive crystals and melts at 136--137'. It is identical with Wallach's P-fenchoneisooxime obtained from f e ncholenamide. (?H2-CH2>CH* CHMe* CO,H, the ultimate prodiict of the hydrolysis of hydroxydihydrofencholeno- nitrile, separates from water or ethyl acetate in hard crystals and melts a t 11 3-1 14'. When heated with water, the acid readily passes OH*CH*CMe, 4-Hydroxydihydrofencholenic acid,108 ABSTRACTS OF CHEMICAL PAPERS, CH,*$?H--GHMe into the Zactone, I ; this substance is volatile in steam and distils alone at 130-150' under 10 mm.pressure, yielding a dis- tillate which solidifies on cooling ; it separates from ethyl acetate in well-defined crystals melting at 72'. The lactone is insoluble in sodium carbonate solution, but slowly dissolves in solutions of the alkali hydroxides. G. T. M. ?Me, 70 UH,-CH---O Characterisation and Classification of the Sesquiterpenes. IV. By OSWALD SCHREINER and EDWARD KREMERS (Pharnz. Arch., 1901, 4, 141--165).-The classification of the terpenes generally is discussed at length. The first frac- tion, boiling below 150°, was redistilled under 32 mm.pressure; the portion collected betwoen 80' and 100' yielded a small quantity of a nitrosite which melts at 105' and is probably not phellandrene nitrite as was supposed by Bertram and Walbaum (Abstr., 1894, i , 201). The second fraction (150-162") consisted chiefly of zingiberene (Soden and Rojahn, Abstr., 1900, i, 605), which boils at 160-161' under 32 mm. pressure, has a sp. gr. 0.8731 at 20°, nD 1,49399, and [ alu - 73.38'. I t s hydrochloride is a white, crystalline substance which melts at 168-169'. The nitrosite crystailises in silky needles, melts at 97-98', find is very unstable. The nitrosate is a slightly yellow powder which melts and decomposes at 86-88'. The nitroso- chloride is a white powder which melts and decomposes a t 96-97'.Caryophyllene hydrochloride (Abstr., 1900, i, 106) is a di-derivative. The sesquiterpene obtained by the action of glacial acetic acid and sodium acetate on it, has a sp. gr. 0.9030 at ZOO, n, 1.49976, and [.ID - 8*96', and is neither regenerated caryophyllene nor clovene. Oil of ginger was distilled under 30 rnm. pressure. E. G. Specific Gravities and Coefficients of Expansion of the Volatile Oils. By OSWALD SCHREINER and W. R. DOWNER (Pharm. Arch., 1901, 4, 165--173).-The sp. gr. of a large number of volatile oils was determined at 15'/15', 20'/20', and 25'[25'. The results show t h a t the change in sp. gr. for each degree is comparatively small, and for any one oil is nearly uniform between 15' and 25", and not very different for different oils. The average change for each degree is 0.00064 ; this figure 'applies fairly accurately t o all the oils examined with the exception of those of cade and wintergreen.The data obtained have been employed for the calculation of the coeffi- cients of expansion of the oils between 15' and 25'. E. G. Constituent of Peppermint-like Odour occurring in many Eucalyptus Oils. By HENRY G. SMITH (J. Roy. SOC. Ar. 8. Tales, 1900, 136--142).-The oil of Eucalyptus diues,on fractional distillation, yielded 2 per cent. below 172', 60 per cent. at 172-200°, 13 per cent. at 200--227', and 20 per cent. at 227-240'. The last fraction, when treated with sodium hydrogen sulphite, furnished a crystalline com-ORGANIC CHEMISTRY. 109 pound which, on decomposition with sodium hydroxide, yielded a colourless oil of strong peppermint-like taste and odour; this oil is soluble in the usual organic solvents and slightly soluble in water, boils a t 224-225', has a sp.gr. 0.9393 a t 17'/15', [a], -0.35' (prob- ably due to the presence of a minute quantity of an aldehyde), and the molecular weight 154. By the action of sodium on an alcoholic solution, a reduction pmduct was obtained which crystallises in colour- less needles, melts at 155-156', and is readily soluble in chloroform and slightly so in alcohol, ether, or ethyl acetate. The fraction of this oil boiling at 227-240' yielded, on hydrolysis, a small quantity of an aromatic alcohol. E. G. Amy1 Eudesmate occurring in Eucalyptus Oils. By HENRY G. SX~TH (J. Roy. XOC. N.S. Wules, 1900, 72--81).-The oil of Eucalyptus u.ggregatcc yielded on fractional distillation 26 per csnt.boiling at 156-164", which consisted chiefly of d-pinene ; 12 per cent. mas obtained between 164' and 245', and 22 per cent, between 245' and 292' ; the residue, on cooling, became partly crystalline. Phell- andrene and eucalypt01 could not be detected. When the oil is hydrolysed with potassium hydroxide, amyl alcohol is produced. If the fraction boiling a t 245-292O is shaken with aqueous potassium hydroxide and the alkaline solution acidified with hydrochloric acid, eudesmic acid, C,,H,7-C)0,H, separates, which crystallises in rhombic prisms, melts a t 160' (uncorr.), is soluble to the extent of 04738 per cent. in water a t 20', and readily so in hot water, alcohol, ether, acetone, or chloroform; it sublimes at a high temperature without decomposition. Its untmoiium, .fin*ic, copper, and silver salts are described. The bs.ornide, CliH1802Br9, forms colourless crystals and melts at 102-103'.By the action of nitric acid on eudesmic acid, a substance is obtained which crystallises in microscopic needles, melts at 113', and is probably cumic acid. The amount of amyl eudesmate present in the oil is 57.7 per cent. E. G. Oriental Storax. By ALEXANDER TSCHTRCH and LEOPOLD VAN ITALLIE (Arch. P?m*mn., 1901, 239, 506 -532).-This is a secretion which forms slowly when incisions are made through the bark of Liquidambar orientalis into the wood. It is almost entirely soluble in ether ; the residue appears to contain vanillin and also a phlobaphen, since it yields phenol, acetic acid, phloroglucinol and protocatechuic acid when fused with potash.Styrene is present ready formed in the balsam. Prom an ethereal solution of the balsam, 0.1 per cent. aqueous sodium carbonate extracts cinnamic acid. Saturated sodium hydrogen sulphite solution then extracts vanillin, which could not be obtained pure, however. Finally, 1 per cent. aqueous sodium hydroxide ex- tracts a resin, at the same time hydrolysing a portion of the latter with formation of a gelatinous mass. I n the ethereal solut,ion a mix- ture of ethyl! phenylpropyl and cinnamyl cinnamates remains. The resin is hydrolysed by prolonged boiling with aqueous sodium hydroxide to cinnamic acid and a resinol, storesinol ; no tannol could be detected. Stoi-esinol, CI6Hz6O2, melts a t 156-161' when quite pure110 ABSTRACTS OF CHEMICAL PAPERS.and dry, otherwise at 93-96O, and is isomeric with benzoresinol (Tschirch and Ludy, Abstr., 1893, i, 480, i666). It is optically ac- tive, with [ u ] ~ 13'3' and 13'32' in 1 and 2.5 per cent. alcoholic solu- tions respectively ; i t gives a n absorption band betheen X = 0.510 and 0 . 