摘要:

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.

ISSN:0368-1769    

DOI:10.1039/CA9028200069

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. 87 Mineralogical Chemistry. Formation of Coal. By S. STEIN (Chem. Centr., 1901, ii, 950; from Mugy. elhem. folySirat, 6, 39-42).-Wood mas heated with water in sealed tubes, as in the experiments of Cagniard de la Tour, and black masses resembling coal obtained ; these gave the following results on analysis : Temperature. 245" 250 255 265 2 75 280 290 Time. H per cent. 9 hours 5.4 6 9 2 5.1 6 9 9 5.2 5 Y , 4.7 6 ?, 4.5 5 9 9 4.1 5 9 ) 3% C per cent. 64-30 69.20 70.3 72.8 74.0 77.6 81.3 The increase in the amount of carbon depends on the pressure as well as on the temperature and duration of the experiment, since at atmospheric pressure for 2 days a t a red heat the amount of carbon never exceeded 78 per cent. L. J. 5. A Variety of Polydymite or Sychnodymite.By WILH. STAHL (%it. Kryst. Min., 1901,35, 289 ; from Be?-g-u. hiittenm. Zeit., 1899, 58, 182).-Light to dark grey, cubic crystals from the Siegthal gave on analysis : 23-46 5.70 26.80 3.86 39.28 0.47 99.57. cu. Ni. co. Fe. S. Insol. Total. This gives the same general formula (Co,Cu,Ni,Fe),S,, as both poly- dymite and sychnodymite, and approaches the latter i n the proportions in which the metals are present. Pyrites and Marcasite. L. J. S. By HENRY N. STOKES (Bull. U.S. Geol. Survey, 1901, No. 186 [Xer. A',, Chem. & Physics, No. 351, 1--SO).-- When pyrites arid mareasite are not distinctly crystallised it is often88 ABSTRACTS OF CHEMICAL PAPERS. difficult to distinguish between them, and the characters usually relied on for this purpose, namely, colour, sp.gr. and ease of oxidation, are not altogether trustworthy. It is pointed out that the true colour of marcasite is tin-white, the usual bronze-yellow being due to tarnish. The author has devised a chemical method for the dis- crimination of these minerals, and for their quantitative determination in mixtures. This method depends on the fact that when pyrites or marcasite is boiled with an excess of a solution of a ferric salt until the latter is completely reduced, the ratio of sulphur oxidised to mineral decomposed is perfectly definite and characteristic of each mineral, provided certain standard and easily controllable conditions are observed. With a boiling solution of iron ammonium alum con- taining 1 gram of ferric iron and 16 C.C. of 25 per cent.free sulph- uric acid per litre, the percentage of s u l p h r oxidised in pyrites is about 60.4, and in marcasite about 18 per cent, of the total sulphur. These figures are the characteristic oxidation coefficients, which depend, however, on the temperature and concentration of the solution. The oxidation of pyrites or marcasite to ferrous salt, sulphuric acid and free suIphur cannot be expressed by any single equation, but takes place according t o two or more, An empirical curve for the oxidation coefficients of mixtures of pyrites and marcasite in known proportions gives a means of quantitatively determining the com- position of naturally occurring mixtures of these minerals. The influence of various impurities on the results is described : the nature of the impurities can sometimes be distinguished by this method, for example, whether chalcopyrite or bornite is present in cupri- ferous pyrites, The determinations are made in an atmosphere of carbon dioxide, and a detailed description is given of the apparatus employed, Some of the experiments which have been made (Abstr., 1895,ii, 316 ; 1896, ii, 108; 1898, ii, 602 ; 1901, ii, 319) with the view of determining the state of combination or valency of iron in pyrites, &c., are here repeated, only to show that the evidence derived from such experiments is inconclusive.L. J. S. Hydrogothite, a Definite Hydrated Iron Oxide. By J. SAMOILOFF (Zed. Kryst. Min., 1901, 35, 272-274).-1n 1889, P. A. Zemjatschensky described as a new mineral, under the name hydro- gothite, a hydrated iron oxide with the formula 3Fe,0,,4H20; it mas found as thin veins in limonite in central Russia, and had a fibrous structure and cochineal-red colour.These observations, which have not been generally accepted, are confirmed by the present author, who considers hydrogothite to be a definite mineral species ; and he records its occurrence in the iron-ores of several localities in the Tula government. I t occurs as thin veins in, and as crusts 2-5 mm. thick on, massive limonite, and also as a later formation in the interior of hollow limonite concretions. Analysis gave : H20, 12.33-13.16 ; Fe203, 86-01 per cent,, agreeing with the above formula: phosphorus, aluminium and traces of manganese are also present. The observed sp. gr., 3.73, is probably too low.The powder of the mineral is tile-red in colour. Under the microscope are seen transparent plates H = 4.MINERALOGICAL CHEMISTRY. 89 or needles with a distinct cleavage in one direction, straight extinction, optically positive in the direction of the length, and very strong pleochroism. L. J. S. Ktypeite and Conchite. By HEINRICH VATER (Zeit. Kryst. Min., 1901, 35,149-17S).-Conchite (Abstr., 1901, ii., 168, 395) is identical with aragonite, and the same is probably also true of ktypeite (Abstr., 1898, ii, 604). L. J. S. Analyses of Magnesite [and Dolomite]. By JOZSEF LOCZEA (Zeit. Kryst. Min., 1901, 35, 282).--The following analyses are given of : I, grey magnesite, and 11, white dolomite, both from Jolsva, Gomor Go., Hungary: MgO. CaO. MnO. FeO.Fe,03. COP FeS,. Insol. Total. I. 44.63 - 0.i6 3.88 trace 51.34 0.19 0.04 100.24 11. 21-10 30.28 trace 0.98 trace 47.61 - 0.04 100*01 L. J. S. Pseudogaylussite. By CHARLES 0. TRECHMANN (Zeit. Kryst. Min., 1901, 35, 283-285. Compare Abstr., 1898, ii, 80).-A description, with photographic reproductions, is given of some crystals dredged up from the Clyde a t Cardross opposite Greenock. They are of a reddish- brown colour, with curved faces and rounded pyramidal terminations ; in cross-section they are square or rhomb-shaped. Sp. gr. 2575 and 2.602, but the material is slightly porous. Thin sections under the microscope show the material to consist mainly of minute (0,165 mm. diam.) spherules of calcite with radialIy fibrous structure. Analysis gave : Ca3(PO,),. CaCO,.MgCO,. Total. 5.52 83.52 9.03 98-07 Traces of silica, iron, manganese, chlorine, sulphuric anhydride and organic matter are also present. No new light is thrown on the origin of these peculiar pseudomorphs, which are also known by the names thinolite and jarrowite. L. J. S. Artificial Preparation of Monetite. By AUGUST DE SCHULTEN (Chem. Centi'., 1901, ii. 1128; from Bull. Xoc. franq. Min., 24, 323--326).-Crystals of anhydrous dicalcium phosphate or monetite have been prepared by slowly dropping a 0-6 per cent. solution of ammonia into a solution containing 70 grams of anhydrous calcium chloride, 226 grams of disodium hydrogen phosphate (Na,HPO,, 12H,O) in 500 C.C. of water and 80 C.C. of hydrochloric acid of sp. gr. 1.19. After remaining 2-3 weeks, dicalcium phosphate was found to have crystallised in transparent, triclinic plates [a : b : c = 1,049 : 1 : 1.0441 having a sp.gr. 2.928 at 15'. This preparation resembles, and may possibly be identical with, Kloos' mnrtinite, Ca,H,(PO,),,&H,O which has a sp. gr. 2.894. E. w. w. VOL. LXXXII. ii. 790 ABSTRACTS OF CHEMICAL PAPERS, Stilbiteand Foresite from the ElbaGranite. B~ERNESTOMANABSE (Jahrb. Min., 190l,ii, Ref. 28-31 ; AttiSoc.~oscanaXci.Nat.Mem., 1900, 17, 203-227).--Stilbi te occurs as a yellowish-white mass encrusting the tourmaline and other minerals in drusy cavities in the Elba granite. Analysis I is of radial aggregates of small crystals, and I1 of globular and sheaf shaped groups ; in both cases, details are given of the amounts of water expelled a t various temperatures.The first of these analyses agrees with the usual stilbite formula, which, according to Clarke's theory of the silicates (Abstr., 1897, ii, SO), is written as [A~(SIO,),A~H~]C~[A~(S~,O~)~C~H~A~],~H,O. This is referred to as typical stilbite. The second analysis with more silica requires one of the (SiO,) groups in this formula, to be replaced by the group (Si308), whilst in an earlier analysis by Grattarola and Sansoni with less silica, there are only two (Si,O,) groups : H,O. SiO,. Al,O,. CaO. Na,O. K,O. Total. I. 17.75 56.59 17.73 7.03 1-73 - 100*83 11. 1494 61.51 15.01 6.74 1.91 - 100.1 1 111. 16.66 48.93 27.56 5.16 1.14 trace 99.45 Foresite occurs like the stilbite, but is snow-white. It gave on analysis the results under 111, agreeing with those required for the formula 13H20, 1 2Si02,4A1203,2(Ca,Na2)0, which is written in con- formity with Clarke's striictural formula of stilbite by replacing H4 by four AI(OH), groups.I n discussing the origin of these zeolites, the following analyses are given of the Elba granite. I (also traces of MnO and Zr02) of the normal biotite-granite; I1 (also trace of MnO) of dark, fine-grained patches in the same ; 111, (also trace of B203) of white veins contain- ing the tourmaline druses : SiO,. A1,03.Fe0,. FeO. CaO. MgO. K,O. Na,O. P,O,. H,O. Total. I. 69.92 15 68 4'57 1.85 0.92 3.18 4-35 0.24 0-59 101.30 11. 70.21 15-72 5-03 2.11 1.07 3.25 3-66 0.29 0.48 101.82 111. 75.17 14.05 0.21 0.32 0.16 4.57 5.00 - 0.45 99.93 The orthoclase of this granite has the following composition ; 1, for the fresh material, 11, for the slightly altered, and 111, for the much altered material; whilst IV gives the composition of a zeolitic mixture representing a still further stage in the alteration of the felspar : SiO,.A1,0,. Fe,O,. CaO. KzO. Na,O. H,O. Total. I. 64-85 18.14 - 0.24 11.41 4.14 0.81 99.59 11. 51.64 23.98 0-18 3.82 15.37 100.00 111. 45.44 32-88 trace 2.08 [:%] 14.97 100*00 IT. 61.54 17.04 trace 4.92 1-75 2.03 13.70 100.98 The alteration of the orthoclase to zeolites has been effected by water charged with carbon dioxide. L. J. S. By H. STAD- LINGER (Zeit. Kryst. Min., 1901,35,313-315; from Sitx.-Bey.phys.-med. Xoc. Erkangen, 1899, 31, 1--63).-Large porphyritic crystals of fresh - Formation of Pseudophite in Granitic Rocks.MINERALOGICAL CHEMISTRY.91 microcline, with some intergrown plagioclase, from the granite of Strehlerberg in the Fichtelgebirge, gave on analysis the results under I ; sp. gr. 2.559. The following stages in its alteration are traced out, the end product being pseudomorphs of pseudophite, of which the composition is given under 11; sp. gr. 2.6397. The microcline first loses its lustre and becomes coated with rusty-brown limonite ; later, in the outer zone and along cleavage cracks, it becomes green; still later, the felspar is completely kaolinised, the colour passing to greyish- green, and finally to dark olive-green. Under the microscope, the following stages are recognised : complete kaolinisation of the enclosed laths of plagioclase ; commencing turbidity of the microcline ; forma- tion of secondary quartz and muscovite ; destruction of the cross- hatched ’ structure ; development in the exterior portions of a green colour and of scales of lithia-iron-mica ; accumulation of rutile needles ; appearance of zircon ; finally, the destruction of the grains of kaolin and the remains of the felspar.The analysis of the “pseudophite” shows it to be a chloritic sub- stance intermediate between pennine and clinochlore ; its composition can be expressed as 62.11 amesite molecules and 41.29 antigorite molecules. A granular dolomite a t the granite contact explains the large increase in the amount of magnesia : H20 Losson SO,. A1,03, Fe203. FeO. MnO. CaO. MgO. K20. Na,O. at 100O.ignition. Total. I. 62.96 19-36 0’40 1‘18 - 0’90 0.86 11.94 2.51 0.09 0.24 100.44 11.30’30 20.06 1.63 5’30 - 0.87 28.28 1.32 1-40 0.74 11.89 101.79 111. 45.80 6.52 18.03 6’13 1.52 4.63 1.76 1-17 1’39 9-90 3-95 100-80 Analysis I11 is of nontronite, which occurs near Strehlerberg as an alteration product of a schistose amphibolite : the material analysed contained some undecomposed hornblende, as well as a little mica, magnetite, and quartz. [Analyses of Garnet and Gold.] By W. REISS and A. STUBEL (Zeit Kryst. Min., 1901, 35, 298-301 ; from Geologische Studien in cler Republik Colombia. 11. Petrographie, Berlin, 1899).-The following mineral analyses are contained in an account of the minerals of Colombia. Rhombic dodecahedra of garnet of a greenish-grey colour, sometimes reddish in the interior, and optically anomalous, from La Topa, gave the following results.The magnesia probably belongs to enclosed malacolite. Loss on L. J. S. SiO,. A1,0,. Fe,O,. CaO. MgO. ignition. Total. 40.03 21.14 2.37 34.46 2.03 0.53 100.56 Alluvial gold from various localities gave, on analysis by Kollbeck, the following results; small amounts of copper and iron are also present : Au. 80’43 83’33 89.00 77-53 84’84 71.13 72.29 87-98 83.49 Ag. 17’89 13.56 9.43 20.89 13.63 24.09 24-42 11-03 14’79 L. J. 5. Theory of Tourmaline Mixtures. By GUSTAV TSCHERMAK (Zeit. Compare Abstr., 1900, ii, 217).-- The author upholds the Kryst. Min., 1901, 35, 209-219. A reply t o Penfield (Abstr., 1900, ii, 602). 7-292 ABSTRACTS OF CHEMJCAL PAPERS. view that the composition of tourmalines can be better expressed by the isomorphous mixing of two definite compounds rather than by tbe substitution formula of Penfield. 11. J. S. A Stony Meteorite which fell at Felix, Alabama. By GEORGE P. MERRILL (Proc. U.8. Nat. Museum, 1901, 24, 193--198).-This stone, weighing 2049 grams, was seen to fall on May 15th, 1900, near Felix in Perry County, Alabama. The broken surfaces are dark smoky grey, almost black in colour, The material is soft and friable and is very fine grained, with numerous small chondrules. Sp. gr. 3.78. The microscopic structure is described as follows : in a very dense, dark grey, seemingIy amorphous base are scattered olivine, augite and enstatite in the form of fragments and chondrules, and interspersed with occasional minute blebs of native iron and troilite. From analyses by P. Fireman of the metallic portion and of the soluble and insoluble silicates, the composition of the stone is : Fe. Ni. Co. Cu. SiO,. Al,O,. Cr,O,. FeO. FeS. 2.59 0.36 0.08 0.01 33.57 3.24 0.SO 26.22 4.76 MnO. Ni0,CoO. CaO. MgO, K,O Na,O. C. H,O. Total. 0.68 1.01 5.45 19.74 0.14 0.62 0.36 0.16 99.79 The mineralogical composition is : metal 3.04, troilite 4-76, chromite 1.17, graphite 0.36, soluble silicate (olivine in part) 72.60, insoluble silicate (enstatite and augite in part) 18.07 = 100*00. L, J. S.