5 4 0 ~ . It forms a crystalline potassium derivative and also a methyl ether, C,,H,,O,Me, when its concentrated methyl alcoholic solution is boiled for a long time with methyl iodide; i t does not form a n acetyl or benzoyl derivative, neither will it react with hydroxylamine or phenylhydrazine ; i t contains no methoxyl or ethoxyl group. When it is mixed with strong sulphuric acid and the mixture diluted with water after a few minutes and heated to boiliug, part of the product is insoluble in ether, but soluble in chloroform and is precipitated from the solution in needles by ether.This substance, styrogenin (Mylius, Yhnrrn. Centmlhalle, 1882, 79), melts above 360' and has the composition C,,H,,O,. When storesinol is treated with hydrogen bromide in chloroform solution, or heated with 50 per cent. hydro- bromic acid in sealed tubes, a poduct, C,,H,,O, is obtained, melting at about 280'; the same product is obtained with hydriodic acid, but in no case is the yield good, When storesinol is brominated in acetic acid solution, hydrogen bromide is evolved and an amorphous product is formed containing a varying amount of bromine. Nitric acid of sp. gr. 1.317 oxidises storesinol to picric and oxalic acids and a sub- stance containing nitrogen ; chromic acid oxidises it t o benzoic acid, dilute aqueous potassium permanganateat 65-70' tophthalicacid and an acid which melts at 199O, is insoluble in Yater, and requires 10.5 C.C.N/10 alkali to neutralise 0.357 gram, with phenolphthalein as indicator. Attempts t o reduce storesinol with sodium amalgam and with zinc and acetic acid had no result, Fusion with potassium or sodium hydroxide leads to the formation of acetic and salicylic acids. Dry distillation yields phenol and cresol, with benzene, toluene, and probably phenyl- acetylene. Distillation with zinc dust yields phenol, with benzene and toluene ; no naphthalene is formed. In 100 parts of a sample of t h e drug, there were contained : In- soluble in ether, 2.4 ; free cinnamic acid, 23.1 ; Tpater, 14 ; aromatic esters, 22.5 ; styrene and vanillin, 2.0 ; resin, 36.0.The acid number was 81.0 ; the saponification number, 1'79.0 ; saponification number of the mixture of esters and styrene, 209-0. About half of the combined cinnamic acid was contained in the resin, the rest in the aromatic esters. C. F. €3. American Storax. By ALEXANDER TSCHIRCH and LEOPOLD VAN ITALLIE (Arch. Phurrn., 1901, 239, 532-541).-This substance, also called sweet gum, is a secretion which is formed gradually after in- cisions have been made through the bark of Liquidurnbar styracifluu into the wood. It was examined in the same way as oriental storax (preceding abstract) and found t o contain much the same constituents.Of aromatic esters, however, ethyl cinnamate could not be detected with certainty, and the resinol obtained, C16H2,02, has [ a ] D 52*, although in all other respects it resembles storesinol ; it is therefore re- garded provisionally as isomeric with this substance, and is named styresinol ; it is present both in the free state and as a cinnamate.ORGANIC CHEMISTRY. 111 I n 100 parts of the balsam there are contained : Insoluble in ether, 3.12 ; free cinnamic acid, 23.4 ; aromatic esters, 25 ; styrene and vanillin, 2.0 ; resin, 45.0. The acid number mas 89.3 ; saponification number, 192.7 ; the saponification number of the mixture of aromatic esters and styrene, 205.1. Rather more than half of the combined cinnamic acid was contained in the aromatic esters, the rest in the resin. C.F. B. By ALEXANDER TSCHIRCH and LEOPOLD VAN ITALLIE (Arch. Phumn , 1901, 239, 541-547).-This substance, the product of Altingia excelsa (Java), has bseii subjected t o a preliminary examination. It contains benzaldehyde, cinnamic acid and cinnam- aldehyde, also a resin and a pentosan ; esters are not present. The balsam is undoubtedly different from either oriental or American storax, with which it has often been confused. Phoenicein, the Dye from Purple Wood. By ESTELLA KLEEREKOPER (Chem. C'entr., 1901, ii, 1085-1086 ; from Ned. Ted. I-'harm.,l901,13,284--288,303-314. Comparethisvol., i, 48).-Further examination has shown that phoenin is not a glucoside. By heating for a long time at looo, or for an hour at 150-160°, or by the action of dilute acids, it is converted quantitatively into phoenicein with elimination of 1 H,O.With alkalis, phoenicein, C14H1406, gives a blue coloration, which becomes violet and finally brown, the alkali salt first formed being reconverted into phoenin and then undergoing further decomposition. Phoenicein crystallises in minute rods, begins to darken a t about 190", and is easily soluble in methyl or ethyl alcohol and slightly so in water containing mineral acids, With alkalis and ammonia, it forms unstable blue salts. The red colour of the product obtained by boiling phoenin with hydrochloric acid is due to the presence of an unstable compound of phoenicein with the acid ; this compound is decom- posed by water, being reconverted into phoenicein. This property of combining with both acids and alkalis is shared by other dyes of the flavone and quercetin groups (compare Perkin, Trans., 1899, 75, 433), and, like these, phoenicein also gives a blue precipitate with sodium acetate in alcoholic solution.When reduced by zinc dust and glacial acetic acid, it forms a leuco-compound, which is very readily oxidised by exposure to the air, and with aluminium hydroxide and ferric hydroxide it forms blue and brown lakes respectively. By the action of acetic anhydride, an acetyl compound, which apparently con- tains three acetyl groups, is obtained as a yellowish-white powder, and with nitric acid,. phoenicein gives trinitroresorcinol and carbon dioxide, Carbon dioxide 1s also eliminated by dry distillation or by the action of an alkali, a phenol being probably formed in the latter case.When treated with bromine, phoenicein yields substitution derivatives ; with sulphuric acid, i t gives a sulpho-derivative, and with benzoyl chloride, a n amorphous benzoyl derivative. The constitution of phoenicein may OH*S=CH*YH--O--YH*CH Y*OH CH:CH*CH* CH( CO,H)*CH- CH:C*OH' possibly be : Rassamala Resin. U. F. B. E. W. W.112 ABSTRACTS OF CHEMICAL PAPERS. Basic Properties of Oxygen. By AUOLF VON BAEYER and VICTOR VILLIGER (Be?*., 1901, 34, 3612-3618. Compare Abstr., 1901, i, 658).-Unsaturated hydrocarbons of the ethylene type do not com- bine with acids. Perricyanic acid is a strong oxidising agent, and most of the oxoninm salts previously described contain small amounts of ferrocyanides. Dirnethylpyrone hydrochloride is readily formed when a solution of the base and acid in mol.quantities is evaporated. I n concentrated solution, it appears to exist as the salt, but in dilute solution is completely dissociated. As regards basic properties, di- methylpyrone closely resembles carbamide ; other oxygen compounds, for example, alcohols and the higher ethers, have basic character- istics analogous t o those of nitriles. The latter dissolve in concen- trated hydrochloric acid and are thrown down unaltered on dilution. With ferrocyanic, ferricyaaic, and cobalticyanic acids, they form crys- talline salts. Salts of the following nitriles have been obtained : pro- pionitrile, n-butyronitrile, valeronitrile, hexonitrile, and benzonitrile, and benzyl cyanide. By JOHN THEODORE HEWITT (Bey., 1901, 34, 3819-3823.Compare Zed. physikal. Chem., 1901, 34, I).-As the result of Werner's publication (this vol., i, 50), attention is drawn to the fact that the author bad previously (Zoc. cit.) noted attention to the possibility of the existence of quadrivalent oxygen in xanthydrol salts. These salts, and also those of phenyl-/3-dinaphthoxanthydrol in dilute solution exhibit strong fluorescence. Xanthydrol and picric J. J. S. Oxonium Salts. _. _- acid yield a compound, C,H,(N0,),*O*O~U6H4~CH, in the form of C,H* " X dark green, glistening crystals. Dihydroxy-derivatives of 2 : 4-Diphenyl-1 : 4-benzopyranol. By CARL BULOW and WALTHER YON SICHERER (Bey., 1901, 34, 39 16-3929).-PyrogalloI, phloroglucinol, and hydroxyquinol all con- dense with dibenzoylmethane, yielding various dihydroxy-2 : 4-diphenyl- 1 : 4-benzopyranols.These are of a strongly basic nature and the formation of their stable hydrochlorides, sulphates, &c., can only be readily explained by the assumption that the ring oxygen atom is quadrivalent (see also Abstr., 1901, i, 400, 599, and 603). When a stream of dry hydrogen chloride is passed for eight hours into a solution in glacial acetic acid of pyrogallol and dibenzoylmethane, a mass of violet-brown crystals is obtained consisting of the hydro- chloride of 7 : 8-dihydroxy-2 : 4-diphenyl-1 : 4-benzopyranol, c 6 H 2 ( 0 H ) 2 < ( p q 0 ~ ) .CH ; this crystallises from alcohol containing a little free hydrogen chloride in claret-ooloured, felted needles with a coppery lustre, and loses hydrogen chloride when placed in a vacuum or when treated with sodium acetate, yielding the base which crystallises in microscopic, violet needles and .dissolves in most solvents except water and light petroleum.The constitution of the base is proved by ( a ) the forma- tion of a t ~ i a c e f y l derivative, which cryktallises from pyridine in short, dark brown prisms aud decomposes at (about) 230", and (6) by its J. J. S. O(HCl)-gPhORGANIC CHEMISTRY. 