ISSN:0368-1769    

DOI:10.1039/CA9028205087

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年代:1902

数据来源: RSC

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92 ABSTRACTS OF CHEMJCAL PAPERS. Physiological Chemistry. Physical and Chemical Phenomena of Respiration at High Altitudes during a Balloon Ascent. By J. TISSOT and HALLION (Compt. rend., 1901, 133, 949--951).-At altitudes up to 3500 metres the proportion of oxygen absorbed and carbon dioxide exhaled increases with the altitude, so that the blood takes up practically the same quan- t i t y of oxygen per minute, whatever the altitude up to the limit stated. The volume of air inhaled, measured a t the actual temperature and pressure, varies little, but tends to diminish at high altitudes. The variations in the respiratory quotient follow an order the inverse of that which would be followed if the exhaled carbon dioxide obeyed the laws of solutions of gases. C. H. B. Changes in the Hamoglobin of Bloodunder low Atmo- spheric Pressure.By J. VALLOT (Compt. rend., 1901,133,947-949). -Experiments mere made a t different heights on Mont Blanc and in a balloon, the quantity and rate of reduction of the hsmoglobin being determined by means of Henocque’s hsmatospectroscope. The resultsPHYSIOLOGICAL CHEMISTRY. 93 show that a reduction in the pressure of the air at once produces an increase in the activity of the exchanges in human blood, and thereby compensates for the diminution in the mass of oxygen in a given volume of the air. The activity of the reduction is practically the inverse of its duration, since the actual quantity of hsemoglobin in the blood varies but little, even a t high altitudes. Mountain sickness is due to an increase in the duration of reduction, and the fatigue of climbing tends to prevent the diminution in the duration of reduction and may produce the same change as accompanies mountain sickness.Rest a t high altitudes promotes the re-establishment of the physio- logical functions, After descent, the return to normal conditions is slower the longer the sojourn at a high altitude and the more complete the acclimatisation t o it. C. H. B. Dissociation of Carboxyhamoglobin. By NESTOR G REHANT (Conzpt. rend., 1901, 133, 951-952).-A dog was allowed to breathe first air containing 1 per cent. of carbon monoxide for 12 or 15 minutes and then air or oxygen, the quantity of carbon monoxide in the blood being determined from time to time. The following figures, representing the quaritity of carbon monoxide in 100 C.C.of blood, show that the elimination is much more rapid with oxygen than with air : Time after poisoning 0 10 20 30 40 50 mins. Breathing air ......... 14.7 14.6 14.5 12.8 11.4 10.2 C.C. Breathing oxygen ... 23.7 16.9 10.1 8.2 5.7 4.2 C.C. C. H. B. Metabolism in Man. By L. SPIEGEL (Virchow's Avchiv, 1901, 166, 364-371).-The investigation relates t o the metabolism of sulphur compounds. I n the oxidative decomposition of proteids in the body, cystin and hyposulphurous acid are constantly formed. These are not final products but are further oxidised under normal circumstances. The appearance of cystin or hyposulphites in the urine points to diminution of oxidation. The condition is compared to what occurs in regard to sugar in diabetics.By (OTTO COHNHEIII (Zeit. physiol. Chem., 1901, 33, 451-465).-The dis- :appearance of peptone when in contact with the intestinal wall, as described by Hofmeister, Neumeister and others, does not depend on its :assimilation or regeneration into ordinary proteid, but on its further c3ecomposition into simpler decomposition products. This is accom- lplished by a special ferment, wepsirf, secreted by the intestinal mucous ]membrane. Erepsin has no action on ordinary proteid, but only on peptone, and on a part of the proteoses. Leucine and tyrosine were W. D. H. The Passage of Proteid through the Intestinal Wall. S*pT%+&$4 f w a +A& yw&U'LC+& ; Ti& +"qT+P*h%n w'xs hZ4-A. v . D. K. Tu% J . ~ W % O L ~ P ~ ~ ~ Of r&w%~&~Tu5 h d U b h k 2 JqT& $8~~. ~tZNt9 FRIEDENTHAL (Pjiiger's A~chiv, 1901, 87, 467--472).-Largely polemical, against Hober.I n continuation of previous work, it is now shown that finely divided metallic mercury is absorbed ; this is mainly attributed to leucocytic action. W. D. H.94 ABSTRACTS OF CHEMICAL PAPERS. Molecular Concentration of the Blood and Tissues of Aquatic Animals. By L ~ O N FREDERICQ (Bull. Acad, Roy. Belg., 1901, No. 8, 428--454).-1n the lowest animals, the blood or haemolymph has the same molecular concentration and. the same percentage of salts as the water in which they live. In the next stage of evolution, the molecular concentration is the same, but t,he amount of salt is less than in the sea-water. Finally, as the surfaces of exchange bezoome more highly developed and less permeable, both the molecular concentration and the amount of salt are very different in the two fluids.The same three stages are seen in the tissues, Numbers obtained with numerous animals are given which support these propositions. By W. BULLOCK (Trccns. Path. Xoc., 1901, 52, 208--245).-As a result of the injection of ox- blood into rabbits, a hsmolysin develops in three days; it consists of two substances, an ‘ immune substance,’ and a thermo-unstable complement. Experiments show it is possible to make quantitative estimations of these substances. The appearance of the immune sub- stance is coincident with an increase of mono-nuclear leucocytes ; it is probably formed in the lymphatic tissues, whilst the complement is probably formed in myeloid tissue.The immune substance is excreted in the milk; this partly explains the immunity of the offspring; the haemolysin, however, reaches the fetus mainly by the placenta. W. D. H. Hzemolysis and Bacteriolysis. There -is a close analogy between hsmolysis and bjcterio1ysis.- W. D. H. Natural Anti-hsemolysins. By BESREDKA (Ann. Inst. Pastew, 1901,15, 785--807).-Both man and animals make normally for their own red corpuscles an anti-hsmolysin which is very probably an anti- aut o-haemoly sin. Influence of Salts on Heart Muscle. By WILLIAM H. HOWELL (Arner. J. PhysioE., 1901, 6, 181--206).--The experiments were per- formed on the ventricular muscle of the terrapin’s heart. Spontaneous contractions depend on the presence of both calcium and sodium com- pounds.Sodium salts tend to produce relaxation; calcium salts in- crease its tone, and this may pass into a condition of rigor. Potassium chloride antagonises this effect of calcium chloride, but only to a marked extent when sodium salts are present in approximately normal proportions. When all these salts are present, automatic contract- ibility is maintained longer. Strips of the ventricle do not contract spontaneously in the animal’s own serum or an equivalent Ringer’s mixture; this is due to the inhibitory influence of the potassium salts. When the heart is placed in a 0.7 per cent. solution of sodium chloride, the effects observed are first due to the gradual loss of potassium from the heart muscle by diffusion, and the final disappearance of the beats is due to a similar loss of calcium.W. D. H. W. D. H. Copper in the Liver of Cephalopods. By MARTIN HENZE (Zeit physiol. Chem., 1901, 33, 417--425).--The relationship of the liver of vertebrates to the iron of the blood suggested a similar investigation of the cephalopod liver in reference to copper. ThePHYSIOLOGICAL CHEMISTRY. 95 blood of these animals is free from iron. The blood-free liver contains a small amount of iron, but the amount of copper is about ten times as great. Both metals are united to nucleo-proteid. Dastre and Floresco (Arch. de Physiol., 1898, 10, 289) describe two pigmerts in the liver of these animals, one is insoluble in water but soluble in chloroform ; this xanthophylloid pigment is free from both metals; the other pigment, which is soluble in water, was prepared in an impure form ‘and contains from 1.3 to 7.7 per cent.of copper, 0.7 per cent. of iron and 4.7 per cent. of phosphorus. Chemical Constituents of Tendon. By LEO BUERGER and WILLIAM J. GIES (Amer. J. Physiol., 1901, 6, 219-231).-The average composition of the tendon Achilles is thus given : W. D. H. Calf. ox. Water ................................................ 67.51 62.87 Solids ................................................ 32.49 37.13 Organic matter .................................... 31.88 36.66 Fat ................................................... - 1-04 Mucoid ................................................ - 1-88 Elastin ................................................ - 1-63 Collagen ............................................. - 31.58 W.D. H. By THOMAS E. THORPE (Arch. Nder. sci. exact. nat., 1901, [ii], 6, 155--161).--Eggs from pure bred hens (Horsley) and from hens of mixed breeds (High Pitfold) gave rstio of yolk to white, 1 : 1.92 and 1 : 1.62 respectively. The percentage of fat in the yolk was 31.7 in the Horsley eggs and 30.6 in the High Pitfold eggs, corresponding with 9.4 per cent. of f a t in the former eggs and 10.2 in the eggs from High Pitfold. The f a t from the Horsley eggs contained 0.6 per cent. of phosphorus, corre- sponding with 15.04 per cent. of lecithin, 61.5 per cent. of neutral fat, and 23.2 per cent. of free acids. The neutral fat had a saponification value of 181 *5 and contained 93.1 per cent. of insoluble and 2-04 per cent. of soluble (total 95.14 per cent.) acids.The saponification value of the insoluble acids was 189.6 (mol. wt. = 296). When calculated on the assumption that only triglycerides were present, there should be 95.93 per cent. of fatty acid (in agreement with 95.14 per cent. found) and 9-86 per cent. of glycerol, whilst if monoglycerides alone were present there should be only 87.79 per cent. of fatty acid and 29.58 per cent. of glycerol. Determination of the glycerol showed 9.6 per cent. (mean) in the fat. Results obtained with the High Pitfold eggs also show that only triglycerides are present in the fat. By GUSTAV SIMON (Zeit. physiol. Chem., 1901, 33, 466-541).-This paper is mainly concerned with quanti- tative methods. A large number of methods for the estimation of total proteids and of the individual proteids are carefully compared.Analyses of cow’s milk and colostrum are given, Inorganic matter.. .................................. 0.61 0 *47 Albumin and globulin ........................... - 0.22 Extractives (creatine, purine bases, &c.) ...... - 0.s9 The Fat of the Egg of the Common Fowl. J. McC. Proteids of‘ Cow’s Milk. W. D. H.96 ABSTRACTS OF CHEMICAL PAPERS. Physiological Action of Decoction of Mussels. By CONSTANT THIBERT (BUZZ. Acad. Roy. BeZg., 1901, No. 8, 494-499).-1n decoction of mussels there exists a substance which on intravenous injection in the dog produces a lowering of arterial pressure, an increased pro- duction of lymph, and a non-coagulable condition of the blood. The action is similar to that produced by ' peptone.' The active substance was not isolated.Glycogen takes no part in the effects. W. D. H. The Action of Pilocarpine and Atropine on Echinoderm Embryos. By ALBERT P. MATREWS (Amer. J. PhpioZ., 1901, 6, 207-2 15).- Atropine sulphate, in small doses, hinders the develop- ment and gives rise to dwarf embryos, Pilocarpine hydrochloride hastens development and gives rise to abnormally large embryos. The action of atropine resembles that of hydrogen ions, the action of pilo- carpine that of hydroxyl ions. Hence atropine and pilocarpine act on animal cells directly, and not merely on secretory nerve-endings. It is suggested that atropine inhibits, and pilocarpine increases, oxidation processes, and that this will explain their action on secretory cells. W.D. H. Pathogenic Properties of Trypsin and the Antitryptic Power of Guinea-pig's Serum. By PIERRE ACHALME (Ann. Inst. Pasteur, 1901, 15, 737--752).-The introduction into animals, subcutaneously or intraperitoneally, of trypsin, a substance capable of profoundly altering ' living proteid, ' provokes immediately a process of defence. This consists of an exudation of blood-serum ('1 plasma or lymph) under the influence of vaso-motor nerves. The exudation opposes the pene- tration of the trypsin and then neutralises its effects. When this is frequently repeated, the process of defence is more perfect and this is due to an increase in the antitryptic power of the serum. W. D. H. Intravenous Indculation of a Diplococcus isolated from Cases of Rheumatic Fever, By F. J. POYNTON and ALEXANDER PAINE (Trans. Path. ~ o c . , 1901, 52, 248-253).-Rheumatism appears to be due to a diplococcus which can be separated from heart, lungs, joints, &c., of rheumatic fever patients. When it is intravenously injected into rabbits, arthritis is the usual result. W. D. H By THOMAS (J. Phai-rn. Chim., 1901, [vi], 14,437-438).-The paper contains com- plete analyses of the urine both before and after administration of cal- cium glycerophosphate. The effect of the calcium glycerophosphate is t o render the urine much more normal in composition. Concretions from the Urinary Duct of a Wild Boar and from the Kidney of a Deer. By CONSTANTIN COUNCLER (Chem. Zed., 1901,25, 872--873).-A concretion from the urinary duct of a wild boar (#us scrofccc) consisted almost entirely of pure crystallised magnes- ium ammonium phosphate. A second concretion from the kidney of a deer (Cervus capeohs) consisted of pure crystallised calcium oxalate, CaC204, 2H20 J. J. 8 Analysis of the Urine in a Case of Osteomalacia. H. R. LE 8.

ISSN:0368-1769    

DOI:10.1039/CA9028205092

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE, 97 Chemistry of Vegetable Physiology and Agriculture. The Effect of Nitrates on certain Bacteria. By WALTER c. C. PAKES (Trc6ns. Path. sbc., 1901, 52, 246-247).-The effect of high percentages of nitrates on the morphology of certain bacteria is described. The bacilli resume their original form when again planted on broth. W. D. H. The Lactic Ferments in' the Arts. By MARTINUS W. BEVERINCK (Arch. Nier. sci. exact. nat., 1901, [ii], 6, 212--243).-The ferments used in producing lactic acid have been exhaustively studied. The bacteria are Lactococci and Lactobacilli. Lactic fermentation is not a m.ere enzymic action, but is a true catabolic process. Experi- ments with pure cultures of lactic ferment prove that the quantity of acid formed is dependent on the temperature (optimum 41') and on the presence or absence of air.The author applies the name Lacto- bcwillus delbriicki to all those species which can be isolated from the fer- ment by the gelatinised must method ; L. delbrzicki is not the active agent of a good industrial ferment. Lactobacillus fermenturn has also been isolated from the ferment and it is shown that this is the bacterium which gives the ferment its particular character. Cultivated under good aGration, it gives only lactic acid and no volatile acids; its optimum is 41-42', i t s minimum 25', and its maximum 50'. L. fermenturn can be transformed into L. delbrucki by cultivation above the optimum temperature and by prolonged cultivation under very profuse aeration ; the reverse transformation can be carried out by an aerobic culture at the ordinary temperature. Decomposition of Butter Fat by Micro-organisms.By 0. LAXA (Arch. Hygiene, 1901, 41, 119--151).-7!he most active agents in thedecomposition of butter fat among those examined were the moulds, Oidium Zactis, Penicillium glaucum, and a species of MUCOT, as well as Bacillus juorescens Ziquefaciens. Several varieties of yeast and of bacteria which are able to peptonise casein were found to have only a slight actior), whilst a number of varietiesof lactic acid bacteria and of l'yyothrix were found to be inactive. The decomposition of the fat is not due to the action of ammonia produced from the nitrogenous matter by the action of the organisms, as has been suggested by Duclaux, since solutions of ammonia do not act on the fatty glycerides a t the ordinary temperature.In the cases of Penicillium and Mucor, i t was found possible, by grinding the mould with glass powder and filtering, to obtain a sterile solution containing an enzyme which decom- posed monobutyrin and butter fat in the characteristic manner. Of the glycerides of the insoluble acids, those of highest molecular weight are first decomposed. On the other hand, the glycerides of the soluble acids of lowest molecular weight are most largely decomposed. This appears to be connected with the fact that the higher soluble acids exert a very strong deterrent effect on the growth of the organisms. The free volatile fatty acids are then further decomposed by the action of the mould. Experiments with casein freed from f a t show that no J.McC.08 ABSTRACTS OF CHEMICAL PAPERS. part of the fatty acid produced is derived from the casein, but that the organism is able to synthesise a small amount of fat which is stored in its cells as reserve material. Formation of Volatile Acids in Alcoholic Fermentation. By W. SEIFERT (Bied. Centr., 1901, 30, 774-776; from Zed. Zandw. Vemuchs- Wes. Oesterv., 1901, 4, 227).--Volatile acids were not pro- duced in any quantity (0.6 gram per litre being the largest amount) in must by Tokay yeast. When greater amounts occur in wines, their presence must be attributed t o moulds or acetic acid bacteria. Differ- ences in temperature had very little effect on the formation of volatile acids, but rather more was produced at 15" than a t 30".The presence of tartaric or malic acid had no appreciable effect. The amount of non- volatile acid was distinctly increased during fermentation ; addition of tartaric or malic acid to the must somewhat diminished the production of non-volatile acid, Production of Hydrogen Sulphide in Alcoholic Fermentation. By W. SEIFERT (Bied. Centr., 1901, 30, 776-778; from Zeit. Zandw. Versuchs- Wes. Oesterr., 1901, 4, 221).-The results of fermentation experiments with 0.2 gram of sulphur in 250 C.C. of must showed that the greatest production of hydrogen sulphide took place after the vigour of the fermentation had begun to diminish. The amount of sulphide produced in two weeks was 0.0073 gram per litre. It was found that the presence of sulphur in the amount employed quickened the fermentation as compared with fermentation in absence of sulphur.This is shown to be probably partly due to mechanical action, wood and paper fibre having a similar effect. In practice, the amount of sulphur would be considerably less than 0.8 gram per litre and insufficient to exercise either a mechanical or an antiseptic action. I n the aeration of must, the stirring and distribution of theyeast is probably of greater importance than the access of air. Fluorine in Musts and Wines. By KARL WINDISCH (Zed. Nab*. w2nussm;, Ct", 4, Ni'-W?)! - &w &k- vml, lit, JW. Chemical Processes in the Killed Yeast Cell. By ROBERT ALBERT and W. ALBERT (Centr. Bakt. Pur., 1901, ii, '7, 737-742)- When yeast which has been killed by treatment with alcohol and ether is suspended in water, coagulable albumin and non-coagulable proteids pass out of the cell and are rapidly digested by the proteolytic enzyme of the yeast, which does not appear to be affected by the treatment with alcohol.The liquid filtered after 48 hours still contains this pro- teolytic enzyme together with the products of its action. Microscopic examination shows that this change is accompanied by the disappear- ance of material from the cell, deeply staining granules being left, which afterwards also disappear, leaving a small mass, capable of being stained, which is possibly the nucleus of the cell. The zymase of the cell, although still active and capable of bringing about the fermentation of the glycogen within the cell or of sugar solution, does not pass out of the cell.It seems probable also that the glycogen is first hydrolysed by another ferment, which, like the zymase, remains in the cell, since glycogen added to the solution is neither hydrolysed A. H. N. H. J. M. N. H. J . M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 99 nor fermented. The zymase itself is destroyed in about 20 hours by the proteolytic enzyme. Invertase also passes out of the cells SO rapidly when they are placed in water that a solution of considerable inverting power is formed which only contains traces of albumins ; attempts are being made to prepare pure invertase by this means. A. H. Respiration of Hydrogen and Hydrocarbons through the Green Parts of Plants. By GINO POLLACCI (Chem. Centr., 1901, ii, 9 3 8 4 3 9 ; from Atti R.1st. Rot. Univ. Pavia).-The production of formaldehyde in the green parts of plants is attributed to the action of nascent hydrogen. Both hydrogen and hydrocarbons were found to be given off by plants. Nutrition of Plants at the axpense of the Cotyledons. By GUSTAVE ANDR~~ (Compt. rend., 1’301, 133, 1011-1013) -The amounts of dry matter, ash, silica, calcium, phosphoric acid, potassium, and nitrogen were determined in Spanish haricots and in the cotyledons and plants at intervals of two days, commencing nine days after sowing the seeds. The results are arranged to show the gradual exhaustion of the cotyledons and the coincident increase in the plants a€ the vain1l.r canstjt,lPAt& Silica and calcium are absorbed from the commencement, being, as previously shown, withdrawn from the soil by the cotyledons. Nitro- gen and phosphoric acid remain unchanged for some time, the grain in the plant being accounted for by corresponding losses in the cotyledons.The assimilation of phosphoric acid from the soil commences a t the same time as the assimilation of soil-nitrogen. The absorption of potasssium from the soil commences as soon as the germinating period ends. N. I€. J. M. Chlorophyllous Assimilation in the Autumn. By JEAN FRIEDEL (Col-rpt. rend., 1901, 133, 840--841).-0n repeating his ex- periments with glycerol extracts of leaves (Abstr., 1901, ii, 411) in October and November, the author obtained negative results. It was, however, found that, at this time of the year, assimilation is very feeble in the leaves themselves.Further experiments will be made in the spring. By EUGI~NE CHARABOT and A. HEBERT (Bull. SOC. Chim., 1901, [iii], 25, 955-959. Compare Abstr., 1901, ii, 619).-Rhodinol is esterified more readily than geraniol ; under comparable conditions, 83 per cent. of the rhodinol, and 67 per cent. of the geraniol are converted into the acetate. I n a sample of Algerian geranium-oil, it was found that the esters contained a larger proportion of rhodinol than the free alcohols, showing that esterification in the plant obeys the usual laws, and that the esterified alcohols found in the plant are those which are most readily esterified under laboratory conditions. Composition of the Reserve Carbohydrates of the Proteid of the Seeds of some Liliaceae, and in particular of Butcher’s Broom.By GEORGES DUBAT (Compt. rend., 1901,133, 942-944).- Air-dried seeds of Busczcs ccculeaituls (with 9.88 per cent. of water) N. ‘K. J. M. N. H. J. M. Mechanism of Esterification in Plants. T. M. L.100 ABSTRACTS OF CHEMICAL PAPERS. yielded 0.97 per cent. of fatty matters and when digested for half-an- hour with 0.3 per cent. sulphuric acid on a water-bath, 13.616 per cent. of reducing sugar, calculated as invert sugar. A certain amount of laevulose was separated as calcium lzevuloeate. When hydrolysed, the seeds yielded 69.S5 per cent. of reducing sugars : mannose, 27.92 ; dextrose (?), 27-64 ; invert sugar, 13.6 1, and pentoses, 0.68 per cent. By PIERRE P. DEHERAIN and C. DUPONT (Con&@ Tend., 1901, 133, 774--77S).-Whilst the total nitrogen of a wheat crop does not increase after the commencement of maturation (Isidore Pierre, Recherches expi+.SUY Zcc diveloppement du bZ2, 1866 ; Dehttrain and Meyers, Abstr., 1883, 493 ; and Berthelot, Chinz. reg. A y ~ i c . , 2, 259), there is a migration of nitrogen from the lower to the upper leaves, followed by a concentration in tbe grain. I n the case of starch, there is a t no period a reserve of amylaceous matter, such as occurs in potatoes, tob;lcco, &c. The rapid accumula- tion of starch during the last weeks is therefore due to the elaboration of new substance, notwithstanding that the green portions of the plants are by this time very restricted. It is now shown that the green upper portions of the stems have the functions of leaves in de- composing carbon dioxide.It is further shown that whilst nitrogen and reducing sugars remain in the upper parts of the stems, the starch, dextrin, and non-reducing sugars migrate for the most part to the ears, where they are concentrated as starch. The late production of starch, and its dependence on the stems re- maining green, is illustrated by the results of field experiments in 1888 and 1889, whan the weather was wet and dry respectively during the period of maturation. I n 1888, the weight of: grain was 3445 kilos., and contained 439 kilos. of nitrogenous matter, and 2689 kilos. of starch; in 1889, the yield of grain was 292% kilos., and it contained 447 kilos. of nitrogenous matter and 1808 kilos. of starch per hectare. N. H. J. M. Origin of Starch in Wheat Grain.N. H. J. M. . Prussic Acid in Sweet Cassava. By PATRICK CARMODY (Lancet, 1900, Reprint). -The presence of hydrocyanic acid in sweet cassava, first pointed out by Francis (Abstr., 1877, ii, 515), is confirmed. It is further shown that the acid is located chiefly in the skin and outer cortical layer, whereas in the bitter cassava it is uniformly distributed throughout the tuber. E. G . Chemistry of Stylophorum Diphyllum. By JULIUS 0. SCHLOTTERBECK and H. C. WATKINS (Yhurm. Review, 1901, 19, 453-4 5S).-StyZop?ioTum diphylluna, commonly known in America as the yellow or celandine poppy, belongs to the Papuveracem and grows in the low woods from Ohio to Tennessee and westward to Wisconsin and Missouri. The following alkaloids were found to be present in the plant as salts of chelidonic acid: (1) chelidonine, for which the formula proposed by Schmidt and Selle is confirmed by analyses of the alkaloid and its snits; it is a tertiary base and contains no methoxy-groups.(2) A new alkaloid, stylopine, C,,H!,O,N, of which the chloride, nitrate, hydriodide, aurichloride, and platinichloride haveVEGETABLE PHYSIOLOGY AND AGRICULTURE. 101 been analysed ; it does not contain methoxy-groups and is probably a tertiary base ; (3) protopine ; (4) a new alkaloid, diphylline which melts at 216O ; (5) sanguarine, identical with that found in Xanguinaria, Chelidonium, and Bocconia. Potassium chelidonate is present in the plant in considerable quantity, Besides the above substances, the plant also contains a crystalline colouring matter probably identical with chelidoxanthin, and a fragrant substance resembling coumarin in odour.H. R. LE S. Does Argemone Mexicana contain Morphine? By JULIUS 0. SCHLOTTERBECK (Pharm. Review, 1901, 19, 458-461).-Mexican or prickly poppy (Argemone mexicancc) does not contain morphine ; the only alkaloids present are berberine and protopine. The alkaloid isolated from this plant by Peckolt, to which he gave the name argemonine, is probably identical with protopine. H. R. LE S. Chemical Composition of the Roots of Dorstenia Klaineans (Gabon Ivy) and D. Brasiliensis. By EDOUARD HECKEL and FREDERIC SCHLAGDENHAUFFEN (Compt. rend., 1901, 133, 940-942).- The root of Dorstenia Klaineccna, a shrub common in the French possessions in Africa, has a brick-red bark and a strong odour of cou- marin.It contains $-coumurin, C12H,0,, which melts a t 180' and is soluble in light petroleum; various red resins, characterised by giving an intense cochineal coloration in contact with bromine vapour ; tannin, and a large quantity of starch. The root 01 D. BmsiZiennsis yie'lds to Tight petrdeum a crystalhe substance which melts at 189O and gives a golden-yellow colour with strong sulphuric acid, a deep brown colour with a mixture of sulphuric and selenious acids ; a golden-yellow colour, becoming violet and then blue, with sulphuric and iodic acids, and a violet tint changing to blue with sulphuric acid and potassium dichromate. The root also contains resins which seem t o be identical with those from D. Kluineccna. Both roots contain a very large proportion of inorganic matter, the ash consisting of calcium and ferric oxides, the latter in large quantity, as also are the sulphates, no chlorides, but a small quantity of phosphates. C.H. B. Feeding Experiments, with Milch-sheep and Goats, on the Effect of Fat on the Amount and Composition of the Milk. By c'. BEGER, P. DOLL, G. FINGERLING, E. HANOKE, H. STEGLIN, W. ZIELSTORFF and AUGUST MORGEN (Chem. Zeit., 1901,25, 951-953). -Fat, when fed in the form of sesame cake or earth-nut oil, has, under certain conditions, a considerable effect on the amount of fat in the milk, and it is probable that these fats serve, at any rate to some extent, as materials for the production of milk-fat. When the f a t of a ration having a nutritive ratio of 1 :3*6-3*7, and containing 1 gram of fat per kilo.of live weight, is replaced. to the extent of four-fifths by an equivalent amount of carbohydrates, the milk-fat produced was reduced by about 14 grams per day, o r about 34 per cent. of the normal amount. Whilst a reduction in the amount of food-fat diminished the fat in102 ABSTRACTS OF CHEMICAL PAPERS. the dry matter of the milk by 7.1 per cent., there was invariably an increase in the amounts of sugar, nitrogen, and ash. An increased amount of food-fat up to a certain point increased the amount of milk-fat but not the other constituents. The effect of food-fat in increasing the milk-fat is limited, and an excess of fat produces different effects with different animals. N. H, J. M. Coru;position 09 Hard Wheat and the Physical Constitution -Analyses are given of Russian and African wheat grain and of Canadian goose wheat.Hard wheat cont.ains above 2.5 per cent. of proteids more than soft wheat, and more gluten than the most highly nitrogenous soft wheats. The sum of the gluten and starch in wheat is a constant amount (65 per cent.), and the sum of the sugars and the soluble nitrogenous matters is also constant (5 per cent.). The results of determinations of gliadin in the flour of hard wheat by means of the two methods described by the author (Compt. rend., 132, 1421, and 133, 327 and 754) are not concordant, owing to hard wheat containing 1 5 to 2 per cent. more soluble matter than soft wheat; even when the densinueter results are subjected to a correction, the results are much too low.This is due to the presence in the gluten of hard wheat of a considerable amount of conglutin. The gluten of flour from Russian wheat, for instance, contained gliadin 46.45, glu- tenin 37.89, and conglutin 15.66 per cent. N. H. J. M. Of its Gluten. By E~II~EFLEURENT(C0mcpt. rend., 1901,133,944-947). Composition of the Products Resulting from the Grinding of Wheat by means of Millstones and Rollers. By L ~ O N LINDET (J. Phnrm. Clhn., 1901, [iv], 14, 433--437).-The superiority of roller milling over the ordinary grinding by millstones is clearly seen from the analyses of the different constituent parts into which the wheat is separated by the two processes. H. R. LE S. Influence of Single Manures on Barley. Cy J. J. VANHA (Bied. Centr., 1901, 30, 745-750 ; from Zed.Zandw. Vevsuchs-Wes. Oesterr., 1901,4,40).-Nitrogenous manure increases the yield of grain and straw much more than other manures, and, like potash, pFomotes root-growth. With increased root-production, there is also an increase in the number and weight of stems. The weight of single stems is, however, only increased by a mixture containing nitrogen, potassium, and phosphorus in moderate quantities. The length of the stems is increased by phosphates or potassium manure (up to lG0 kilos. per hectare) and diminished by much nitrogenous manure. The number of ears is influenced much more by nitrogen than by phosphoric acid and potassium ; the latter are without advantage in quantities greater than 100 kilos. per hectare. Nitrogenous manu&s, and in a much less degree, potassium and phosphoric acid, increase the number of grains by increasing the number of ears.All these manures, but especially nitrogen, increase the weight of grain ; potassium seems to influence the volume of the grain the most. Phosphoric acid increases, whilst large amounts of nitrogen and potassium diminish, the mealiness of theVEGETABLE PHYSIOLOGY AND AGRICULTURE. 103 grain. The amounts of total nitrogen and of proteids are considerably reduced by phosphoric acid and potassium. Pot,assium is deposited to a greater extent in the straw than in the grain, whilst phosphoric acid is deposited chiefly in the grain. By JOSEPH HANAMANN (Chem. Cent?., 1901, ii, 1126-1127 ; from Zeit. landw. Yersuchs- Wes. Oesterr., 4, 993--1006).-The results of experiments with old Bohemian and different Scotch varieties of barley showed that the heaviest and best variety (goldfoil) deteriorated most, notwithstanding the favour- able climatic conditions.The other acclimatised varieties remained unaltered, The local conditions greatly affected the percentage of nitrogen. The application of kainite resulted in a satisfactory gain in yield, whilst the amount of proteids was reduced. The average percentage of nitrogen in a large number of samples of barley grown during ten years was 1.44. N. H. J. M. Experiments with Varieties of Barley. N. H. J. M. Influence of Manuring on the Composition of Potatoes, By WALTER F. SUTHERST (Chem. News, 1901,84,258-259).-Analyses were made of potatoes grown (1) without manure, (2) with 20 tons of farmyard manure, and (3) 5 cwt. of superphosphate, 2 cwt. of potassium chloride, and 2 cwt. of ammonium sulphate per acre. The following - . _ obtained : percentage results were Dry Matter. N. 1. 23.76 0.506 2. 21.92 0.516 3. 24.05 0.493 The similarity in the Starch. Ash. K20. CaO. P20,, 17.76 0.967 0.628 0.025 0.124 13.56 0.973 0.635 0.022 0.147 17.14 0.964 0.630 0,028 0.121 composition of the tubers from plots 1 and 3 is attributed to-the absence of sufficient moisture in the' soil to dis- solve the artificial manures. The starch was determined gravimetrically with Fehling's solution, after heating 3 grams of the dried substance successively with water a t 108O and with dilute hydrochloric acid. Value of the Nitrogen in Pyrenean Phosphates. By JULES JOFFRE (Bull. Soc. Chinz., 1901, [iii], 25, 960-96l).-The small amount (0.14 per cent.) of nitrogen in phosphates from the Pyrenees was found to be of no agricultural value. Mixtures of Martin-slag and Degelatinised Bone-meal 88 Diluents f o r Basic Slag. By PRANZ W. DAFERT and F. PILZ (Chem. Cent?., 1901, ii, 895 ; from Zeit. Zandw. Versuchs-Wes. Oesterr., 4, 960-963).-An alleged sample of basic slag was separated by means of bromoform into a light portion (57 per cent.) consisting of degelatinised bone meal, and a heavy portion (40 per cent.), found to be martin-slag. The phosphate contained total P,O,, 16.63 per cent. and 14.3 per cent. soluble in citric acid solution. N. H. J. M. T. M. L. N. H. J. M,