113 bydrolysis to acetophenone, 1 : 2 : 3-trihydroxybenzophenone, pyrogallol, and benzoic acid. The picrate crystallises in small, lustrous, brownish- violet needles, which begin to soften at 200" and $0 melt and decom- pose at 242'. The plutinichlwide crystallises in lustrous, copper- coloured, felted needles, which begin t o soften at 150' and melt a t 178".5 : 7-Dihydroxy-1 : 4-benxopys*anol, prepared by condensing phloro- glucinol with dibenzoylmethane, is obtained as small, pinkish, cubical crystals ; the hydrochloride forms lustrous, red, prismatic crystals, is very slightly soluble in water, alcohol, or acetic acid, and decomposes above 260"; the triacetyl derivative crystallises from nitrobenzene in dark brown prisms, which gradually decompose above 200' ; the 8-nitroso- derivative, obtained when the hydrochloride dissolved in acetic acid is treated with nitrous acid, crystallises in slender, reddish-brown needles and decomposes above 230". 6 : 7-Dihydroxy-2 : 4-diphenyl-l :4-benxopyranol, obtained from hydroxy- quinol by analogous methods, crystallises from alcohol i n ruby- red prisms ; the hydrochloride crystallises in lustrous, ochre-yellow plates, which, when heated, begin t o decompose at 250' and melt and evolve gas at 272"; the picrate crystallises in small, red needles, which soften at 220' and melt and decompose at 236".New Banzopyranol Derivatives from Benzoylacetaldehyde and Polyhydric Phenols. By CARL BULOW and WALTHER VON SICHERER (Bey., 1901, 34, 3889-3897, Compare Abstr., 1901, i, 400, 55 9, 603) .--7-Hydroxy-2-pheny I- 1 : 4-benxopyranol hydrochloride, R. H. P. OH*C,H,<~,(~~>CH,HCl, is formed when a solution in acetic acid of benzoylacetaldehyde and resorcinol in mol. proportion is saturated with dry hydrogentchloride ; it forms brownish-orange crystals melt- ing at 152-153', dissolves in alkalis with a brownish-red colour, and in solution in concentrated sulphuric acid gives an intense green fluor- escence.7-lzydroxy-2-pJ~enyl-1 : 4-benzopyranol, C,,H,,O,, prepared by treating an aqueous solution of the hydrochloride with sodium acetate, forms reddish-brown, amorphous flakes ; when boiled with aqueous potassium hydroxide it is decomposed into acetophenone, resorcinol, and benzoic acid. The picmte, C,,H,,0,,C6H307N3, crystallises in dark yellow needles melting and decomposing at 232-234' ; the platinichloride forms small, orange-yellow scales, which darken a t 240' and melt and decompose at 244" ; the aurichloride crystallises in brownish-yellow needles melting and decomposing at 178". 7-Acetoxy-2-phenyl-1 : 4- benxopyyanol acetate, C~,H,,03Ac,, prepared by boiling the hydro- chloride with acetic acid and acetic anhydride, forms a violet-grey amorphous powder which begins to melt at 160".7-Methoxy-2-phenyl- 1 : 4-benzopyrunoZ, C,,H,,O,Me, prepared by treating the hydrochloride with methyl iodide and sodium methoxide, is a brownish-violet, amor- phous powder and does not exhibit fluorescence when dissolved in sulDhuric acid. L O--yHPh 7-Acetoxy-2-phenyl-1 : 4-dihydrobenxopyan, OAc*C,H,<CH_ CH, 9 is obtained by reducing the hydrochloride with zinc dust an& acitic1 I4 ABSTRACTS OF CHEMICAL PAPERS. acid in presence of acetic anhydride, and is an amorphous powder melting, but not sharply, at 112-114O. 5 : 7-Dihydroxy-2-phenyl-1 : 4-benzopyranol hydrochlovide, C6H2( 0 H ) 2 < ~ 6 ~ ~ > c H , H c 1 , prepared by saturating with hydrogen chloride a solution of phloro- glucinol and benzoylacetaldehyde, is a brick-red, crystalline powder ; the bccse is a brownish-red, amorphous powder.7 : S-Dij~~di’oxy-2-p~~enyl-l : 4-benxopyranol hydrochloride, prepared from pyrogallol and benzoylacetaldehyde, was obtained only in an amorphous form, and mas converted into the base by means of sodium acetate ; the latter is a dark brown, amorphous powder. Physiological Properties and Composition of Iboga. Presence of a New .Alkaloid, Ibogaine. By J. DYBOWSKI and EDOUARD LANDRIN (Compt. rend., 1901, 133, 74S-’750).-Iboga is a plant which grows in French Congo. The woody portions are stated by natives to have an effect when consumed similar to that of alcohol.The active principle, ibogaine, C,,HGGO,N~, is present in the bark and wood and particularly in the roots of the plant, which yielded 0.6 to I per cent. of the alkaloid. Ibogaine forms long, slightly amber-coloured prisms which melt at 1 5 2 O and dissolve very readily in alcohol, ether, chloroform, light petroleum, and most other solvents. It is lsvorotatory, [.IU - 4S032’ at 1 5 O . The deviation is 1’56’ for 1 gram dissolvedin 50 C.C. of alcohol. When exposed to air, ibogaine becomes yellowish-brown and seems to be converted into a non-crystalline substance. Saline solutions are precipitated by Mayer’s reagent, by tannin, and by phosphoantimonic acid. Bismuth potassium iodide produces a gold-coloured precipitate. The sulphccte, nitrate, acetate, and benzoate are neutral, but not crystal- line ; the hydrochloride is crystalline.As regards the physiological effect of ibogaine, it was found that large doses produce analogous effects to those resulting from excessive consumption of alcohol. Ipoh Arrow Poisons and some Plants that are used to prepare them. By C. HARTWICH and P. GEIGER (Arch. Pharm., 1901, 239, 491--506).-A list is given of plants which are used to prepare poisons with which the heads of arrows are smeared; it is noteworthy that such arrows are almost invariably projected from a blowpipe. The chief of these plants are Antiaris toxicaria, which con- tains antiarin ; species of Xtrychnos, containing strychnine and brucine ; and Derris elliptica, which contains derride. Samples of poison were examined for these substances : antiarin was detected by the golden-yellow coloration, with subsequent fluor- escence, which it gives with sulphuric acid, and by the brown colora- tion with hot aqueous sodium picrate ; derride by the blood-red colora- tion which i t gives with sulphuric acid containing a trace of ferric chloride ; strychnine by its reaction with vanadosulphuric acid ; brucine by its reaction with nitric acid.Of 25 samples, 2 contained derride, 5 brucine, 11 strychnine, and 21 antiarin. With antiarin there is commonly associated a substance closely resembling the fluavil K. J. P. 0. N. H. J. M.ORGANIC CHEMISTRY. 115 of guttapercha, and also a new alkaloid, ipohine, :which was found in 12 out of 19 specimens examined. This alkaloid is a virnlent poison, causing cessation of the heart's action, much as digitoxin does but a great deal more quickly, Antiarin has a comparatively feeble action. A morphological description of Alatiaris toxicaria and Derris elZipticc6 is given ; also the results of the examination of various Indian species of Strychnos for strychnine, brucine, and strychnochromin.The last is detected by the green coloration which it gives with concentrated sulphuric acid and with nitric acid ; in its occurrence it seems to bear no relation to strychnine or other alkaloids generally. Conversion of Pyrrole into Pyrroline. By GIACOMO L. CIAMICIAN (Ber., 1901, 34, 3952-3955. Compare Knorr and Rabe, this vol., i, 54).-The names A1-, A2- and h3-pyrrohe are suggested for the ,CH-FH, CH:QH and C. F. B. three isomeric compounds, N<CH,*CH: ~ ~ < c r r , a x : L L O Y CH2DEH The compound obtained by the reduction of pyrrole NH<CH,.CH- I is most probably A3-pyrroline, as such a constitution harmonises best with Thiele's theory.The reduction is most economically brought about by the aid of zinc dust and acetic acid, since all unaltered pyrrole can be recovered. When hydrochloric acid is employed, all unreduced pyrrole is resinified. Hielscher's base (Abstr,, 1898, i, 338) is 1 -methyl-A2-pyrroline and differs altogether in properties from AS-py r r o h e . J. J. S. By GIORGIO ERRERA (Ber., 1901, 34, 3700--3704).