ISSN:0368-1769    

DOI:10.1039/CA9028205097

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

104 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Simple Gasometric Method of Estimating Chlorine, Hydro- chloric Acid, Silver, and Phosphates. By E. RIEGLER (Zeit. and. Chem., 1901, 40, 633-638).-Silver chloride, treated with hydrazine sulphate and sodium hydroxide, is decomposed according to the equation 4AgC1+ N2HqH2S0, + 6NaOH = 4Ag t 4NaClf Na,SO, +6H,0+N2. By calculation 1 part of nitrogen corresponds with 20.424 parts of silver chloride: experiment gives 20.2 parts. The silver chloride (not more than a gram), precipitated and washed in the usual manner, is placed, together with about 0.5 grain of hydrazine sulphate, in the reaction flask of a KnopWagner azotometer, the inner vessel of which is charged with 10 C.C. of a 10 per cent. sodium hydroxide solution. After the temperature has been adjusted, as usual, the contents of the flask are shaken for 15 minutes, the temperature readjusted, and the volume of gas read off.For the estimation of phosphoric acid, a quantity of a phosphate containing not more than 0.16 gram of P20, is dissolved in dilute nitric acid, treated with 1-2 grams of silver nitrate and then with sufficient sodium hydroxide to produce a permanent precipitate, the precipitation of brown silver oxide being avoided. Dilute ammonia is then added until the liquid is alkaline to litmus paper, and the mixture boiled for 5 minutes. The silver phosphate is collected and washed, then dissolved in nitric acid. The silver is precipitated as chloride and estimated as above. One milligram of nitrogen is obtained for each 3.33 mg.of P,O,. Fluorine in Musts and Wines. By KARL WINDISCH (Zeit. Nahr.-Gelzussm,, 1901,4, 961--968).-Mention is made of several in- stances where the must from Spanish grapes could not be induced to ferment, owing, as i t appeared afterwards, to the presence of a fluoride. The various methods for the qualitative detection of fluorine are re- viewed, and preference is given to the test by etching glass. An accurate estimation of fluorine in foods is still a desideratum. The great difficulty seems to be the prevention of loss of fluorine by By R. AUZENAT (Chem. Centr., 1901, ii, 1093 ; from Mon. sci. 1901, [iv], 15, 11, 635).-0-5 gram of the sample is oxidised with nitrohydrochloric acid with addition of 20 C.C. of a 10 per cent. solution of sodium chloride.The excess of acid may then be evaporated a t 120° without any fear of losing sulphuric acid. At least six hours should elapse before collecting the barium sulphate. M. J. S. volatilisation when reducing the substance to ash. L. DE K. Estimation of Sulphur in Iron Pyrites. L. DE K. [Discrimination between and Estimation of Pyrites and Marcasite in Mixtures.] By HENRY N. STOKES (Bull. US, Geol. Survey, 1901, No. 186, Xer. E., Chem, and Physics, No. 35)--See this vol., ii, 87.ANALYTICAL CHEMISTRY, 106 Estimation of Persulphates. By CHARLES A. PETERS and SETH E. MOODY (Amer. J . Xci., 1901, [ iv], 12, 367-376).-The authors have investigated the various processes in use for the estimation of persul- phates. The process introduced by Leblanc and Eckardt (reduction with ferrous sulpliate and titration of bhe excess with permanganate) is simple, rapid, and convenient.Grutzner’s method (reduction at the boil- ing point with arsenious acid in alkaline solution and titration of the excess with iodine) is not trustworthy without a correction. Mon- dolfo’s process (heating with potassium iodide and titrating the liber- ated iodine with thiosulphate) is simple and fairly rapid, but tends to give too low results. The method recently proposed by Namias where the potassium iodide is allowed to act for twelve hours i n the cold also gives low results. Gooch and Smith’sprocess for the estimation of chlorates (Abstr., 1892, ii, 236) by means of arsenic acid and potassium iodide may also be applied to persulphates ; the results are accurate, but the process is less simple than the other methods.L. DE K. Estimation of Alkali Persulphates. By G. ALLARD (J. Pharm. Chim., 1901, [vi], 14, 506-508).-The method usually employed for the estimation of alkali persulphates, which consists in the estima- tion of the iodine liberated when a solution of potassium iodide is added to the persulphate solution, is accurate only when carried out in neutral solution. If carried out in sulphuric acid solution, as recom- mended by Moreau (Bull. Xoc. Pharm., 1901, 3, 179), the results are too high, due to the fact that the sulphuric acid liberates iodine from the potassium iodide. H. R. LE S. R61e of Phosphoric Acid in Wine Analysis. By RUDOLF WOY (Zeit. ofentl. Chem., 1901, 21, 415-420).-Phosphoric acid, although no longer regarded as of much importance in judging the purity of a wine, is to be considered as a diotnrbing factor in estimating the other constituents of wine ash.The author has already explained that part of the acid may be converted into pyrophosphoric acid and so escape precipitation with molybdate solution (Abstr., 1901, ii, 344). It is now shown that the potassium carbonate of the wine ash acts t o some extent on the calcium phosphate with formation of calcium carbon- ate and potassium phosphate. The estimation of the alkalinity, according to the German official process, becomes, therefore, slightly incorrect in the presence of much phosphoric acid, The matter Methods for the Analysis of Artificial Manures. By F. KRETSCHMER (Zeit. ungew. Chem., 1901, 14, 1136-1 138).-Conven- tional methods are given for the partial or full analysis of phosphatic requires further investigation.L. DE K. and nitrogenous artificial manures. L. DE I(. Analysis of Mixtures of Alkali Silicates, Carbonates, Sulph- ates and Hydroxides. By GEORG LUNQE and W. LOHOFER (Zeit. angew. Chem., 1901, 14, 1125--1134).-The idea that sodium silicate is completely decomposed by barium chloride is incorrect; about 40 VOL. LXXXII. ii. 8106 ABSTRACTS OF CHEMICAL PAPERS. per cent. remains in solution and apparently increases the free alkalinity. The presence of silicic acid introduces an error when phenolphthalein is used as indicator on account of its acidic properties ; the silica is, however, rendered inert if the liquid contains sufficient sodium chloride.Solutions containing carbonate may be fairly accurately titrated with phenolphthalein as indicator, provided they are sufficiently diluted and contain sodium chloride, or, what amounts to the same thing, a fair proportion of sodium hydroxide ; the concentration of the alkali should not exceed one gram-mol. of sodium chloride per litre. For the estimation of the total alkali, the best process is titration with hydrochloric acid in the presence of methyl-orange. The following scheme is given for the technical analysis of the soda cake used in the manufacture of fibre: 1. Insoluble mutter is estimated as usual. 2. AlAuZinity. Twenty C.C. of the solution (50 grams dissolved to 500 c.c.) are titrated with N-hydrochloric acid and phenolphthalein until colourless and the titration is then continued with methyl-orange as indicator.3. Sodium suZphide and sul'phite. Twenty C.C. are diluted to 200 c.c., acidified with acetic acid, and rapidly titrated with N/10 iodine. 4. Sodium sdphite only. One hundred C.C. are precipitated with an alkaline solution of zinc acetate, the whole is diluted to 250 c.c., and filtered; 50 C.C. of the filtrate are then again acidified with acetic acid and titrated with iodine. 5. Sodium silicate. Twenty C.C. are evaporated with addition of hydrochloric acid and the silica separated as usual. 6. ,Sodium sulphate. The filtrate from the silica is precipitated with barium chloride as usual. The usual calculation is then applied. L. DE I(. Modifbation of Schumann's Apparatus for Estimating the Specific Gravity of Cement.By P. BECK (Zeit. anal. Chem., 1901, 40, 646-649).-Instead of oil of turpentine, carbon tetra- chloride is employed ; its lower viscosity shortens the operation materially. The adjustment of the liquid to the zero of the graduation is facilitated by having a hole in the side of the neck, and another in the graduated tube, which can be brought into communication by rotating the tube in the neck. Several additional devices enable a series of estimations to be performed rapidly, M. J. S. Examination of Mixtures of Portland Cement and Slag Meal. By P. BECK (Zeit. anal. Chem., 1901, 40, 649--666).-Recent experiments by W. Fresenius show that a high consumption of permanganate (see Abstr., 1884, 876) can no longer be regarded as a criterion of the adulteration of Portland cement with slag meal. Atten- tion has therefore been directed to the estimation of the sulphur existing as sulphide, this being the most characteristic constituent of slag when compared with genuine cement.Three methods were employed : (1) The total sulphur was estimated by fusing the substance with alkali carbonates and nitrate and heating the solution with nitric acid ; the sulphur present as sulphate was also estimated after boiling the substance with hydrochloric acid. The difference was assumed t o represent, the sulphw of the sulphides. (2) The substance was decom- posed by boiling with hydrochloric acid in a current of carbon dioxideANALYTICAL CHEMISTRY, 107 and the hydrogen sulphide absorbed by cadmium chloride, as i n Fresenius’ method of estimating sulphur in cast iron.(3) The con- sumption of permanganate by the substance was ascertained, and also the amount of permanganate required after the substance had been digested in the cold with dilute sulphuric acid and a cadmium salt. The difference, calculated according t o the equation GKMnO, + 5s = 3K,O + 6Mn0 + 5SO,, agreed closely with the amount of sulphide-sulphur estimated according to method (1 ) in the slag-meal itself, and with the calculated amount in mixtures of the slag-meal with a sample of Portland cement which did not contain sulphides. This method is the most rapid of the three. It is carried out exactly as follows: The weighed sub- stance (1 gram) is made into a paste with 50 C.C. of water in a flask, 100 C.C.more water are added and an excess of permanganate solution (5 grams per litre) with vigorous shaking, then immediately 50 C.C. of dilute sulphuric acid in small portions. By adding the reagents in this order, all loss of hydrogen sulphide is prevented. An excess of titrated ferrous ammonium sulphate solution is then added and the excess titrated back with the permanganate. A similar experiment is then made, in which 1-2 grams of cadmium carbonate are added to the wetted cement instead of the permanganate. Sulphuric acid is added as before and the flask is filled with carbon dioxide and corked. When the mixture has become clear, it is filtered and the filtrate immediately titrated with a permanganate solution one-fifth the strength of the former one.Volumetric Estimation of Manganese. By FRED IBBOTSON and HARRY BREARLEY (Chem. News, 1901, 84, 247-248).-1n the bismuthate process, 1.1 grams of the metal are dissolved in 35 C.C. of nitric acid of sp. gr. 1.20, and bismuthate added to the cooled solution until a permanganate colour persists or manganic oxide separates on boiling. The solution is cleared with hydrogen peroxide, sulphurous acid or ferrous sulphate, cooled, treated with 10 C.C. of water and excess of bismuthate, filtered, washed with 3 or 4 per cent. nitric acid, mixed with excess of ferrous ammonium sulphate, and titrated with deci- normal permanganate. With hydrogen peroxide, the results are liable to be too high. The presence of chromium only affects the results in warm solutions or when contact with the bismuthate is prolonged.Tungsten does not affect the reaction, but any hydrofluoric acid must be elimi- nated. Titanium and vanadiummay prove troublesome and molybdenum is so when hydrogen peroxide is used, but not with ferrous sulphate (compare Ramage, this vol., ii, 50). By LAWRENCE DUFTY (Chenz. News, 1901, 84, 248).--0.1 gram of steel is dissolved in 2 or 3 C.C. of nitric acid according to the amount of carbon present, the carbon estimated, the solution diluted with nitric acid in a test-mixer to 20 c.c., when the manganese is under 0.8 per cent. or otherwise t o 25 c.c., and then mixed with 0.2 gram of bismuthate. After settling, 5 C.C. of the clear solutionare compared colorirnetrically with a standard. The process is a modification of that of Reddrop and Ramage (Trans., 1895, 67, 268).M. J. S . D. A. L. Volumetric Estimation of Manganese. D, A. L. 8-2108 ABSTRACTS OF CHEMICAL PAPERS. Volumetric Estimation of Manganese. By HUGE RAMAG E (Chem. News, 1901, 84, 269. Compare preceding abstracts).-l'h e author defends his statements against criticisms of Ibbotson and Brear - ley, and expresses disapproval of the use of ferrous sulphate or ammo - nium ferrous sulphate as a substitute for hydrogen peroxide in the manner suggested by those authors. Moreover, he prefers titration t o the colorimetric method of Dufty. D. A. L, New Process for the Estimation of Manganese. By GEORG VON KKNORRE (Zeit. angew. Chern., 1901, 14, 1149--1162).-Marshall (Trans., 1891, 59, 771-786) has stated that manganous salts when mixed with potassium persulphate yield manganese dioxide.The author has succeeded in making this the basis of a quantitative esti- mation. Solutions of manganous salts, which must first be converted into sulphate, on boiling with excess of ammonium persulphate yield the whole of the metal as dioxide, which may then be collected and treated either gravimetricalIy or volumetrically, I n the presence, however, of copper, nickeI, zinc, iron, or cobalt, t h e dioxide carries down a portion of these metals; in the absence of cobalt, good results may even then be obtained by applying the volumetric process with standazd hydrogen peroxide (or ferrous sulphate) and standard potass- ium permanenate. The process may be successfully applied to the estimation of not too small proportions of manganese in iron-spar and nickel-steel ; also in By OTTO SC'HMATOLLA (Chem.Centr., 1901, ii, 1094; from Pharm. Zeit., 1901, 46, 810).--When reduced iron is tested by the process of the German Pharmacopceia, the addition of potassium iodide retards the solvent action of the iodine ; the following modification is therefore proposed : 0.3 gram of the sample is put into a stoppered flask with 5-10 C.C. of water and 1.6 grams of coarsely powdered iodine, the flask is placed in cold water and frequently shaken until the iodine has dissolved. After remaining for half an hour at the ordinary temperature, the excess of iodine is titrnted with N/10 thiosulphate. When pulverised iron is tested, the freshly prepared sulphuric acid solution should be diluted to 200 C.C.A portion is placed in a burette and slowly added to about 2 C.C. of a 2-3 per cent. solution of potass- ium permanganate until this is perfectly clear and decolorised. It is then mixed with iodine (? potassium iodide) and treated according to the Pharmacopaeia process. '' spiegeleisen " and ferromanganese. L. DE I(. Volumetric Estimation of Iron. L. DE K. Method of Quantitatively separating Nickel and Zinc. By ARTHUR ROSENHEIM and ERNST HULDSCHINSKY (Bey., 1901, 34, 3913-3916. Compare Abstr., 1901, ii, 533).-Zinc forms a complex salt with ammonium thiocyanate, (NH,)2Zn(SCN),,4H,0, which crys- tallises in white needles readily soluble in cold water; it closely resembles the corresponding cobalt compound (Zoc. cit.), and like the latter is insoluble in a mixture of ether and amyl alcohol.This property is used to separate zinc from nickel for the purposes ofANALYTICAL CHEMISTRY. 109 quantitative estimation of a mixture of the two metals. The details of the process are similar to ,those previously described in the separation of nickel and cobalt (Zoc. cit.). Alloys of copper, zinc, and nickel, argentan, nickellin, and german silver, have been analysed by this process and the results compared with those obtained by the usual method ; the agreement is very good. [Detection of Olefines in Light Petroleum.] By LUIGI BALBIANO and V. PAOLINI (Chem. Zeit., 1901, 25, 932-933).-Two or three C.C. of the rectified sample boiling below 100' are shaken for 2 to 3 minutes with 10-12 C.C. of a cold saturated solution of mercuric acetate and then set aside in a closed tube for 24 to 36 hours.If then the aqueous liquid is turbid from the presence of small, white, lustrous lamells, the presence of an olefine is proved. The aqueous layer may contain aldehydes or ketones; processes are given for their K. J. P. 0. identification. L. DE K. Determination of the Refractive Index of Ethereal Oils. By F. UTZ (Chem. Centr., 1900, ii, 1130; from Apoth. Zeit., 16, 742-746). -The author used for his recent determinations a n Abbe refracto- meter with prisms that can be heated. It became necessary to ascertain whether the index-division shown on the sector, which is calculated for the ordinary temperature, is available for higher temperatures ; it appears that a correction is only requisite when the temperature exceeds 50°, but, considering the other sources of error, this is not of much practical interest.The same may be said about the increase of the dispersion of the glass with increase in temperature. However, at every observation the temperature should be recorded. The refrac- tive index of a large. number of ethereal oils is given for 1 5 O , 2OC, 2 5 O , and 30°, and also the degree of dispersion at 15'. As a result of this investigation, the author has somewhat modified his previous view that the refractive index may serve to distinguish oils free from terpenes from the ordinary ethereal oils. This is only true in the case of a comparatively small number of ethereal oiIs, for instance, oils of lemon, fennel, juniper, sassafras, &c. The determination of the refractive index may, however, give a valuable clue as to the age of the oil, as i t increases by long keeping; it mill detect admixture of foreign ingredients if these possess a different refractive index from that of the oil and it will often tell the particular part of the plant from Detection and Decomposition of Iodoform.By C. H. L. SCHMIDT (Chern. Centr., 1901, ii, 1095 ; from Arch. internat. Pharm. Therap., 1901, 8, llO).-A starch solution, coloured blue by the presence of iodine, is mixed with dilute sulphuric acid and filtered from the iodide of starch. The filtrate is mixed with nitrite, which will then show the presence of hydriodic acid. Any precipitate is collected, and the filtrate mixed with zinc dust, which decomposes the iodoform and causes a further blue precipitate.By means of this reaction the author has found that iodoform gives off iodine at 100' and even at 80' in the presence of air; in the presence of water or which the oil has been prepared. L. DE K.110 ABSTRACTS OF CHEMICAL PAPERS. glycerol and air, part of the iodine is converted into hydriodic acid. Besides iodine, some carbon dioxide and carbon monoxide are also formed. The presence of the latter may be proved by heating the iodoform a t looo in a current of air and passing the vapours first through water and then through blood. L. DE K. Detection of Iodoform in the Presence of some Organic Iodine Compounds. By C. H. L. SCHMIDT (Chem. Centr., 1901, ii, 1095; from Arch. internat. Pharm. Themp., 1901, 8, 187).-Iu the presence of isopropyl iodide, allyl iodide, or di-iodohydrin, iodoform may be detected by taking advantage of the fact that, like allyl iodide, it may be decomposed or extracted by mercury or chloroform, whilst impropy1 iodide is only extracted by chloroform, and di-iodohydrin is neither decomposed by mercury nor extracted by chloroform.The presence of albumin does not interfere with the reaction. When iodoform, suspended in glycerol, is heated for a long time a t looo, carbon monoxide and carbon dioxide are evolved and the liquid con- tains free iodine, hydriodic acid, and traces of isopropyl iodide. The latter is formed by the action of hydriodic acid on the allyl iodide, obtained by the action of iodine on glycerol. Ally1 iodide is only temporarily present in the liquid and may be detected by its odour and physiological action.L. DE K. Detection of Methyl Alcohol in Ethyl Alcohol. By JOSEF HABERMANN and A. OESTERREICHER (Zeit. anal. Chem., 1901, 40, 721--724).-The method is based on the fact that an alkaline solution of potassium permanganate is decolorised much more rapidly by methyl alcohol than by ethyl alcohol. To 10 C.C. of the liquid to be tested, which must contain nobhing except water and the respective alcohols (10 per cent.), two drops of a 10 per cent. solution of potassium hydr- oxide, and then one or two drops of N/10 permanganate are added. With ethyl alcohol, the colour takes about 5 minutes to pass through violet and green to yellow, the green stage lasting for several minutes ; if methyl alcohol is present, however, the change to yellow is so rapid that the intermediate colours can scarcely be observed.Liquids con- taining less than 5 per cent, of methyl alcohol require a preliminary fractional distillation. M. 5. S. Detection and Estimation of Methyl Alcohol in Commercial Formaldehyde. By MAURICE DUYK (Ann. Chim. anal. appE., 1901, 6, 407--409).-0ne hundred C.C. of the sample previously diluted with half its bulk of water are placed in a cooled flask and ammonia is slowly added in slight excess; if after a few hours the liquid still does not react with phenolphthalein, a little more ammonia should be added. A little sodium carbonate is added in order to render the hexamethyl- enetetramine more stable and the liquid is distilled until 100 C.C. have passed over.The distillate is neutralised with dilute sulphuric acid and redistilled in a bulb apparatus, and the fractions passing over between 65' and 100' are collected. These are again rectified so as to obtain a distillate containing three-fourths of its bulk of methyl alcohol. The methyl alcohol is finally estimated by converting itANALYTICAL CHEMISTRY. 111 into methyl iodide. For every 5 c.c., 10 grams of iodine and 2 grams of amorphous phosphorus are added; after a few hours the mix- ture is heated in a reflux apparatus and the whole distilled. The methyl iodide is collected in a gradilated measure over water and from its volume that of the methyl alcohol is calculated, Commercial samples of formaldehyde have been found t o contain from 3 to 10 per cent.of methyl alcohol. L. DE K. Estimation of Glycerol. By SIMON ZEISEL and R. FANTO (Chem. Centr., 1901, ii, 1131 ; from Zeit. Zandw. Versuchs-Wes. Oestevr., 4, 977-979).-The glycerol is boiled in a reflux apparatus with hydriodic acid (b. p. 127O), which soon converts i t into isopropyl iodide. This may then be distilled and its iodine estimated by means of Zeisel's alcoholic solution of silver nitrate. L. DE K. Quantitative Separation of Cholesterols from Fats. By E. RITTER (Chem. Zeit., 1901, 25, S72).-Fifty grams oE fat are heated on the water-bath in a large porcelain basin with 100 C.C. of alcohol and a solution of 8 grams of sodium in 150 C.C. of 99 per cent alcohol. When the alcohol has volatilised, 75 grams of saIt are added and then so much water that the greater part of the mass dissolves. Theliquid is afterwards evaporated to dryness, first over the naked flame, then on the water-bath, and finally in a drying oven a t 80'.The residue is finely powdered, put into a paper cartridge, and extracted with ether in a Soxhlet tube for 9 hours. Sand or paper cannot be substituted for the salt. To remove traces of soap and glycerol, the ether is distilled, the residue dissolved in as little alcohol as possible, and reprecipitated by water. The choIestero1 is collected on a filter and dried at 60' ; the bulk of it is then transferred to a weighed flask and thelast adhering particles are rinsed off with ether. The ether is evaporated and the residue dried a t 100-1 2 0'. L. DE I(. [Estimation of Sugar in Beets.] By R.S. HILTNER and R. W. THATCHER (J. Amer. Chem. Xoc., 1901, 23, 863--868).-A polemical reply to the criticism of Ewe11 (J. Arne?*. Chem. Xoc., 1901, 23, 432) on the method described by the authors for the estimation of sugar in beets (Abstr., 1901, ii, 535). E. G. Estimation of Volatile Acidity of Wines. By XAVIER ROCQUES and G. SELLIER (Ann. Chim. anal. appl., 1901, 6, 414--417).-The authors had previously devised (i6id., 1898, 3, 222) an apparatus based on the same principle as that of Curtel (this vol., ii, 55). They think, however, that the sources of error mentioned by Curtel are not of sufficient importance notably t o affect the results of the distillation process. Another possible source of error, however, is that, if the wine should contain bisulphates and be concentrated to a very small volume, the tartaric acid will be acted on with formation of carbon dioxide and112 ABSTRACTS O F CHEMICAL PAPERS.an aldehyde which collects in the distillate and renders the titration Estimation of Uric Acid. By ADOLF JOLLES (Zeit. plysiol. Chem., 1901, 33, 542-546).-The author maintains, in opposition to Fohn and Shaffer (Abstr., 1901, ii, SSS), that his method (Abstr., 1900, ii, 450, 515) is accurate. Detection of Benzoic Acid and Alkali Benzoates in Food By J. DE BREVANS (J. Plmrm. Chim., 1901, [vi], 14,438-440).-The sample to be tested is extracted with water (if a liquid, 200 C.C. are taken), the solution filtered, acidified with dilute sulphuric acid, and extracted three times with 50 C.C. of a mixture of equal volumes of ether and light petroleum.The residue left on evaporation of the ethereal solution may contain “ saccharin,” salicylic acid, and benzoic acid. If the first two are absent, the benzoic acid may be tested for in the following way. A small portion of the residue is placed in a dry test-tube, 2 C.C. of aniline containing 0.02 gram of rosaniline hydrochloride per 100 C.C. are added, and the mixture boiled for about 20 minutes, when, if benzoic acid is present, the liquid becomes red, then blue, and finally violet in colour. A few drops of dilute hydrochloric acid are next added, and the solid portion, which is now blue in colour, is collected, washed until all the violet colouring matter is removed, and finally dissolved in alcohol, when, if benzoic acid was originally present, the blue colour due to the aniline-blue formed is clearly seen.slightly inaccurate. L. DE K. W. D. H. H. R. LE S. Application of Iodine Monobromide in the Analysis of Fats and Oils. By Jos. HANUS (Zeit. Nnhr.-Genussm., 1901, 4, 9 13-920).-10dine monobromide may be easily, prepared by slowly adding 13 grams of bromine to 20 grams of powdered iodine with constant stirring, and cooling to 5-8’. The reaction takes about 10 minutes for completion and the product is freed from any un- combined bromine by passing a rapid ciirrent of carbon dioxide over it, It constitutes a grey, crystalline, metallic-looking substance which should be preserved in a stoppered bottle. The author prefers to use its solution in glacial acetic acid instead of tho well-known Hub1 solution for the followiug reasons.Its strength is readily ascertained by adding potassium iodide and titrating with sodium thiosulphate, it keeps for a considerable time and it acts on fats with great rapidity, so that an iodine absorption takes only 10-15 minutes. I n practice, it has been found convenient to dissolve 10 grams of the compound in 500 C.C. of glacial acetic acid. 0-6-0.7 gram of solid fats, 0.2-0.25 gram of oils having an iodine figure below 120, or 0.1-0.15 gram of oils showing a higher figure is dissolved in a beaker or stoppered flask in 10 C.C. of chloroform and 25 C.C. of the standardised iodine monobromide solution are then added from a burette. After. standing for 10 minutes (fats) or 15 minutes (oils), 15 C.G. of solution of potassium iodide (1 : 10) are added, and the liberated iodine titrated with sodium thiosulphate without using starch.The results agree with those af Hiibl, L. DE K.ANALYTICAL CHEMISTRY. 113 Sydtematic Inspection of Milk for Preservatives. By ALBERT E. LEACH (,4naZyst, 1901, 26, 289-291).-Formaldehyde is tested for by heating t o boiling in a porcelain casserole 10 C.C. of the sample with 10 C.C. of hydrochloric acid containing 1 C.C. of 10 per cent. ferric chloride per 500 C.C. The presence of formaldehyde is indicated by a more or less intense violet coloration. Although objection has been taken to this test on account of other colour reactions taking place, the author has never met with a sample giving this reaction, where the presence of formaldehyde could not also be proved by other tests.The ash obtained in due course is moistened with a drop or two of dilute hydrochloric acid, when any effervescence will show the presence of sodium carbonate; the original sample is examined by the rosolic acid test for carbonate. A few C.C. of water are then introduced into the crucible and when the ash is dissolved it is tested in the usual way for boric acid with turmeric paper. L. DE K. Detection of Margarine in Butter. By CHARLES ANN AT^ (Chem. Centr., 1901, ii, 836; from Pharm. Zeit., 46, 693).-The butter prepared from the milk of three cows, which, in addition to their usual food, had also partaken of sesame cakes, gave with the furfuraldehyde test a decided reaction for sesame oil. The mere fact of this test being obtained does not, therefore, prove the presence of margarine.On account of its liquid nature, sesame oil itself cannot be employed as a butter adulterant, but only so when in combination with tallow or similar fats. L. DE K. Detection of Margarine in Dairy Products by means of the Sesame Oil Test. By HERMANN BREMER (Chem. Centr., 1901, ii, 955 ; from Pharm. Zed., 46, 757-758).-The author strongly doubts Annatb’s statement that butter prepared from the milk of cows which have been fed on sesame cake gives the furfuraldehyde test for sesamh oil, and suggests that the test has been improperly applied. It is of the utmost importance that the butter-fat should 5e carefully filtered, so as to remove every trace of casein. I t is, however, thought possible that a chemical extraction of the milk might yield a fat giving the By PAUL SOLTSIEN (Chem.Celztr., 1901, ii, 1095; from Phawn. Zeit., 46, 771--772).-A reply to Bremer. Even now the author would prefer the sugar t o the furfuraldehyde test if the use of the latter had not been made obligatory [in Germany]. The fact, stated by Schrott and Fiechtl, that a solution of furfuraldehyde in hydrochloric acid gradually turns red, had been :By CHARLES ANN AT^ (Chm. Centr., 1901, ii, 1095-1096; from Phccrm. Zeit., 46, 772).-A reply t o Bremer. The author was fully aware of the precautions to be taken to ensure a successful sesame oil reaction. reaction. L. DE K. Detection of Sesame Oil. noticed independently by the author. L. DE K. The Sesame Oil Reaction in Butter Analysis. L. DE K,114 ABSTRACTS OF CHEMICAL PAPERS, Detection of Margarine by means of the Sesam6 Oil Reaction.By HERMANN BREMER (Chem. Centr., 1901, ii, 1096 ; from Phurm. &?it., 46, 818-819. Compare Abstr., 1900, ii, 325).-A reply Is the Sesame OilReaction of a Butter a sufficient Proof of Adulteration. By A. REINSCH (Chew,. Centy., 1901, ii, 1096; from Milch. Zeit., 30, 643--644).-1n the author’s experience, every sample of butter which gave the sesame oil reaction was found t o contain margarine. Undoubtedly genuine butter never gave the reaction. It is a matter of regret that the feeding experiments of Yieth artd By FERNAND RANWEZ (Rev. intern. FuZs$., 1901, 14, 125--127).-Soltsien has stated that the test with hydrochloric acid and furfuraldehyde is untrustworthy and has recom- mended the use of a solution of stannous chloride instead.The author states that the latter test is not delicate enough for the detection of small quantities of sesame oil in butter, and has also proved by a number of experiments that the furfuraldehyde test may be safely used. I n the absence of sesame oil, no colour is developed for several hours and only on a prolonged contact is a brownish-yellow coloration gradually formed ; this is not likely to be mistaken for the red colour caused by Occurrence and Detection of Sesam6 Oil in Commercial Arachis Oils. By PAUL SOLTSIEN (Chem. Revue, 1901, 8, 202-203). -Tambon has stated that the fatty acids obtained from arachis oil, give, like sesame oil, the Baudouin furfuraldehyde reaction. The author has fully investigated this matter and states that there is hardly any commercial arachis oil which does not contain sesame oil either by actual adulteration or from the fact that often arachis oil is pressed after sesame oil.Samples prepared by the author never gave the reaction. When applying Baudouin’s test to the fatty acids, i t must be borne in mind that the active principle of sesame oil is somewhat soluble in mineral acids and, in consequence, gets partly removed ; however, the presence of 1 per cent. of sesame oil in arachis oil may be safely detected when operating with the fatty acids ; stannous chloride should not be substituted for furfuraldehyde as i t causes the fatty acids to Some Analyses of Bulgarian Butter derived from Buffaloes and Sheep, also of Bulgarian Lard and Walnut Oil.By NIKOLAUS PETKOW (Zeit. iVcd.r.-Genussm., 1901, 4, 826-828).- Analyses are given of fourteen samples of buffalo and 12 samples of sheep’s butter, showing the amount of water, fat, non-fatty matters, sp. gr. of the fat a t loo”, refraction, Reichert-Meissl number, Kottstorfer number, iodine number, insoluble fatty acids, and free acids (Burstyn’s method). Both varieties of butter show no practical difference from cow’s butter except in so far that the Reichert-Meissl numbers of the buffalo butter were higher than is mostly the case with cow’s butter; they varied from 31.02 to 38.2, to Soltsien and Annatb (preceding abstracts). L. DE K. Siegfeld have not been carefully repeated. L. DE I(. Detection of Sesame Oil. sesame oil. L. DE K. turn brown.L. DE K.ANALYTICAL CHEMISTRY. 115 Similar analyses of three samples of Bulgarian lard showed that this does not materially differ from other European lard. The average analysis of 5 samples of cold-pressed Bulgarian walnut oil gave : sp. gr. 0.9258, at 1 5 O : refractometer number 67.7, at 40": iodine number 148.21 and acidity (Burstyn) 4.38. L. DE K. A Sharp Indicator for Titrating Dark Coloured Fats. By J. FREUNDLICH (Chem. Centr., 1901, ii, 1094-1095 ; from Oestew. Chew. Zeit., 1901, 4, 441-442. Compare Abstr., 1900, ii, 41).-When phenolphthalein cannot be used as an indicator, the author recommends that for each titration 10 C.C. of a 2 per cent alcoholic solution of Alkali Blue I1 OLA should be used. L. DE K. New Gravimetric Estimation of Formaldehyde.By LUDWIG} VANINO (Zeit. anal. Chem., 1901, 40, 720--721).-When added to a t mixture of silver nitrate with an excess of sodium hydroxide, formalde - hyde is oxidised to sodium formate with reduction of a corresponding; amount of silver oxide to the metallic state. After being left for 1Ei minutes in the cold, secluded from light, the precipitate is digested thret3 or four times with an excess of 5 per cent. acetic acid. This dissolves tht? unreduced silver oxide and the reduced metal can then be collected 011 a weighed filter, washed, dried, and weighed. M. J. S. Microchemical Examination of Tea and Observations or 1 Caffeine. By P. KLEY (Rec. Frau. Chim,, 1901, 20, [ii], 344-351)-- About one-third of a tea leaf is mixed with an equal quantity of quicklime and of water, dried at looo, and moistened with two to three drops of alcohol in a small filtering tube.The filtered solution is evaporated, the residue placed on a small mica plate, surrounded bJy a ring of asbestos and sublimed on to a glass cover slip. The subi- limate generally consists of an amorphous centre with radiatinl; needles; if the latter do not show, the plate is breathed on afteir drawing across it a platinum wire with which a crystal of caffeinc3 has been broken. The whole of the amorphous mass gradually becomeis crystalline, Tea leaves which have once been extracted do not give L L sublimate of caffeine under these conditions. On crystallising caffeine from water a t 70", short, thick needles are obtained with a rectangular extinction between crossed nicols , which are totally different from those of ordinary caffeine, the extinction of which is at 36'; the former crystals are anhydrous, the latter. hydrated.On subliming anhydrous caffeine to which a little water has beenl adheti, anhydrous crys'tah are deposi'ted, unless the sur'face 01 deposikion has upon it a trace of the hydrated substance; when this is present, the sublimate is hydrated. Hydrated caffeine loses the whole of its water over sulphuric acid. W. A. D. Detection of Nicotine by means of Formaldehyde. By SCHINDELMEISTER (Rev. intern. B'ahif., 1901, 14, 129).-If a trace of nicotine is mixed with 1 drop of 30 per cent. formaldehyde, a solid residue is formed after some hours which gives an intense rose colora-116 ABSTRACTS OF CHEMICAL PAPERS. tion when touched with a drop of strong nitric acid ; if resinous matter is present, a blood-red colour appears.After some time, the colour changes to green. A more permanent colour is obtained when instead of formaldehyde pure formic acid is used. The test is characteristic for nicotine and is not given by conicine and similar organic bases formed By EDUARD SPAETH (Zeit. Nahr.- Genussm., 1902, 4, 920-930) (continued from Abstr., 1901, ii, 291). -Full details are given for the detection of sugar substitutes (starch- syrup, ‘‘ saccharin,” dulcin), preservatives (salicylic acid, benzoic acid, calcium P-naphtholsulphonate [abastrol], alcohol, boric acid), organic acids, and esters by already known processes. Raspberry juice, or syrup, when pure, is characterised by freedom from unfermentable polarising substances (dextrin) after treating the fermented solution with basic lead acetate, and also by the fact that the fixed acidity is mainly due t o malic acid.The author also observes that the test for artificial colours as laid down in the German Pharmacopmia, namely, agitation with amyl alcohol, is not conclusive, but that it should be supplemented by the ‘‘ wool test” and Estimation of the Alkalinity of Blood. By AUGUSTE LUMI~RE, LOUIS LUMI~RE, and HENRI BARBIER (Compt. rend., 1901, 133, 692--695).-The various methods of estimating the alkalinity OF blood yield variable results, and the authors find that greater accuracy is secured if, after mixing the blood with excess of acid, the residual acid is determined by causing it to act on R mixture of potassium iodate and iodide and titratiog the liberated iodine. With a constant quantity of acid and varying quantities of blood, however, the alkalinity decreases as the quantity of blood increases, but constant results are obtained if the quantity of acid added is proportional to the weight of blood taken. The alkalinity as thus determined repre- sents the true alkalinity and a fraction of the total basicity of the blood. C. H. B. Detection of Peptone in Urine. BY ZDENEO CERNY (Zeit. anal. Chem., l901,40,592--595).-Urine is commonly examined for peptone either by saturating with ammonium sulphate or by precipitating with phosphotungstic acid and testing either precipitate for the biuret reac- tion. Prom urine rich in urobilin, that substance is also precipitated by both reagents, and likewise gives the biuret reaction. Bang has shown that the ammonium sulphate precipitate can be freed from urobilin by washing with alcohol. The author finds that if the phosphotungstic acid precipitate of urobilin is decomposed by barium hydroxide and the warm alkaline solution shaken with air, the urobilin becomes oxidised, with the possible exception of traces which are too small to produce the biuret reaction. The phosphotungstic precipitate obtained by Hofmeister’s method is more easily oxidised than that prepared by Salkowski’s method. by putrefying meat. L. DE K. Analysis of Raspberry Juice. the usual tests for vegetable colours. L. DE K. M. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9028205104