-The three modifications of the imide of ethyl dicarboxyglutaconate, CH<@,@$"~~>NH, are probably not desmotropic as considered by Guthzeit (Abstr., 1894, i, 71, and 1895, i, 557), for the change of form is not reversible, and the action of dilute alkalis on the imide yields a nitrile, CO,Et*CH(CN)*CH:CH*CO,Et. I n the light of analogous facts (following abstract) the author considers that the action of ammonia on Guthzeit's coumalin derivative gives an isoimide, thus : C(C0,Et):-C OEt CH(C0,E t)--F(NH,)*OEt CH'C(CO,Et)~CO*O + EtOH- Desmotropism in the Pyridine Series.CH%(CO,Et)* cod + NH3 + C H ~ c ( c o , E t ) * C o * o CH(CO,Et)-y:NH The action of both heat and of alkalis is then explicable by the following scheme : CH(C0,Et) --Q:NH CH%( CO,Et)* co* 0 -> CO,Et*CH(CN)*CH:CH*CO,Et + CO, CH(CN)*CO,Et /+ CH~C(C02H)*C0,EC 5 C ( C O , E t ) x - f ! *OH CH%(CO,E~)*CO*NH W. A. D.116 A BSTHACTS OF CHEMICAL PAPEJIS.Action of Halogens and of Ethyl Bromocyanoacetate on Ethyl Sodiocyanoacetate. By GIORGIO ERRERA and F. PERCIA- BOSCO (Ber., 1901, 34, 3704-3717. Compare Abstr., 1901, i, 18, and Thorpe and Young, Trans., 1900, 77, 936).-The action of halogens (iodine in ethereal solution or bromine) on ethyl sodium cyanoacetate gives the same products as the action of ethyl bromocyanoacetate (Zoc. cit.), but the yield is smaller ; in addition to ethyl tricyanotrimethyl- enetricarboxylate (m. p. 11 9*5O), considerable quantities of ethyl sodio- dicyanoaconitate, CO,Et*CNa(CN)*C(CO,Et):C(CN)*CO,Et, are formed ; this separates from alcohol in large, yellow, monoclinic crystals, with 4H20, melts and decomposes at about 245') and is hydrolysed by boiling water with loss of 1 CO,, yielding ethyl sodiodicyanoglut- aconate, C0,E t * CNa( CN)*C'H: C( CN) CO,Et, which crys tallises in needles with 2H,O.Ethyl dicyanoaconitate, C0,Et *CH( CN) C(C0,Et): C(CN)*CO,E t, obtained by acidifying an aqueous solution of its sodium derivative, crystallises in leaflets, with iH,O, melts and decomposes when rapidly heated at 145-146", and cannot be recrystallised. If, in t h e preceding decomposition by acid, the solution of the sodium derivative be very dilute, further hydrolysis occurs, and ethyl isoirninodicarboxgaconitate, CO,Et*C~C(Co~~t).CO,d , is formed (compare preceding abstract,) ; it does not contain a carboxyl group since it is not acid in character, and crystallises from dilute alcohol in needles, with 1H,O, which melt at 70". By warm dilute alkalis, i t is dissolved, and, on acidifying, ethyl cyanonconitate, is precipitated as a heavy, yellowish oil with acid properties.On boiling the isoimide with absolute alcohol, i t undergoes isomeric change into ethyl 5-cccrboxy-2 : 6-dihyd~oxycinchomeronate (ethyl 2 ; 6-di- Irydroxypy~idine-3 ; 4 ; 5-tricarboxylate) or its isodynamic form, ethyl 6 - h y d r o x ~ - 2 - k e t o - A 3 ~ ~ - d ~ h ~ ~ ~ ~ ~ o p ~ r ~ ~ ~ n e ~ r ~ c c ~ ~ ~ o x ~ ~ c ; the product crys- tallises from benzene on adding light patroleurn in soft, white needles, melts at 137' and is converted by boiling hydrochloric acid of sp. gr. 1.06 into etlql 2 : 6-dihydroxy-3 : 4-cinchomeronate (ethyl 2 : 6-dihydroxy- 3 : 4-pyridinedicarboxyZate), which crystallises from benzene or methyl alcohol in white leaflets and melts at 157'; citrazioic acid is also formed.Jlonoethyl 2 : 6-dihydroxycinchomeronate (ethyl 3-ca~boxy-2 : 6-dihy- droxypyridine-4-carboxylate or ethyl 4-carboxy-2 ; 6-dihydroxypyridine- 3-carboxyZate), obtained by boiling ethyl 5-carboxydihydroxycincho- meronate with aqueous sodium hydroxide (2 mols.), crystallikes from dilute alcohol in small needles and decomposes a t 215'. Ethyl tricyanotrimethylenetricarboxylate (Zoc. cit.) melts when pure at 119.5' ; tricyanotrimethylene crystallises from alcohol in white leaflets and melts a t 188-1893. Ethyl dicyanotrimethylenetetmcarboxyZate, CO,Et. ),(CN)>C( CO,Et),, is always formed as one of the products of the interaction of ethyl bromocyanoacetate and sodiocyanoacetate ; it crystallises best from CH( C0,Et)-C:NH C0,Et *CH(CN)*C( CO,Et):CH*CO,Et, C0,Et C( CN)ORG A N IC C IT E MI STRY.117 alcohol in large, transparent, triclinic crystals and is easily hydrolgsed by barium hydroxide to trimethylenetetracarboxylic acid (Schacherl, Abstr., 1885, 1125). W. A. D, Mixed Methenyl Compounds, IV. Synthesis of 2 : 5-Lutidine [Z : 5-Dimethylpyridine]. By GIORCIIO ERRERA (Ber., 19 0 1, 34, 3 6 9 1--37OO).-Ethyl ~-cynno-s-ethoxy-P-hexanone-r-ctcrbox!/lb- oxykcde, CH,*CO* CH( C0,E t) CH( OE t)*CMe( CN)*CO*NH,, obtained by the interaction of ethyl a-ethoxymethyleneacetoacetate and methylcyanoacetamide (in the form of cyanoacetamide, methyl iodide, and sodium ethoxide in alcoholic solution), crystallises from water in flat, lustrous needles, and melts a t 202-203'; it is accompanied by considerable quantities of ethyl 5-cyano-6-hydroxy-2-methylpyridine- 3-carboxylate, formed from unchanged cyanoacetamide (Abstr., 1900, i, 43), and of ethyl 6-hydroxy-2 : 5-dimethylpyridine-3-carboxylate (infia).~-Cyano-~-et7~oxt~-~-hexano~ze-~-carboxylcc,mide-ycc~cl.boxyZic mid obtained by hydrolysing the ethyl ester, separates from water in hard, opaque, white crystals, and melts and decomposes at 256'; if the hydrolysis is effected by boiling hydrochloric acid, alcohol, ammonia, and carbon dioxide are eliminated and ring formation occurs with the production of ethyl 6-ht~droxy-2 : 5-dimethylpyridine-3-carboxyEate ; this crystallises from alcohol in soft, coloiirless needles, melts a t 216-2117') and is easily hydrolysed by boiling dilute alkalis into the corresponding acid, which crystallises from glacial acetic acid in slender needles and when rapidly heated melts and decomposes at 300-305'.6-Hyd~oxy-2 : 5-dimethylpgridine, obtained by heating the acid with hydrochloric acid of sp. gr. 1.1 for several hours a t I 50°, forms monoclinic crystals [a : b : c = 1.54256 : 1 : 1.43626 ; /3 = 46'52'57"], with &H,O, and melts at 138-139'; the potassium salt, C7H,0NK,5$H,0, crystallises in lustrous leaflets. 3-Bromo-6-hydroxy- 2 : 5-dimetl~?/Zz)yricline, formed by the action of bromine in glacial acetic acid solution, crystallises from alcohol in long, lustrous needles and melts a t 218-219'. 2 : 5-DimethyZpyridine, formed on distilling its hydroxy-derivative with zinc dust, boils at 159-160°, and yields a, crystalline hydrochloride and two mercurichlorides, C7H,,,NC1,6HgCI, (small, hard prisms) and 2C7H,,NC1,5HgC1, (long, lustrous needles) ; the picrate melts a t 165 *5'.W. A. D. Action of Pyridine Bases on Tetrahalogen Derivatives of Quinones. By HENRI IMBERT (Compt. rend., 1901, 133, 937-938).- The compound obtained by the action of pyridine on tetrachloroquinone (this vol., ii, 55), when treated with hydrochloric acid and potassium chlorate, yields a p?jridtJEtricl~lorotri~to~ntamethylene hydrochloride, HCI,C,NH, C C l < ~ ~ : ~ ~ 2 , forming white crystals some what soluble in cold water. With phenylhydrazine, i t yields a trihydrazone, and with o-tolylenediamine it yields an azine. It follows that this oxidation product contains three ketonic groups, two of which are adjacent, and consequently the only admissible formula for the original product (Zoc.cit.) is C,NH,* C,CI,O,*OH. C. H. B. VOL. LXXXII. i. k118 ABSTRACTS OF CHEMICAL PAPERS Tertiary and Quaternary Tetrahydroisoquinoline Bases ; a Contribution t o the Stereochemistry of Nitrogen. By EDam WEDEKIND and E. OECHSLEN (Ber., 1901, 34, 3986-3993. Compare Abstr., 1900, i, 155).