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

General and Physical Chemistry. Dispersion of Ultra-violet Rays. By I?. F. MARTENS (Ann. Phys., 1901, [ iv], 6, 603-640).-A theoretical and physical paper, not suitable for abstraction. J. C. P. Radioactivity of Uranium By HENRI BECQUEREL (Compt. rend., 1901, 133, 977-980).-The author has previously found (Abstr., 1900, ii, 518) that if solutions of uranium compounds are mixed with a small quantity of a barium salt and the latter is pre- cipitated, the radioactivity of the precipitate is considerably higher than that of the original uranium compound, whilst by several repeti- tions of this process the radioactivity of the uranium compound is greatly reduced. After the expiration of eighteen months, he has again examined the various products and finds that the uranium preparations have regained their original radioactivity, with practically the same intensity in all cases, whereas the barium precipitates have entirely lost their radioactivity, or, in other words, have behaved as if their very marked radioactivity was simply induced.The author considers that these results shorn that uranium compounds have a radioactivity of their own, although the possibility that the uranium may contain a small quantity of some specially radioactive substarice not separated in the various operations is not excluded. The recovery of radio- activity is in all probability a phenomenon of auto-induction, and supports the author’s view that the emission of rays not deviated in a magnetic field is due to the emission, by the same substance, of deviable rays, just as Rontgen rays are produced by the impact of cathode rays.The author has repeated his observations on the radio- activity of uranium compounds a t the temperature of liquid air, and confirms his previous result. C. H. R. Researches on Contact Electricity. By OSCAR KNOBLAUCH (Zeit. physikal. Chem., 1901, 39, 225--244).-The author determined the sign of the charge left on plates of platinum, paraffin, glass, and sulphur, on the removal of various powders which had been placed on the plates. Seventy-five different compounds were employed, including acids, bases, neutral salts, and various organic products. Platinum and paraffin become positively charged if the powder is of an acid nature, negatively if it is alkaline, whilst for neutral compounds the charge left is sometimes positive, sometimes negative.Sulphur be- comes positively charged by contact with acid powders, but negatively in almost all other cases ; glass, however, becomes negatively charged, except when the powder is of an alkaline nature. These results are satisfactorily explained on the assumption that plates and powders are coated with a film of the saturated aqueous solution ; when an acid powder is placed on the platinum or parafEn plate and the films are hence in contact, the hydrogen ions, on account of their greater velocity, pass in excess into the platinum surface film, so that when yot. LXXXII. ii. n118 ABSTRACTS OF CHEMICAL PAPERS. the powder is removed, the plate is positively charged. Similar reasoning explains the negative charge with alkaline powders, whilst in the case of neutral salts, the charge is dependent on the relative velocities of the two ions.The differences between the results obtained with glass and sulphur plates are due to the fact that the films on the plates themselves are respectively alkaline and acid solutions, The author further discusses the law enunciated by Ccehn that, of two dielect,rics in contact, the one with the higher dielectric constant becomes positively charged (Abstr., 1898, ii, 363). L. M. J. The Discharge Potential of Hydrogen at a Mercury Cathode. By ALFRED COEHN and EDGAR NEUMANN (Zed. physikcd. Chem., 1901, 39, 353-354).-The difference between the discharge potential of hydrogen a t a platinum and a t a mercurycathode a t -85' is nearly the same as the difference at 1 8 O , and the authors conclude that, since in one case the mercury is solid and in the other case it is liquid, the dificharge potential of hydrogen a t metal cathodes is depen- dent, not on accidental properties of the metal, such as the form and nature of the surface, but on the chemical individuality of the metal.J. McC. Potential Differences in Vapours and in some Solid Electro- lytes. By RUDOLF VON HASSLINGER (Monatsh., 1901, 22, 907-916)- The author has measured the potential differences assumed by metals when placed in a bunsen burner into which solutions of various salts are sprayed. The potential difference is influenced by the basic a s well as the acid constituent of the salt, but the greater part of the potential difference measured seems to be due to the latter.The most remark- able result observed was that, in the vapour of certain salts, iron and nickel assumed a positive potential towards platinum. In fused lithium chloride, iron is negative towards platirrum. The difference of potential varies with the temperature, the maximum value being reached at about 800'. On further raising of the temperature, the E.M.F. decreases, and in lithium chloride, vapour passes through zero to the change of sign. The same phenomenon is well-shown with the solid electrolytes, calcium and magnesium oxides. G. Y. Dielectric Constant of Paraffins. By WILL G. HORMELL (Amer. J. Sci., 1901, [iv], 12, 433-446).-The paper is mainly physical. By means of an electric wave method, the author finds that the higher the melting point of the paraffin, the greater is the dielectric constant.As the wave-length diminishes, the dielectric constant increases. Cauchy's formula for calculating the index of refraction for infinitely long waves gives results inconsistent with experiment. Electrical Properties of Alloys of Copper and Cobalt. By G. REICHARDT (Ann. Phys., 1901, [iv], 6, 832-S55).-The effect of small quantities of cobalt on the electrical properties of copper is almost as great as that of manganese and about three times as great as that J. C. P.GENERAL AND PHYSICAL CHEMISTRY. 119 of nickel, The addition of 3-5 per cent. of cobalt gives an alloy with a minimum ternperature coefficient of resistance ( + 0*00077), and with a maximum thermoelectric effect (against copper) of 33 microvolts for lo temperature difference.Up to this composition, the specific resist- ance of the alloys increases rapidly, but further addition of cobalt pro- duces only a slow increase of resistance. The only practical application that could be made of the alloys is in the construction of thermo- electric batteries. The addition of small quantities of copper has a great effect on the properties of cobalt. The specific resistance has a maximum, the thermoelectric effect a minimum, value between 0 and 10 per cent. of copper. All alloys except those containing less than 1.5 per cent. of cobalt can be magnetised, the magnetism being destroyed only a t a bright-red heat. It is noted that alloys of copper and nickel cannot be magnetised. J, c* P, Electrical Conductivity of Flames and Gases.By ALEXANDRE DE HEMPTINNE (Zed. physikcd. Chern., 1901, 39, 345-352. Compare Abstr., 1893, ii, 563).-The deflection of a galvanometer needle con- tained in a battery circuit was observed when gas explosion took place in a tube containing free ends (electrodes) of the circuit. The deflec- tiondecreases with decrease of E.M.F. of the battery, but not exactly proportionally. It decreases as the distance between the electrodes is increased. When the electrode connected with the positive pole of the battery is large and that connected with the negative pole is small, R large deflection is obtained, whilst if the connections be reversed only a small deflectlion is noticed, thus indicating that the conductivity of an explosion (like that of a flame) is unipolar.The deflection is greatest when the explosion tube is open to the air, and is very small when the whole apparatus is kept at a temperature much above looo. Prac- tically the same results were obtained when the electrodes consisted of platinum, gold, or iron wires, and a magnetic field is also without influence. These experiments were made with an explosive mixture of hydrogen and oxygen. With a dry mixture of hydrogen and chlorine, or of oxygen and carbon monoxide, no deflection was obtained, but when the mixture was moist, the needle moved through 0.5 mm. From the experiments, i t is deduced that no ions take part in the gas reaction, but the electricity is solely transported by condensed water, for conditions under which condensation may take place favour the trans- portation.J. McC. A Peculiar Cell containing Chromic Chloride (Electro- chemical Equilibrium between Different Degrees of Oxida- tion). By ARRIGO MAZZUCCHELLI (Gaxxetta, 1901, 31, ii, 371-395). -In 1886, Case described a cell (Proc. Roy. Xoc., 1886, 40, 348) con- sisting of tin and platinum poles in chromic chloride solution, which he stated had an E.M.F. 0 a t the ordinary temperature, and 0.25 volt a t 95O. I t was found later, however, by Skinner (Abstr., 1896, ii, 3), that this cell has the E.M.F. 0.44 volt at 15' and 0.40 volt at 97', but that it polarises much more readily at low than at higher temper- atures. The reactions taking place in the cell are, a t high temper- 9-42120 ABSTRACTS OF CHEMICAL PAPERS. atures, the solution of tin by the liquid with the production of chromous chloride, and reprecipitation of the tin- in the cold.As was shown by Case, the cell is very variable in its action ; the B.M F. is altered by shaking and exhibits a steady decrease when the cell is left to itself on open circuit, the fall being more rapid at high than a t lower temperatures. The author explains these changes as due in the first instance to the action of the chromic chloride on tin, which takes place as a local action, even when the cell is an open circuit, producing stannous and chromous chlorides; the latter are then always present in ihe liquid of the cell in proportions depending on the amound of surface presented by the tin, on the time of standing, &c., and further, their distribution throughout the liquid is not uniform.The potential of the platinum is, of course, dependent on the exact com- position of the liquid in contact with it. The author derives, from theoretical considerations, the action of a cell containing both oxidising and reducing compounds, and endeavours to determine chemically the equilibrium between tin and chromic, chromous, and stannous chlorides, but the numbers obtained do not agree with the theoretical values. The only interest attaching to this cell is not, as was stated by Haber (“ Electrochemie,” p. 177), that it allows of the direct transformation of heat into electrical energy, or, as was mentioned by Skinner, that it is capable of executing a Carnot’s cycle, but that owing t o the very high temperature coefficient of the reaction taking place in it, the chemical and electrical equilibria between the different states of oxidation are readily attained.T. H. P. The Decomposition-tension of Molten Sodium Hydroxide and of Lead Chloride. By JULIUS FRIEDRICH SACHER (Zed. anorg. Chem., 1901, 28, 385-460).-When sodium hydroxide is fused in an iron vessel it soon assumes a red tinge, and when this has happened the iron has become passive so that on immersion of an iron wire into the fused mass there is no polarisation current ; up to the time when this passive state has been induced, a polarisation current of very variable strength is obtained. The only metals suitable for electrodes in the electrolysis are iron and platinum, the former being preferable. The discharge potential and the cathodic and anodic decomposition- tensions of fused sodium hydroxide have been determined in an iron vessel with an iron electrode, arid with a platinum vessel and electrode, at temperatures varying between 385’ and 563’, and between 575’ and 694’.The curve of cathodic decomposition shows two well-marked breaks, as also does that of the anodic decomposition ; the values found for the points at which the curve shows a sudden change are : for the cathodic discharge, 1.16 volts (at 390’) and 2.06 volts (at 389O), and for the anodic, 0.11 volt (at 395O) and 1.31 volts (at 393’). The higher cathodic point corresponds with the separation of sodium and the lower with the separation of hydrogen. The higher anodic point is due to the discharge of hydroxyl ions and the lower to that of 0” ions.This lower anodic point disappears as the hydroxide becomes free from water and the author concludes that the sodium hydroxide dissociates into Na- and OH’, and the water either itself gives the ions If* and 0’. vr causes these to be formed from the OH‘CfaNERAL AND PHYSICAL CHEMISTRY. 121 The polarisation of fused lead chloride was determined by the decomposition method in glass vessels of various forms, using carbon electrodes. Two breaks occur in the curves obtained; the position of the lower break varies greatly with the distance between, and the size of the surface of, the electrodes. At 575O, the higher break occurs a t 1.256 volts, at 681°,it is at 1.190 volts. When the electrodes are encased, the lower break entirely disappears. This lower break is due to R depolarisation effect produced by the depolarising action of a cloud of lead vapour which diffuses from the cathode to the anode. The higher break corresponds with the reversible action : PbCl, t Pb+Cl,. Similar conclusions are to be drawn from the results obtained by determining the discharge potentials.Considerable doubt must be entertained as to the interpretation of results given by Garrard (Zeit. EZekt?*ochem., 1899,6, 214), who assumes that the electrolytic decomposition of salts of bivalent metals takes place in two stages : MR, = MR* + R (corresponding with the higher break in the decomposition curve) and MR- = M* + R’ (corresponding with the lower break). Influence of the Addition of a Salt with one similar Ion on the E.M.F.of Electrolytic Cells. By OTTO SACKUR (Zeit. physikal. Chem., 1901, 39, 364-368. Compare Abstr., 1901, ii, 636).-Planck’s formula for the influence of a salt with one similar ion on the E.M.P. of an electrolytic cell becomes identical with that of Abegg and Bose when the concentrations of the electrolyte, C, and c2, are the same. It is shown that diffusion can take place against the fall of con- centration, and that the ions do not only follow Dalton’s law of partial pressure but their motion is influenced by osmotic and electrical forces. By WLADIMIR A. KISTIA- KOWSKY (J. Rum. Phys. Chem. Xoc., 1901, 33, 480-496 and 592-621). -The author indicates a new method of calculating the electrolytic potentials of the alkali and alkaline earth metals from the heats of formation of the haloid salts in dilute aqueous solution.The numbers given, which are calculated from results obtained by Thomsen and by Berthelot and refer to the potential of the hydrogen electrode in a normal solution taken as zero, differ from those of Wilsmore (Abstr., 1901, ii, 2). The conditions of concentration and temperature necessary for the formation of the two complex salts, Ag,T(NO,), and Ag21N0,, have been investigated (compare Hellwig, Abstr., 1900, ii, 723). By measurements of the electromotive force of the concentration-cell, Ag I AgNO,, AgI 1 AgNO, (concentrated) I AgNO, 1 Ag, the author shows that the salt Ag,I(NO,), is resolved into the ions Ag,I and 2N0,. I n the case of Ag,INO,, the ions are probably Ag,X and NO,.A relative measure of the free energy of formation of double salts of potassium cyanide with other cyanides has been obtained by deter- mining the electromotive force of the element, R I KCN I EX I R, R being a metal and RX one of its salts. Where R represents Mg, Al, Zn, Cd, H, or Cu, it is found that the electromotive force increases as J. McC. J. McC. Electro-chemistry of Double Salts.122 ABSTRACTS OF CHEMICAL PAPERS. the electro-affinity decreases, as is required by the principle put forward by Abegg and Bodlander (Abstr., 1899, ii, 542). The exceptions to this rule, namely, Ni, Pb, Hg, and Ag, are due to the capacity possessed by these elements for forming complex cathions, The author has determined experimentally the relative velocities of migration of the ions of the double salts, Ag,Cr(C,0,),,4K20, K4Fe(CN),,3H,0, and K,Co(CN),, the results showing that Kohl- rausch's law holds €or such complex salts.A sketch and description of the special apparatus employed in these measurements are given. Measurements hare also been made of the electrical conductivity of very dilute solutions of the salts, KAg(CN),, E,Ni(CN),, K3Co(CH)6, K ,Fe (CN),, 3H,O, and K,Cr ( C204),, 3H,O. T. H. P. Production and Maintenance of Low Temperatures. By ARSBNE D'ARSONVAL (Compt. rend,, 1901, 133, 980--983).-Tempera- tures down to - 60' are readily obtained by means of methyl chloride contained in a porous battery cell from the walls of which the neces- sary evaporation takes place spontaneously. Temperatures of - 112' to - 115' are obtained by means of solid acetylene or solid carbon dioxide, the former being as manageable as the latter, whilst it evaporates more slowly and a t a lower temperature, - 85'.Both dissolve readily in acetone and the temperatures specified are produced by the evapora- tion of these solutions, the air which is bubbled through the liquid being previously cooled by passing through a metal worm cooled by the gases escaping from the liquid. For temperatures below - 115', liquid air must be used, and with its aid any low temperature down to -194' can be obtained and kept constant. The object to be cooled is immersed in a bath of paraffin of low boiling point, the bath being cooled by allowing liquid air to drop into and evaporate from n small metal vessel placed in the paraffin a t its surface.The temperature is controlled by the rate of flow of the liquid air, which can be regulated in various ways. I n the cylindrical double-walled vessels with a vacuous space between and with silvered walls, the loss of liquid air at the ordinary temperature by spontaneous evaporation from a vessel of about 1000 C.C. capacity is only about 20 grams per hour. New Furnace Heated by the Oxyhydrogen Blowpipe. By HENRI MOISSAN (Ann. Chim. Phys., 1901, 24, [vii], 289--298).-This furnace consists of a cylindrical box of hydraulic lime, perforated concentrically through its cover and bottom. The oxyhydrogen blowpipe is introduced into the lower aperture and the products of combustion escape by the hole in the cover. The crucible is made of quicklime, or of graphite with a protective outer coating of quicklime and is supported on three quicklime prisms placed on the floor of the furnace.This apparatus is employed in melting refractory siibstances and difiers from the furnace devised by Deville and Debray in being heated from below instead of from above. As the 5ame does not come into contact with the contents of the crucible, the furnace may be used for fusing oxidisa ble substances, G. T. M. [Thermodynamics of Concentrated Solutions. J By J. J. VAN LAAR (Zed. physikal, CAena., 1901, 39, 342--344).-The author C. H. B.GENERAL AND PHYSICAL CHEMISTRY. 123 considers that the deductions made by Schukareff (this vol., ii, 4) are founded on false premises and are quite worthless. Thus he assumes that y, is only a function of m,, and p2 is only a function of m,, whereas ~t is well known that p1 aud p2 are very complicated functions of T, p , ml, and m,, and known only for some few simple cases.Further, there can be no distinction between ‘‘ determinate ” and “ undeter- minate )’ potential as supposed by Schukareff. J. McC. Heat of Formation of Chlorine Hydrate. By ROBERT DE FORCRAND (Conapt. rend., 1901, 133, 1304--1306).--Direct deter- minations of the heat of dissolution of chlorine hydrate, corrected for the uncombined water present, and the quantity of chlorine that i t holds in solution, gave - 15.63 Cal. as the mean of three experiments, and hence C1, gas + nH,O liq. = Cl,, nH,O, sol. develops + 18.57 Cal, The value of the heat of formation, calculated from the curves of dissociation representing the observations of Isambert, Roozeboom, and Le Cliatelier respectively, is + 18.16 Cal.C. H. B. Investigations with the Micromanometer. By A. SMITS (Proc. K. Akad. Wetensch. Amstedam, 1901., 4, 163-169. Compare Abstr., 1900, ii, 388, 389, 708 ; 1901, ii, 304, 436).