-2-Methyltetrahydroisoquinoline can be readily prepared by reduction of isoquinoline methiodide by tin and hydrochloric acid (compare Ferratini, Abstr., 1893, i, 227). It is a colourless oil, distils at 212', and has strongly basic properties. With ethyl iodo- acetate, i t forms an additive product, C,,H,,O,NI, which forms yellow crystals melting at 156-167'.2-EthyltetrahydyoisoquinoZhae, C,NH,Et, obtained from isoquinoline etbiodide, is a pale yellow oil boiling a t 225-227' ; the platinichloride crystallises in reddish-yellow leaflets melting at 169'; the piwale in yellow needles melting at 121'; the normal oxalccte in colourless needles melting at 110' ; the hydriodide in pale yellow needles melting at 170"; the additive compound with ethyl iodoacetate forms small crystals decomposing a t 109-1 10'. isoQuinoZine benxyliodide crystallises in large, monoclinic plates [cc : b : c = 0,5842 : 1 : 1.3498 ; p= 82'16.5'1, and melts at 175-176". On reduction, 2- benxyltetrahydroisogzcinoline, CIGHl7N, is obtained as a pale yellow, viscous oil boiling a t 194-197' under 18 mm. pressure; theplcctinichloride crystallises in brown pyramids decomposing a t 2 19' ; with ethyl iodoacetate, an additive compound is obtained as crystals decomposing at 148 - 149".Benzy ZethyltetrahydroisoquinoZinium iodide is formed very readily from 2-ethyltetrahydroisoquinoline and benzyl iodide, far more slowly from 2-benzyltetrahydroisoquinoline and ethyl iodide ; by both methods of preparation a salt is obtained crystallising in large plates which decompose a t 133'. The crystal8 of both specimens are monoclinic, have p=63'40', and are in all respects id en t ical. K. J. P. 0, Condensation Products from Aromatic Nitroso-compounds and Methylene Derivatives. By FRANZ SACHS (D.R.-P. 121974). -The compound produced by condensing benzyl cyanide and p-nitroso- phenol in alcoholic sodium hydroxide solution, crystallises in brown needles, melts at 155', and is converted by dilute mineral acids into the original cyanide and paminophenol.Corresponding condensation products are obtained from p-nitrosophenol and phenylmethylppr- azolone, ethyl acetoacetate, and cyanoacetamide. G. T. M. Nitroso-m-phenylenediamine and Nitroso-2 : 4-tolylenedi- amine. ERNST TAUBER and FRANZ WALDER (D.R.-P. 123375).- Nitroso-compounds are formed when cooled aqueous or slightly acid solutions of m-phenylenediamine and its tolyl homologue are rapidly treated with 2 mols. of nitrous acid. These substances are always ac- companied by Bismarck-brown which is separated by the addition OF sodium chloride, whilst the nitroso-derivatives are isolated by saturating the filtrate with ether and adding sodium carbonate.Nitroso-m-phenylenediamine, NO*C,H,(NH,), (compare Abstr., 1901, i, 141), crystallises in red, monoclinic plates and melts a t 210'; its hydrochloride separates from water in reddish-brown needles. Nityoso-2 : 4-toZyZenediccmine, NO*C,H,Me(NH,),, closely resembles its lower homologue and melts at 195". G. T. 31.ORGANIC CHEMISTRY. 11 0 Condensation Products from Aromatic p-Nitrosoamines and Toluene or Xylene Compounds. By FRANZ SACHS (D. R.-P. 121 745).-2 4-Dini~robenxylidenedimetT~~~-p-phen~lened~c~mine, C',H,(NO,),*CH:N*CGH,.NMe, . produced by condensing 2 : 4-dinitro- toluene and nitrosodimethylaniline in boiling alcoholic solution in the presence of a small amount of sodium carbonate or trisodium phosphate, separates from glacial acetic acid as a brownish-violet, crystalline powder with a bronzy lustre; it melts a t 196" and is sparingly soluble in the ordinary solvents, 2 : 4 : 6-Trinitrotoluene, 2 : 4 : 6-trinitro-m-xylene, and 2-chloro- $-nitrotoluene also yield similar condensation products obtained as dark brown powders.This reaction takes place only when the nitro-com- pound contains in its molecule a t least one other negative radicle, negative results being obtained with 0- and p-nitrotoluene. These condensation products on hydrolysis yield the corresponding benz- aldehyde derivatives (compare Abstr., 1901, i, 230). G. T. M. m-Amino tolyloxaminosulphonic Acids. SCHOELLKOPF, HART- FORD & HANNA Co. (D.R.-P. 121746).-m-Aminotolyloxa1mino-5-sulphonic wid ('( A " acid), NH,*C,H,Me(NH*CO*CO,H)*SO,H, obtained by heating 2 : 4-tolylenediamine-5-sulphonic acid with a 25 per cent.solu- tion of oxalic acid, separates from the product of reaction in a crystal- line form ; it yields a sparingly soluble calcium salt, a stable diazo- compound which is precipitated even from dilut,e solutions, and a scarlet azo-derivative with R-salt. The corresponding 2-c~mi~~otoZ~l-6-oxamino-4-sz~Z~Aonic acid ( '' B " acid), produced from 2 : 6-tolylenediamine-4-sulphonic acid,. yields a soluble calcium salt and diazo-compound, the azo-derivative with R-salt being orange. G. T. M. Condensation Products from the Diaminoanthraquinones and Formaldehyde. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 123745)-1 : 5-, 1 : 3-, and 1 : 8-Diaminoanthraquinones when heated with formaldehyde in methyl or ethyl alcohol, acetone, acetic aoid, or carbon disulphide solution yield crystalline condensation products which are insoluble in water, acids, or alkalis, but dissolve in alcohol, giving red solutions, G.T. M. Naphthacridine Derivatives. CARL ULLMANN (D.R.-P. 123260. Compare this vol., i, 55,56).-Phenonaphtha~ridine,C~~H~<~-->c~H~, (rn. p. 1 2 9 5 O ) , is obtained by heating together trioxymethylene, p- uaphthol, and aniline a t 160° ; o-tolunaphthacridine, produced in a similar manner from o-toluidine, melts a t 143". Dimetily~he~2onc~phthucridine, prepared by heating the condeneat ion product of formaldehyde and m-xylidine with P-naphthol, crystallises from alcohol or benzene in pale yellow needles and melts at 152". obtained from scetyl-p-phenylenediamine and formaldehyde, forms white crystals melting a t 195-200" ; when treated with p-naphthol at 150-lSO", CH Acet?/l~netk?lZene-p-yhen?l Zenediamine, NHAc CGH+* N : CH,, I,.2120 AESTRACTS OF CHEMICAL PAPERS. it yields acetylaminophenonaphthucridine, C l o H , i < ~ ~ C ' , H 3 * N H A ~ , a compoiind crystallising from alcohol in yellow needles and melting a t 255'. The corresponding aminophenonaphthc6crid~ne, obtained by hydrolysing the acetyl derivative, crystallises in needles melting at 238'. G. T. 31. 1-Phenyl-2 : 3-dimethyl-5-thiopyrazolone. AUGUST MICHAELIS (D.R.-P. 122281).--1-Phenyl-2 : 3-dimethyl-5-thio~~/1.ccxolone, C,,H,,N,S, obtained by treating the metho-chloride, -bromide, or -iodide of 5-chloro- l-phenyl-3-methylpyrazole, C,,H,,N,Cf,, with an alkali sulphide or hydrosulphide, separates from water or alcohol-ether in white crys- tals and melts at 1 6 6 O ; it forms a crrstalline hydrochloride (compare Abstr., 1901, i, 52).By J. BURACZEWSKI and LEON MARCHLEWSKI (Ber., 1901, 34, 4008-4015. Compare Abstr., 1901, i, 415, 615).-o-Nitro- benzoylformic acid condenses with o-phenylenediamine hydrochloride G. T. M. Isatin. - - in the presence of sodium acetate, forming 2-hyd~oxy-3-okitropheny I- >C,H,, which crystallises in yellowish quinoxu line, N 02*06H4* ?: N OH*C:N needles melting at 295O and is soluble in alkalis ; its alkaline solution is reduced by ferrous sulphate with the formation of 2-hydroxy-3-0- aminophenylyuinoxaline ; the constitution of the latter compound, which is also obtained from acetylisatin and o-phenylenediamine, is therefore confirmed (Zoc.cit.). 2-iPj/droxy-3-o-nitr'ophen?/i-6-(or 8-)rneth ylquinoxa line, NO,*C,H,mF:N OH*C:N >C&&Me, prepared from o-tolylenediamine and 0-nitrobenzoylformic acid, crystal- libes in yellowish needles melting at 293-294'. 2-Hydroxyl-6-(or s-) ethoxy-3-o-nitrophenyZquinoxaZine, from ethoxy-o-phenylenediamine [NH2:NH,:OEt = 1 : 2 : 41 and o-nitro- benzoylformic acid, is a yellowish solid melting a t 215-216'. 2-Hydroxy-3-phenylquinoxcdine, prepared in an analogous manner, crystallises in pale yellow needles melting a t 247' ; 2-BydYoxg- 6-(or 8-)ethoxy-3-phenyZquinoxccZine, crystallises in yellow needles melting a t 205". 2-Hydroxy-3-o-arninophenyZ-6-(or S-)rnetlylquinoxa line, which crystallises in dark yellow needles melting a t 208-209', is formed as an acety 1 derivative from acetylisatin and o-tolylenedi- amine together with acetyimethylindophenazine ; it is separated from the latter by treatment with alkalis, in which the quinoxaline alone dissolves ; the acetyl group is eliminated by prolonged boiling of the alkaline solution.Methyl-+-isatin and o-phen ylenediamine condense when heated in acetic acid solution, forming 1 1-methylindophenccxine, I >C,H,, (Abstr,, 1896, i, 236), which forms yellow crystals melting at 148') and with concentrated hydrochloric acid gives an orange hydrochloride. This substance is also formed when indophenazine is methylatod, No2*C,H,*y: N ,>C,H,*OEt,, prepared OH*C:h H *C:N NBle-CNORGANIC CHEMISTRY.121 11-Benxylindophenazine is obtained from indophenazine and benzy 1 chloride, and crystallises in orange-yellow needles melting at 17 1 -5' ; it is also produced by the condensation of benzyl-+-isatin and o-phenylene- diamine. With 4-ethoxy-o-phenylenediamine, isatin yields a mixture of two ethoxyindophenazines (see Abstr., 1899, i, 719). These can be separated by conversion into the ftcetyl derivatives and recrystallisation of the latt,er from alcohol. a-d-Ethoxyindophenazine is obtained from the more sparingly soluble acetyl derivative (m. p. 208") and crystallises in yellow needles melting at 265" ; P-d-ethox$adophen&ne, obtained from the soluble acetyl derivative (m. p. 165O), is a yellow substance melting at 230'. Isntin and 3 : 4-diaminobenzoic acid condense to a n indophenaxifie- 7-(or 8-)curboxyZic m i d , which is obtained as a crystalline powder Q 6~4*C--N N=C*NMo melting above 300' ; 1O-methyZ-+-indop~enaxine, ' >C,H,, is prepared from isatin and o-aminomethylaniline and crystallises in red needles melting at 175-176' ; the hydrochloride forms a yellow, crystalline powder.10-Phenyl-+-indophenaxine, prepared from isatin and o-aminodiphenylamine, crystallises in lustrous needles melting a t 265-266'. Treatment of these two derivatives of +-indophenazine with concentrated acids leads to the formation of indophenazine and not of $-indophenazine. p-Tolylpyridazine and its Derivatives. By A.KATZENELLENBOGEN (Bey., 1901, 34, 3828-3839. Compare Gabriel and Colman, Abstr., 1899, i, 390)-A 71 per cent.yield of /I-ptoluoylpropionic acid (Abstr., 1888, 951) is obtained when succinic anhydride, toluene, and aluminum chloride are shaken for fifteen hours at the ordinary temperature. When warmed with hydrazine sulphate and sodium hydroxide, the acid is transformed into 3-p-tolylpyriduxinone, C,H,*C<gSg%>CO, which crystallises from alcohol in prisms melting at 155-156'. An acetic acid solution of bromine converts the pyridazinone into 3-p-toZyZpyridazone) C , H , * C < ~ E ~ E > C O , which crystallises from acetic acid in hexagonal plates melting a t 2 2 5 O , and is soluble in dilute alkalis, but only sparingly so in ether, alcohol, or benzene. When methylated, it yields 3-p-toZyZ-l-methyZpyriduzone, C,H,*C<N.NMe>CO, crystallising in colourless needles and melting K.J. P. 0. CH:CH at 125'. The corresponding ethyl derivative melts at 96-95''. GHTH 6-ChZoro-3-p-tolyJpyridaxine, C , H , * C < N i N>CCl, obtained by the action of phosphorus oxychloride on the pyridazone, crystallises in pointed prisms, melts a t 153', and is readily soluble in most organic solvents. 6-Methoxy-3-p-toZyZpyridccxine crystallises in four-sided plates melting a t 114-1 15' ; its plutinichloride forms golden-yellow crystals melting a t 177-1 79'. The ethoxy-derivative crystallises in needles melting a t 1 0 6 O , its picrate forms lemon-yellow needles melting at 118", tbe122 ABSTRACTS OF CHEMICAL PAPERS. platinnichlovidc melts and decomposes a t 146", the aurichloride softens a t 130' and melts a t 150-151', and the dichromate, is an orange-red powder softening at 65" and melting a t about 106'.6-Phanoxy-3-p-tolylpyridaxine forms slender, colourless needles melting at 135'. 6-lodo-3-p-t oly lp yridaxine forms, minute crystals me1 ting a t 188', and when reduced with hydriodic acid and phosphorus yields 3-p- tolplpyridaxine, which crystallises in glistening, four-sided plates melting at 106-107O and is readily soluble in most organic solvents ; thepicrate crystallises in prisms melting a t 151', the platinichloride decomposes a t about 125', and the aurichloride softens a t 147" and melts a t about 198'. Nitro-3-p-tolyZpyridccxine, N02*C7H6* C4N2HY, crystaliises in colourless needles molting at 133' ; thepicrate sinters a t 170' and melts at about 184' ; the platinichloride melts and decomposes a t 258O, and the auri- chloride melts at 211-212".Amino-3-p-tolylpyridazine, obtained by reducing the nitro-compound with stannous chloride, crystallises from water in needles melting a t 142--143O, the picrate melts and decomposes a t 170-171°, the ptatini- chloride does not melt at 260', and the benxoyl derivative melts at Hyd~oxy-3-p-tolylpyridazine crystallises from alcohol in prisms, and melts at; 210-21 1" ; its hydrochloride forms colourless needles, the dichromate, orange-yellow crystals, and the platinichloride pointed prisms melting and decomposing a t 175'. On oxidation with alkaline permangannte, p:tolylpyridazine yields pyridaxyl-3-p-benxoic acid, C,N,H3*C,H4*C02H, in the form of needles, sparingly soluble in the usual solvents and infusible at 270'.p-Tolylpyridazine and methyl iodide unite to form a methiodide, C,,HI,N,I, which turns red at 94' and melts at 182-183'. The pacrate of the methyl base, C,,HloN2Me,C,H207N,, forms lemon- yellow prisms sintering at 174" and melting at 183-184', and the platinichloride, (C11Hl,,N2Me),PtCl,, melts and decomposes a t (C13H140N2)2,H2Cr207, 178-1 79". 214-215'. p-Tolylpyrrolidine, C,H4MdH< CH2*yH2 ~ H . CH, , obtained by reducing ptolylpyridazine with sodium and alcohol, is-an oil and is volatile with steam; the picrate sinters at 145O and melts at 150"; no other salts were obtained in a crystalline state. A further product formed on reduction is 3-p-folylhexahydropyridcsxine ; its nityate forms colourless prisms melting at 186' and the picrate melts and decomposes at 16 7-1 68'.Action of Hydrochloric Acid on Pyruvic Acid. By A. W. K. DE JONU (Annalen, 1901, 319, 121-128. Compare Abstr., 1899, i, 483; 1901, i, 446)-The phenylhydrazone of the ay-lactone of a-keto-y-hydroxybutane-ay-dicarboxylic acid, when heated with hydrochloric acid of sp. gr. 1.14 yields 3-keto-2- phenyl-4-methyl-3: 3-dihydro- 1 : 2-diazine-6-carboxylic acid, J. J. 8. NP h-N>C CO,H Co<CMe *CHORGANIC CHEMISTRY. 123 (compare Ruhemann, Abstr., 1894, i, 425). The employment of stronger acid of sp. gr. 1.20 in this experiment leads to the production of the compound, Cl2H1,,O3N2, crystallising from glacial acetic acid in white needles and melting at 280O. This substance is insoluble in a solution of alkali carbonate, but dissolves in one of sodium hydroxide ; the addition of hydrochloric acid to the alkaline solution causes the precipitation of the monobasic mid, C,,H,O,N,H,O, a conlpound separating in yellow needles or plates and melting at 237-238'.The new acid forms a readily soluble potassium salt and the compound, when boiled with strong hydrochloric acid, regenerates the anhydrous acid, C,,H,O,N,. which has the same melting point as its hydrate. Zoth forms of the acid, when treated with hydrochloric acid of sp. gr. 1.14, yield a compound, crystallising in white needles, which is readily decomposed by water. By ST. ANGERSTEIN (Ber., 1901, 34, 3956-3963. Compare Gabriel and Colman, Abstr., 1899, i, 638).- 2-Chlos.0-4 : 6-dinaet?~y~yrimidiize, CCl<N:CMe N.CMe>CH, obtained by the action of phosphorus oxycliloride on oxydimethylpprimidine ( Abstr ., 1894, i, lll), melts a t 38', distils at 223.3' under 756 mm.pressure, dissolves readily in water, alcohol, or ether, and gives a crystalline compound with mercuric chloride. When reduced with zinc dust and water, it yields 4 : 6-dimethylpyrimidine (Gabriel and Colman, loc. cit.), which, on oxidation with permanganate, yields pyrimidine.4 : 6-dicarb- oxylic m i d , crystallising in needles and decomposing a t 222'. The acid yields a colourless hydrochloride, a yellow platinichloride, and a pale green copper salt, C,H,O,N,Cu. When less permanganate is em- ployed, 4-methylpyrimidine-G-carboxy Zic acid, CH<NG(C02H)>CH, N-CMe is obtained ; i t crystallises in needles, melts and decomposes at 165-1 66O, and is readily soluble in water.The copper and silver salts have been prepared. C hlorodime th y lpyrimidine readily reacts with an alcoholic solution of sodium methoxide, yielding 2-methoxy-4 : 6-dimethylp~rimidine, which crystallises in prisms, melts a t 35-36', and distils at 208-209' under 144 mm. pressure. It combines with hydrochloric acid, whilst with mercuric chloride it yields a compound, which crystallises in needles soluble in hot water or alcohol. 