-With a slightly modified form of his manometer, the author has determined the decrease of vapour tension for solutions of sodium chloride, sulphuric acid, and potassium nitrate. I n the first two cases, a minimum value of i is found near the concentrations 0.45 gram-mol. and 0.1 gram-mol. per 1000 grams of water respectively. With potassium nitrate, on the other hand, there is a regular decrease in the value of i up to the most concentrated solution investigated - 0.93 gram-mol. per 1000 grams of water, These results are in qualitative agreement with those obtained by the boiling point method.The author thinks that the existence of a minimum value of i for sodium chloride will be satisfactorily proved by the freezing point method also, although this is not the case as yet (see Raoult, Abstr., 1899, ii, 203; Chroustchoff, Abstr., 1900, ii, 86 ; Kahlenberg, Abstr., 1900, ii, 540). I n referencg to Kahlenberg’s recent paper (Zoc. cit.), the author, whilst admitting that the values of i deduced from the conductivity differ in general from those obtained by a non-electrical method, does not regard this as sufficient ground for rejecting Arrhenius’ theory. I t is probable that the conductivity is a correct measure of the dissociation, and that the different values given by other methods are due to the simultaneous occurrence (in moderately concentrated solutions) of ions and the products of polymerisation or association.J. C. P. Polymerisation of Inorganic Chloro-anhydrides. By GIACOMO L. CIAMICJAN (Atti Real. Accad. Lirtcei, 1901, [v], 10, ii, 221-226).- The fact that the molecular weights obtained from ebullioscopic measurements of certain inorganic chloro-anhydrides seem to indicate polymerisation of these compounds has been explained by Odd0 (this vol., ii, 6) as due to the volatility of the dissolved substances at the temperature of the boiling solution, On determining the value of the ratio, a, of the concentrations of phosphorus oxychloride in the124 ABSTRACTS OF CHEMICAL PAPERS.vapour given off from a benzene solution and in the solution itself, and allowing for the volatilisation by multiplying the observed molecular weight by (1 - a), Oddo (Zoc. cit.) found that the numbers obtained still exceeded the true molecular weight. On repeating these experiments, however, the author finds for a a mean value of 0.515, Oddo's numbers being 0.27, 0.31, and 0.27; correcting by means of the value 0,515, the experimental molecular weights agree well with the normal value, T. H. P. New Methods for the Determination of Molecular Weights of Substances in Dilute Solution. By GIOVANNI GUGLIELMO (Atti Real. Accnd. Lincei, 1901, [ v], 10, ii, 232-239).--811 those methods used in hygrometry to determine the tension of the aqueous vapour of the air and the relation between this tension and that of saturated water vapour at the game temperature may.be employed to measure the tensions of vapours in contact with (1) a solution, and (2) the pure solvent, and from these the molecular weight of the dissolved sub- stance can be deduced, The author describes in detail three different methods of working, in all of which very simple apparatus is made use of.(1) In the first method, a layer about 1 em. deep of the solution is placed in a small flask furnished with a stopper containing +axe bJm, + 3 l ~ w ~ g h +arcs QA .ark,%&. ymx, +$fimd~d+&~rs ~wxking +a within 1 cm. of the surface of the liquid, the bulb of one being surrounded by two or three thicknesses of filter paper fastened to the thermometer; through the third hole passes a rod for stirring the liquid.When the solution is in the flask, the stopper is raised for a moment, and by means of a pipette the covered thermometer bulb is thoroughly moistened with the solvent ; the stopper being replaced, the temperatures indicated by the two thermometers soon becomeconstant and are read off. The molecular weight of the solute is given by the formula M= C.p/(t - tl), p being the weight of the dissolved substance per 100 parts of the solvent, t and t, the temperatures of the dry and wet thermometer bulbs respectively, and C a constant depending on the vapour pressure of the solvent, on the atmospheric pressure, and on the change of the latter per 1"; C may be calculated from these magnitudes, but it is preferable to determine i t experimentally by measurements made on a solution of a compound of known molecuIar weight.(2) In this method, no thermometer is needed, as the rate of evaporation, and hence the rate of cooling, of a rod o r tube surrounded at its lower part by filter paper and moistened with the solvent, is measured by its loss in weight in a certain time when placed in the flask employed in the previous method. (3) The third method makes use of a wide-mouthed flask containing a little of the solution and fitted with a perforated stopper which carries a wide, nickelled tube, closed at the bottom and containing a little of the solvent; the top of this tube is closed by a trebly-bored stopper, through which pass a thermometer and a tube drawn out to a fine point a t the bottom, both dipping in the liquid, and another shorter tube open at both ends.Air is caused to bubble through the solvent by means of the drawn- out tube, the evaporation thus produced serving to cool the nickelled tube, which acts as the essential part of a Regnault's hygrometer.CfENERAL AND PHPSICAL CHEMISTRY. 125 The practical details and precautions to be attended to in the work- ing of these three methods are given. T. H. P. Volume and Density Changes in Liquids due to the Absorp- tion of Gases. By E. WENZEL (Ann. Phys., 1901, [iv], 6,520-532). -A form of dilatometer is described by which the changes referred tocan be accurately determined. The liquid used in the investigation was water, and the gases absorbed were hydrogen, oxygen, carbon dioxide, sulphur dioxide, and ammonia.Following Angstrom (Abstr., 1882, 687 ; 1888, 401), and defining the absorption-dilatation coefficient (6) as the relative increase of volume of the liquid caused by absorption of 1 C.C. of gas at 0" and 760 mm. pressure, the author finds that, in the case of hydrogen and oxygen, the values of 6 ars nearly independent of the quantity of gas absorbed ; in the case of carbon dioxide, the value of 3 diminishes at first, then becomes constant, and finally, when the water is nearly saturated with the gas, rises slightly. For sulphur dioxide, there is a steady rise, for ammonia a steady fall, in the value of 6. The law, therefore, according to which the increase of volume is proportional to the quantity of gas absorbed, holds only for gases which are but slightly soluble.The specific gravities of the dissolved gases have been calcu- lated with the help of 6 ; the values thus calculated are in each case much greater than the specific gravities of the liquefied gases. J. C. P. A New Method for the Determination of the Surface Tension of Liquids. By WILLIAM HENRY WHATMOUGH (Zeit. physikacl. Chem., 1901, 39, 129- 193).-The method consists essentially in the determination of the pressure necessary for the formation of bubbles a t the end of a capillary tube dipping into the liquid, the value being compared with that required with the same capillary in a liquid of known surface tension. The precautions necessary to ensure accur- acy are investigated, and the results show that when these are ob- served the method is both speedy and accurate.I n salt solutions, the surface tension is a linear function of the concentration, and the author finds that an equal increase of surface tension is produced by equivalent weights of chlorides of lithium, sodium, potassium, barium, strontium, and magnesium; the effect of ammonium chloride was, however, slightly less, whilst that of calcium chloride was greater. The effect of sulphates is less than that of chlorides, and the effect of nitrates slightly lower than that of sulphntes. The author does not find that keeping for 24 hours produces any alteration of surface tension of SL solution, a result not in accord with the early observations of Quincke (Ann. Phys, Chem., 1877, 160, 337). A number of binary mixtures were examined and may be divided into classes.(1) Mixtures in which the surface tension could be directly calculated from the surface tensions of the components, as in the case of chloroform and ethyl ether, benzene and toluene. (2) Mixtures for which the surface tension is throughout less than the calculated value, as for water and acetic acid, ethyl ether and benzene, &c. (3) Mixtures in which a minimum value is attained, as in the cases of toluene and xylene, acetic acid and benzene, and others. (4) Mixtures in which a maximum value is found ; the126 ABSTRACTS OF CHEMICAL PAPERS, only mixture of this class examined was that of sulphuric acid and water, the maximum being reached when the mixture contains 46 per cent. of the acid, and it is noteworthy that the compressibility reaches a minimum at the same composition.A number of liquid mixtures which form two phases were also examined, and, as expected, the differ- ences in thesurface tensions of the twophases decreased with rise of temperatwe, becoming nil a t the critical point. Solutions of two salts gave results in accord with those calculated additively. Some ternary mixtures were examined, and curves are given representing the results. L. M. J. Number of Ions in Metallo-ammonium Compounds. By EMIL PETERSEN (Zeit. physikal. Chew., 1901, 39, 249-252).-A reply to Werner’s criticisms on the author’s work (Abstr., 1901, ii, 638). L. M. J. Solvent and Dissociative Powers of Liquid Cyanogen and Liquid Hydrogen Cyanide. By M. CENTNERSZWER (Zeit. physikul. Chem., 1901, 38, 217-224, and J.RUSS. Phys. Chem. Xoc., 1961, 33, 545-547, 547-549).-Liquid cyanogen has but slight solvent power, and it is shown that its dissociative power is likewise very small. Experiments with liquid hydrogen cyanide showed, however, that the salts examined (potassium iodide and trimethylsulphine iodide) were far more highly dissociated in this solvent than in water, a result in accord with the Nernst-Thompson rule connecting the dissociative power and the dielectric constant (compare Schlundt, Abstr., 1901, ii, 299). Boundaries between Polymorphism and Isomerism. By RUDOLF WEGSCHEIDER (Monatsh., 1901,22,917-938).-The theoretical distinction between polymorphism and isomerism is held to be useful in spite of the vagueness of the dividing line.Polymorphism may occur along with polymerism as well as with isomerism. A detailed discussion of the miteria by which these may be distin- guished leads to the conclusion that, whereas isomerism may be sharply characterised, i t is not possible to determine the presence of polymerism to the complete exclusion of isomerism (compare Schaum, Abstr., lS9S, ii, 372; Bancroft, Abstr., 1899, ii, 145). -V eiocity of Beaction in Organic Bdlvents. Decomposition of Chloro- and Bromo-acetic Acids by various Bases in Solution in different Alcohols. By A. SCHWEINBERGER (Gaxxetta, 1901, 31, ii, 321--333).-The following table gives the mean values of R for the hydrolysis by means of different bases of bromoacetic acid dis- solved in various alcohols and in water, the temperature in each case being 60’.It will be seen that methyl alcohol acts irregularly, since in some cases it gives a quicker, and in others a slower, reaction than is obtained with ethyl alcohol. Further, in ethyl alcoholic solution, sodium methoxide has a less rapid hydrolysing action than the ethoxide, whilst from a consideration of the dissociation in the two cases, the contrary would -be expected. This anomalous behaviour of methyl L. M. J. G. Y.GENERAL AND PHYSICAL CHEMISTRY, 127 Base Sodium hydroxide.. .......... Potassium ,, ............ Sodium methoxide.. .......... Sodium ethoxide ............ Sodium propoxide.. .......... Ammonia ..................... Alcohols. Water. I 1 Ethyl. 0.75 0-70 0.32 0 '37 0 *55 0.75 Methyl. 0.54 0.596 0.59 0-54 0.39 0-326 Propyl.alcohol has been noticed in other reactions by various observers, and may be explained as due to some kind of chemical action taking place between the solvent and the solute, and influencing the general relations of the solvent as predicted from its physical properties. T. H. P. Law of the Action of Invertase. By VICTOR HENRI (Zeit. physikal. Chent., 1901, 39, 194-216; Compt. mzd., 1901, 133, 891--894).-The velocity of inversion of sucrose by invertase is not represented by the equation dx/dt = k(a -%)leading tok = Z/t[log a/(a-x)], but the author shows that the reaction velocity may be expressed by dx/dt = k,( 1 + ./a)(. - x) or 2k, = Z/t[log(a + x)/(a - x)]. Experiments were also made in which, after various intervals of time, additional quantities of sucrose were added to the solution undergoing inversion by diastase, and it was found that time had no effect on the activity of diastase, the velocity depending only on the concentrations of a and x.The value of k, varies with the initial concentration, but the value ka, is not constant ; it increases with a a t low concentrations, attaining a maximum at from 0.1 N to 0.4 N solutions (Abstr., 1901, i, 438 ; ii, 647). L. M. J. Pseudocatalytic carrying of Oxygen. By CARL ENGLER and LOTH~R WOHLER ( Z e d . anorg. Clem., 1901, 29,1-21. Compare Abstr., 1897, ii, 403 ; 1899,,i, 189, 221 ; 1900, i, 399 ; 1901, i, 657).-Pseudo- catalysis (Wagner, Abstr., 1899, ii, 275), in which oxidation takes place, can be divided into three categories where the oxygen carrier is (1) a noble metal or its easily reducible oxide, (2) an oxide or salt of au element the valency of which varies, (3) an animal or plant oxidation- ferment.The results of Mond, Ramsay, and Shields (Abstr., 1895, ii, 492; 1898, ii, 599) on the occlusion of oxygen by platinum black have been confirmed and the following facts also observed. Platinum black turns potassium iodide starch solution blue; it is somewhat soluble in dilute hydrochloric acid, the weight of platinum in solution is less than the weight of platinum black dissolved, and if the difference be attributed to oxygen it is found that the ratio of platinum to oxygen agrees well with YtO ; the amount of oxide present in the platinum sponge depends on the state of division. It does not easily amalgamate,128 ABSTRACTS OF CHEMICAL PAPERS, and the amalgam formed becomes covered with a film of the black oxide; hydrogen peroxide does not reduce it in the cold, but on boil- ing, complete reduction takes place, and it is also reduced by alcohol, ether, and other organic substances; in absence OF air, it oxidises arsenious to arsenic acid, and the residue loses its spongy character and becomes granular.It is further shown that the properties of active platinum sponge closely resemble those of platinous oxide, in confirma- tion of the theory of de la Rive that in the catalysis by platinum black, the intermediate active agent is this oxide. However, platinum sponge free from oxide causes more active oxidation than does platinous oxide, and this is explained by the Engler-Wild theory (Abstr., 1897, ii, 402) of the intermediate formation of peroxide and secondary formation of oxide, which takes place more readily with the finely divided sponge than with the more compact platinous oxide.I n like manner, the authors attribute the solution of gold in potass- ium cyanide in presence of oxygen to the formation of gold peroxide, which dissolves as expressed by the equation Au20, + 4KCN = 2KAu(CN), + K,O,. Pseudocatalysis by means of oxides or salts of chromium, iron, cobalt, nickel, copper, mercury, and, in a less degree, by those of titanium, zirconium, cerium, thorium, tin, and molybdenum, and even by the non-metals phosphorus and carbon, is also explained by the intermediate formation OF peroxide. Catalysis in the plant and animal world is also due to formation of peroxides, and analogies are drawn bet ween the oxidation-ferments and platinum sponge.J. McC. By REGINALD B. BROWN and JOHN MCCRAE (J. Xoc. C?henz. Ind., 1901, 20, 1092-1093. Compare Abstr., 1901, i, 99; Trans,, 1896, 1334; J. Xoc. Chem. Id., 1901, 20, 226).-The authors conclude from their experiments that within wide limits of concentration a constant percentage of dye is taken up by wool, when the relative amounts of wool and water, the tempera- ture, and the duration of the experiment are constant. The authors favour the view that in certain cases the operation of dyeing consists simply in the formation of a solid solution, and to this solution 'Henry's law is strictly applicable, but at the same time they recognise that this does not hold good in general, for the non-reversibility of the process in most cases favours the view that a chemical or physical change takes place during the fixing, By GR~GOIRE WYROUBOFF (Bull.Xoc. China., 1'301, [iii], 25, 1016-1022).-A controversial paper, not suitable for abstraction. Sonie Stereochemical Views on the Question of the Unity of Matter. By PAUL HELLSTROM (Zeit. anorg. Chern., 1901, 29, 95--106).-The author believes that the elements have been formed from a primordial matter, the differences between them being due to the different polyhedric forms into which it has aggregated. H e explains valency as due t o attractions in particular directions in the aggregated mass, The periodicity of the properties of the elements leads to the conclusion that one series occurs in each of The Solution Theory of Dyeing.H. R. LE S. Colloids. T. 14. L. Origin of the Elements,GENERAL AND PHYSICAL CHEMISTRY. 129 the seven tiolohedral forms of the regular crystallographic system. The elements of the eighth series have a form with varying para- metral ratio. J. McC. By H. STAIGMULLER (Zeit. physikal. Chem., 1901, 39, 245-248).-Another variation of the classification of the elements for which the author claims that the elements fall into more natural groups, and that the non-metals become sepsrated from the metals. Third Report of the Committee [of the German Chemical Society] on Atomic Weights. By the Members of the Committee : HANS LANDOLT, WILHELM OSTWALD, and KARL SEUBERT (Rer., 1901,34, 4353-4384. Compare Abstr., 1899, ii, 86 ; 1900, ii, 533).-Further inquiry has been made by the Committee in order to discover the views of chemists on the question whether the basis of atomic weights shall be taken as H= 1 or O= 16.00.Of the total number of answers received, 106 were in favour of H = 1 and 78 in favour of 0 = 16.00. Since the last report, the Committee have recommended that the atomic weight of iron be changed from 56 to 55.9, and that of calcium _frc,m 40 so 40.1. By F. WILLY HINRICH- SEN (Zeit. physikal. Chem., 1901, 39, 304-310).-The assumption is made that atoms have an invariable affinity or saturation capacity, and reasons must be sought in order to explain why this does not reach its maxirnum.in certain cases. Temperature is one cause, as van’t Hoff (Ansichten ueber oyganische Chemie) has shown, and another cause is the electrochemical character of the components.Blomstrand (Chemie der Jetxtxeit) points out that when a strongly positive or negative ele- ment acts with its full positive or negative force, i t is always foundin its lowest degree of saturation ; thus, when the halogens form salts, that; is, act decidedly negatively, they are always univalent. Blom- strand further points out that the energy content of an atom is the greater, the fewer affinity units come into play. The author believes that all cases of unsaturated compounds are to be explained by assuming that the valency is constant, but part of the affinity, from one or both of the above causes, remains in abeyance. Baeyer’s tension theory, and Thiele’s theory of partial valency, do not agree with the behaviour of many organic compounds, and there is now no reason to believe that carbon may not occur with free valeacies, as in carbon monoxide (C:O), hydrocyanic acid (CtNH), iso- nitriles (C:NR), and fulminic acid (C:N*OH). The explosive nature of acetylene (:CH*CH:) is explained by the great content of energy of the bivalent carbon which i t contains, according to Blomstrand’s hypothesis. The 1 : 4 rule for the formation of additive compounds can also be explained by the assumption of free valencies. J. McC. i Simple Leoture Experiments to Demonstrate the Dissoci- ation, on Eeating, of the Chloride and other Salts of Ammonium. By DIOSCORIDE VITAL^ (L’Ovosi, 1901, 24, 332-334). -The dissociation of smmolaium chloride may be shown by heating‘it The Periodic System of the Elements. L. M. J. *K. ,J. P. 0. Theory of Unsaturated Compounds.130 ABSTRACTS OF CHEMICAL PAPERS. in presence of a small quantity of a mixture of potassium iodide and iodate ; the hydrogen chloride evolved acts on these two salts, forming hydriodic and iodic acids, which react to yield iodine, the latter then volatilising as a violet vapour. The ammonia also formed in this reac- tion may be detected, not only by its odour, but also by its action on turmeric paper and by the white fumes formed in presence of a rod moistened with hydrochloric acid. Also, in solution, iodine is obtained by heating ammonium chloride or sulphate in presence of potassium iodide and iodate. Instead of the iodine salts, a mixture of potassium bromide and bromate, or of chloride and chlorate, may be employed. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9028205117