2-Ethoxy- 4 : 6-dimethylpyrimidine is a colourless, strongly refractive oil boiling at 220.1' under 764 mm. pressure ; it is appreciably soluble in water, and yields a compound, C,H,,ON,,HgCI,, sparingly soluble in water. The hydrochloride is readily soluble and precipitates are not obtained with auric chloride, platinic chloride, potassium dichromate, or sodium picrate.On treatment with bromine water, 5-bromo-2-ethoxy-4 : 6- dimethylpyrinzidine, melting at 40-41' and boiling a t 254' is obtained. 2-Phenoxy-4 : 6dimethylpyrimidine melts at 81', distils a t 305-312", and is very sparingly soluble in water. With mercuric chloride, it yields the compound C,,H2,0N,, ZHgCI,, crystallising in needles and G. T. M. 4 : 6-Dimethylpyrimidine. C7H,,ON,(HgC1,)2,124 ABSTRACTS OF CHEMICAL PAPERS. soluble in alcohol or hot water ; the hydrochloride is readily soluble in both water and alcohol. 2-AniZino-4 : 6-dimethylpyrimidine crystallises from toluene in hexagonal plates melting a t 8s-89' and is insoluble in water ; the pkatinichloride, (C,,H,,N,),,H,P tC1,: crystallises in yellow needles and the picrate in yellow plates melting a t 186'.It yields a nitroso-derivative, C4N2HMe,*NPh*N0, which crystallises in well-developed prisms melting a t 130-131' ; the picrate melts at 184' and the platinichloride crystallises in yellow needles. 2-Amino-4 : 6-dimethylpyrimidi.ne, obtained by heating the chloro- base with alcoholic ammonia a t loo', crystallises in needles melting at 150-152'. The platinichloride forms yellow prisms melting at 225'. The hydy*ochloi-ide melts a t 181' and is readily soluble in alcohol or water. The picrute crystallises in yellow plates and melts a t 230°, and the compound with mercuric chloride, C,H,N,,HgCl,, crystallises in colourless needles. 4 : 6-Di.?-i~ethyl~yrimidyl 2-mercaptaln, C4N2HMe,* SH, crystallises in yellow, glistening needles melting at 198' and on oxidation yields 4 : 6-dimetl~yZ~yrimidine 2-disuZphide, S,(C4N2HMe,),, melting a t 162-163' and soluble in acids and in most organic solvents. J.J. S. Synthesis of Uracil, Thymine, and Phenyluracil. By ENIL FISCHER and GEORG ROEDER (Ber., 1901,34,3751-3763. Compare Abstr., 1901, i, 2Y4).-Bromol~ydrouraciZ separates from water or alcohol as a colourless, granular powder; i t dissolves in about 5 parts of boiling water or 10 parts of boiling alcohol, but is insoluble in ether or carbon disulphide. HgdroxyhydrouraciZ, C,H,O,N,, a substance the constitution of which was not determined, but differs from that of uracil in containing an additional H,O, is the chief product of the action of alkalis on bromo- hydrouracil ; it dissolves in 12 times its weight of water, crystallises on cooling in colourless, flat needles, and melts at 228' (corr.) with partial decomposition when quickly heated.By heating bromohydro- uracil with pyridine, uracil itself (C,H402N,) is formed ; it crystal- Iises from hot water in minute, colourless needles, and when quickly heated becomes brown at about 280' and melts with liberation of gas a t 335'. NH-CO CHPh>CH2, prepared from carb- amide and cinnamic acid, crystallises from alcohol in prismatic needles, melts a t 202--203° (corr.), and dissolves in about 26 parts of hot water or 20 parts of boiling alcohol ; it dissolves readily in cold dilute alkalis or in concentrated hydrochloric acid. 4-PhenyZbromouraciZ, CloH,02N,Br, crystallises in minute, pointed needles and melts a t about 214" (corr.) with liberation of hydrogen bromide.4- Phenyluracil, CloH802N2, crystallises in microscopic needles and melts and decomposes a t 267' (corr.). Condensation Products of 1 : 8-Naphthylenediamine and its Derivatives with Acetone. BADISCHE ANILIN- & SODA-FABRTK (D. R.-P. 122475).-1 : 8-Naphthylenediamipe sulphate, or the sodium 4-Phenylhydrourctcil, T. 35. L.ORGANIC CHEMISTRY. 125 salt of one of its sulphonic acids, readily condenses with acetone in slightly acid solution. The condensation p o d u c t from the diamiue itself has the formula C,,H6<~~>CMe2 ; the substance C1,H1,O3N,S, has also been prepared from 1 : 8-naphthylenediamine-4-sulphonic acid. 1 : 8-Naphthylenediamine-2 : 3-disulphonic acid and 4-chloro-1 : 8-naph- thylenediamine give rise to similar derivatives.G. T. M. Homologues of Xanthine. C. F. BOEHRINGER st SOHNE (D.R.-P. , is produced by /NH*C CO *NH 121 224).-8-MethyZxanli~ine,~ CMeNN--jNH. & heating uric acid with acetic anhydride (10 parts) until the ineoluble residue no longer reduces ammoniacal silver nitrate ; the crude base, purified by conversion into its potassium derivative and reprecipitatiorL with dilute acid, crystallises in colourless prisms or plates which are very sparingly soluble in water and melt above 400'. The hgdrochlor- ide separates from a concentrated hydrochloric acid solution in colourless, lustrous prisms. The methylxanthine readily dissolves in solutions of ammonia or the alkali hydroxides and yields a stable, gelatinous silver derivative with ammoniacal, and a flocculent double salt with neutral, silver nitrate.The condensation is accelerated either by adding a tertiary base (pyridine, quinoline, or dimethylaniline) or by conducting the operation under pressure at 180-185'. 8-Ethgllxanthine results when propionic anhydride is employed ; this base resembles its lower homologue, but is more soluble in water ; it darkens at 350' and decomposes at 390'. 8-isoPropyZxccnthine, prepared in a similar manner from isobutyric anhydride, crystallises in short prisms, darkens a t 340°, and decomposes at 380'; it is twice as soluble in water as the etlhyl compound, but otherwise resembles the latter in dissolving in dilute acids or in solutions of ammonia or- the alkali hydroxides, and in yielding a stable silver derivative with ammoniacal silver nitrate.ing 3-methyluric acid (Abstr., 1900, i, 63) with acetic anhydride in the presence of pyridine, crystallises from water in colourless, felted needles containing 1H20 ; it darkens at 320° and decomposes at 350'. 1 : 3 : 8-TrirnethgZxanthine, CMe<N--C.NMe,CO , derived from 1 : 3.dimethyluric acid, crystallises in needles or prisms, melts a t 325', and is the most soluble of these xanthine derivatives, dissolving in 40 parts of water ; with silver nitrate and nitric acid, it yields a crystal- line, double salt, and with an ammoniacal solution of the same reagent a gelatinous, silver derivative. By RUDOLF NIETZKI and JOSEF SLABOSZEWICZ (Bey., 1901, 31, 3727-3732).--5'-C?~loro-2' : 4'-dinitvo- 2-aminod~lzenyZamine, NH2* C6H,*NH* C6H2Cl(N02)2, prepared from ' The positions are numbered in accordance with the scheme proposed by l?, Fischcr (BCT.~ 1897, 30, 557 ; compnre Abstr., 1897, i, 268, lino 4, wvhtle positions 8 and 0 should be interchanged).NH*E--CO-rMe G. T. M. New Synthesis of Fluorindine.126 ABSTRACTS OF CHEMICAL PAPERS. o-phenylenediamine and dichlorodinitrobenzene, forms orange-yellow crystals and melts a t 232' ; o-diccminodiphenyl-4 : 6-dinitro-1 : 3-phenyl- enediumine, C,H,(NO,),(NH* C,H,*NH,),, cry s t a k e s from xylene in glistening, yellow flakes and melts a t 253". Lbiamiitodiphen~ltetrffinzino- benzene, C,H,(NH,),(NH- C6H,*NH2)2js forms a hydrochloyide and a crystalline double salt with zinc chloride.ArninophenyZdiaminophen- _- powder and forms a hydrochloride. Phenojluorindinlze (homojluorindine), C,H,<~~~~,H,GN-_>C,H,, NH is formed on boiling the preceding compound with dilute hydrogen chloride, and is identical with the substance prepared by Caro. Divnethyljluorindine (tolufluorindine), prepared from o-tolylenediamine, [(NH,),:Me = 3 : 4 : 13, was prepared by a similar method, and is perhaps identical with the compound prepared by Fohrenbach (Diss., Basel, 1898). T. 11. L. Derivatives of the Phenyl Ethers, By CARL HAEUSSERMANN and OSCAR SCHMIDT (Ber. 1901, 34, 3769-3771).--o-AxoxyphenyZ ether, obtained by reducing o-nitrophenyl ether dissolved in alcohol contain- ing sodium acetate in the cathode cell with an electric current of 2 amperes and 6 volts, crystallises in yellowish-red leaflets and melts a t 95'.p-AzoxyphenyZ ether, produced in a similar manner from pnitrophenlyl ether, crystallises in orange-yellow needles and me1 ts a t 115'. p-AxoxyphenyZ p-tolyl ether from p-nitrophenyl tolyl ether (m. p. 69') crystallises in lustrous-yellow leaflets and melts a t 142'. Quinol p-axoxydiphenyl ethey, from quinol p-nitrodiphen y1 ether, obtained by the action of a current of 2 amperes and 25 volts on a dilute alcoholic solution of the nitro-derivative, crystallises, in light yellow leaflets and melts a t 183". The corresponding amino-derivatives are obtained by the use of a tin cathode (compare Boehringer & Sons, Abstr., 1901, i, 684). p-Aminophenyl p-tolyl ether, produced in this way, crystallises from water in white needles and melts a t 123". p-AxoplLenyZ p-tolpl ether is prepared by reducing p-nitropheny 1 p-tolyl ether with zinc dust and alcoholic potassium hydroxide and oxidising the resulting hydrazo-derivative with atmospheric oxygen ; it forms small leaflets melting a t 175". Quinol p-axod-iphenyl ethev crystallises from benzene in lustrous, yellowish-red leaflets melting a t 2 1 0'. G. T. M. Action of Monochloroacetic Acid on p-Hydroxyazobenzene. By JUL. MAI and FRITZ SCHWABACHER (Ber., 1901,34, 3936- 3941)- Neither diazobenzene chloride nor p-diazobenzenesulphonic acid react with phenoxyacetic acid ; benxeneano-p-phenoxyacetic: acid, N,Ph*CGH,*O*CH2*C0,H, is, however, obtained by the action of sodium chloroacetate on the sodium derivative of p-hydroxyazobenzene ; it crystallises from water jn long, yellow needles, melts at '193O, and forms a sodium salt insoluble in alcohol and an ethpl ester, which is n green, cryst'alline compoundORGANIC CHEMISTRY. I27 melting a t '70". The corresponding p-sulphonic acid was obtained by the action of sodium chloroacetate on phenolazo-p-benzenesulphonic acid and forms slightly soluble potassiunz sodium, potassium hydrogen, and buriurn salts. The p-nitro-derivative, obtained from p-nitrobenz- eneazophenol, crystallises in lustrous red needles, melts a t 205', and forms a crystalline, violet-coloured sodiunz salt. The phenoxy-acid, when reduced with stannous chloride, yields a compound which melts a t 2 2 5 O , forms a soluble barium salt, and is probably the semidine, NH,*C,H,*NH*C,H,*O*CH,*CO,H ; the sodium salt, when similarly reduced, yields a compound which crystallises in colourless needles, melts a t 239O, forms a slightly soluble, crystalline barium salt, and is probably the hydrazo-compound, NHPh*NH.C,H,*O.CH,*CO,H. p-Cresolazobenzene, when treated with chloroacetic acid, yields the compound, N,Ph=CGH,31e.0*CH,*Co~H, which melts a t 133' ; p-tolueneazophenol yields, similarly, the compound, C,H4Me N2-CGH,*0 CH, C O,H, which melts a t 300"; the dibasic acid fromp-aminobenzoic acid melts a t 285' and forms an easily soluble socliunz salt ; the acid obtained by treating diphenyltetrazophenol with chloroacetic acid crystallises in brown needles.and melts a t 255". R. H. P. Diphenyl Derivatives. By ERNST B~RNSTEIN ( B ~ T , , 1901, 34, 3963-3969. Compare Ullmann and Forgan, this vol., i, 89).--When aniline (1 mol.) is diazotised in hydrochloric acid solution and ' then mixed with a colourless solution of copper sulphate (1 mol.) in sodium thiosulphate (6 mols.), in other words, with cuprous sodium thio- sulphate, it yields phenyl sulphide and benzeneazodiphenyl (Griess, Bey., 1876, 9, 132). 0- and y-Toluidine and sulphanilic acid yield sulphides but not diphenyl derivatives on similar treatment; a-naphthyl- amine yields a-azonaphthalene. J. J. S. Reduction, in an Alkaline Solution, of 2 : 4 : 5-Trimethyl- benzalaeine and the Preparation of some Derivatives of the Reduction Products. By EVERHART P. HARDING (J. Anzer. Chew. Soc., 1901,23,829-S42).-A more detailed account of work previously published (Abstr., 1900, i, 613-614). E. G. Conversion of o-Aeiminobenzaldehyde into Anthranil. By EUGEN BAMBERGER and ED. DEMUTH (Ber., 1901, 34, 3874-3S77).- When heated with water a t 110' for 2 hours, or alone at 120', o-aziminobenzaldehyde, CHO*C,H,*N3, is converted into anthranil, N -- for which the constitution C,H,< I >O is suggested ; the anthranilic C H acid formed by the action of alkalis (Abstr., 1901, i, 391), represents a product of further change. Similarly, 3 : 5-dichloro-6-azimino- 1-benzaldehyde and 4 : 6-dimethyl-1 -azimino-2-benzaldehydo are con- verted respectively into dichloroant hranil and dimethylanthranil by heating with water. The melting point of dichloroanthranil is 1 12.5-1 13.2' (corr.) and not 96-97" (Friedlander and Schreiber, Abstr., 1895, i, 524). T. 31, L.128 ABSTRACTS OF CHEMICAL PAPERS. The Present Condition of the Chemistry of Albumin. Ry ALBRECHT KOSSEL (Bela., 1901, 34, 3214-3245).-A review of the recent advances in the chemistry of albumin, with an extensive bibliography of the subject. G. T. M. The Present Condition of the Chemistry of Albumin. By ERNST SALKOWSICI (Ber., 1901, 34, 3884 -3885).-A question of priority in relation to Kossel's lecture (preceding abstract). I<. J. P. 0. Decomposition of Albumin. By MAXIMILIANO DENNSTEDT (Chem. Zed., 1901, 25, 832-836. Compare Ahstr., 1901, i, 780),- It is thought probable that albumoses and peptones are formed simultaneously during the decomposition of proteids. Chittenden's name, proteoses, for all proteid-like decomposition products of proteids is suggested as a general term in place of 'albumose and peptone, whilst, when the source of the proteose is known, special names, for example, caseinose, fibrinose, albumose, Bsc., are used. The method of formation can also be indicated by prefixes such as pepto-, trypto-, bacteri-, acid-, alkali-, &c. When wheat fibrin or zein is boiled with baryta water, part of tbe nitrogen of the proteid is evolved as ammonia and part of the sulphur converted into barium sulphide or sulphate. From wheat fibrin, five distinct proteoses have been isolated and analysed. They all have strong acidic properties and may be titrated by the aid of standard alkali; the results vary, however, with the indicator employed, and they are all probably polybasic acids. Two definite products have been obtained from zein, and these also have acid properties. When zein is heated with water at pressures below 0.22 atmosphere, it is transformed into an insoluble modification having the same composition. As the pressure is increased, ammonia and hydrogen sulphide are formed, together with proteoses which have acidic properties and are present as ammonium salts in the final product. Three of these proteoses have been obtained and analysed; they appear to be more nearly allied to zein than the proteoses obtained by the aid of baryta water, and all give the Millon and biuret reactions. It is thought that the formation of proteoses from proteids is not merely a hydrolytic action, but is a complex chemical decomposition accompanied by loss of nitrogen and sulphur ; water is taken up, and oxidation probably occurs. J. J. S . Nature of Enzymes. By THOMAS BOKORNY (Chew,. Cent?., 1901, ii, 1210 ; from Phccrm. Centvalhcclle, 42, 681-684).-The similarity of the behaviour of the enzymes to that of protoplasm indicates that the former substances are active albumins (protoplasmaproteln) belonging to the group of nucleoalbumins. The original paper contains a table in which descriptions of the properties of these substances are placed side by side. The enzymes are contained in, and secreted by, the living proto- plast, and can be regenerated in the necessary quantity. E. W. W.