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

129 Organic Chemistry. Law governing the Formation of Additive Products and their subsequent Decomposition. By ARTHUR MICHAEL [with T. H. MIGHILL] (Ber., 1901, 34, 4215--4226).-Comparative experi- ments on the elimination of bromine by means of zinc from the bromides of various unsaturated compounds shorn the general applicability of the law that, in a series of isomeric or homologous additive products, those which are formed the most readily are also those which are most readily decomposed. I n the case of the dibromides of the series ethylene to iso- butylene, the amount of bromine which zinc eliminates increases as the series is asoended. Experiments with the isomeric ethyl di bromo- succinates, ethyl dibromomethylsuccinates, and methyl up-dibromo- crotonates are also described, Of the two isomeric P-bromocinnamic acids, the one with the higher melting point is the more readily con- verted into phenylpropiolic acid.The methyl ester of the up-dibromocrotonic acid, which melts at 94', is a colourless liquid which boils at 94' under 11 mm. pressure; the methyl ester of the isomeric acid (m. p. 120') is a colourless liquid which boils :tt 102-104' under 14 mm. pressure. R. H. P. Fluorobromo-derivatives containing Two Atoms of Carbon. IV. By FREDERIC SWARTS (Bull. Acad. Roy. Belg., 1901,7, 383-414. Compare Abstr., 1898, i, 457 ; 1899, i, 254).-B~uorobromoetha~, CHF2*CH,Br, obtained in theoretical quantity by heating together, at loo', 2 mols. of antimony trifluoride and 3 mols. of tribromoethane, is a colourless, very volatile liquid with an agreeable ethereal odour; it has a sp.gr. 1.82443 a t 18*5*, and 1.83685 at 10.5'; %a 1.39300, nD 1.39400, and 'n, 1.4047 at 10.5'. It is only slightly soluble in water, and mixes in all proportions with organic solvents. When cooled in liquid air, it solidifies to a crystalline mass which melts at - 74.5". It is not acted on by oxidising agents. When heated at 180' with bromine and ferric bromide, it yields tetrabromoethane, and when reduced with zinc in sodium b ydroxide solution yields fluoroethylene. Elzcoroethylene, C,H,F,. is a colourless, odourless gas, which does not solidify when cooled in liquid air andis insoluble in water, but alcohol dissolves four times, and acetone 5.5 times its own volume of the gas at 20'. It burns in air with a green edged flame. It is readily absorbed by bro- mine, fluorodibromoethane being formed.FZuorodibromoethane, C1HFBr*CH2Br, boils at 1215', has a sp. gr. 2.26333 at 10*5', and ma 1.51235, n,, 1.51'759, and nH 1.53278 at 10.5'. I t crystallises at - 554 and melts at - 54'. Wlien ditluoro bromoethme is heated with potassium hydroxide dis- solved in ethyl alcohol, it yields difluorodiethyl ether and difluoro- ethylene. The yield of difluoroethylene in this case is 32 per cent, of the theoretical ; if methyl alcohol is employed instead of ethyl alcohol, then the yield is 26 per cent., whereag with propyl alcohol it is 40 pep VOL. LXXXII, i. 2130 ABSTRACTS OF CHEMICAL PAPERS. cent., and with amyl alcohol 61 per cent. I n all cases, the corre- sponding difluoroether is also produced, DiJEuoyoethylene, CF,: CH,, is a colourless, odourless gas of density 2.21, corresponding with a mol.wt. of 63.84, the calculated mol. wt. being 63.9. Alcohol or chloroform dissolves 14 times its own volume of the gas. It neither polymerises nor oxidises when exposed to the air, and when cooled in liquid air, i t solidifies to snow-like flakes. It readily absorbs bromine, a-dzj2uorodibromoethane being formed. a-Dzjhorodibrornoethane, CF2Br*CH,Br, is a colourless liquid, boils at 93') has a sp. gr. 2,4228 a t 12*2', na 1.44957, rzD 1.45249, (nH 1.46555 a t 12.2'; i t solidifies a t - 58" and melts a t 56.5". DZj2uorodiethyl ether, CHF,*CH,*O*C,H,, is a very volatile, colourless liquid with an ethereal odour, is somewhat soluble in water, and has a sp.gr. 1,039 a t 15". It is oxidised by nitric acid or chromic mixture. DiJluoroethyl methyl ether, CHF,*CH,*O*CH,, boils at 47" ; 100 vols. of water dissolve 5 vols. of this compound. On oxidation with chromic mixture, it yields difluoroacetic acid. Barium dzjfuwoacetate is very soluble in water, but almost insoluble in alcohol. It crystallises in star-like aggregates of slender needles. Dzjhoroethyl propgl ether boils at 89'. Since ditluoroethyl methyl ether on oxidation gives difluoroacetic acid, it follows that i t must contain the group CHF,*CH,-, which must also be present in the difluorodiethyl ether. Difluoroiodoethane, C,H,IF,, produced by heating difluoro bromo- ethane with calcium iodide in alcoholic solution, is a colouriless liquid, boils a t 89*5', has a sp.gr. 2.24328 at 12*2O, and ma 1.46455, rz, 1046807, and m 1.48467 at 12.2". When oxidised with nitric acid, it yields difluoroacetic acid. When tribromoethane is treated with a mixture of antimony tri- fluoride and bromine, both difluorobromoethane and fluorodibromo- ethane are produced. The fluorodibromoethane thus produced is in every way identical with that obtained by the action of bromine on fluoroethylene. Pluorobronaoethylene, CH2:CBrF, is obtained by the action of a mix- ture of potassium acetate and carbonate on fluorodibromoethane. It is a very volatile liquid boiling at 30-33', and readily polymerises and oxidises on exposure to air (compare fluorobromoethylene, CHBr:CH F, Bull. Acad. Roy. Belg., 1897, [iii], 33, 456). Action of Normal Propyl and Butyl Alcohols on their re- spective Sodium Derivatives ; Synthesis of Dipropyl and Dibutyl Alcohols, By MARCEL GUERBET (Compt.rend., 1901, 133, 1220-1222. Compare Abstr., 1899, i, 471, 472; 1901, i, 182, 307, 625).-When propyl alcohol is heated under pressure for 24 hours at 220-2304 sodium propionate, propyl propionate, and a hexylic alcohol are formed ; much hydrogen is produced during the operation. The hexylic alcohol is P-methylamyl alcohol (b. p. 148') being oxidised by chromic acid to P-methylvaleric acid (b. p. 193.5'). Under the same conditions, butyl alcohol yields corresponding pro- ducts ; the octylic alcohol (dibutyl alcohol}, C,HI7*OH, obtained is a H. R. LE S.ORGANIC CHEMISTRY. 131 colourless, oily liquid boiling at 181" under 758 mm.pressure, and has a sp. gr. 0.8483 at 0'. Preparation of Trichloroteyt. butyl Alcohol. By MARCEL GU~DRAS (Compt. rend., 1901, 133, loll).-If a mixture of equal volumes of acetone and chloroform is allowed to drop on potassium hydroxide heated at 30°, and the mixture is afterwards heated at 50' for an hour, tricldorotert.butyZ alcohol, CCI,. CMe,* OH, is formed, and can be isolated by distilling in steam, after removal of unaltered acetone and chloroform by heating a t a temperature below 70". It melts a t 80--81", boils a t 16'7O, has a characteristic camphoraceous odour, is almost insoluble in cold water, but soluble in most organic solvents, and is not affected by dilute acids or alkalis, It produces local anzesthesia and has anti- septic proper ties. K.J. P. 0. c. H. 33. Fermentation Amy1 Alcohol, By GUSTAVE BEMONT (Compt. rend., 1901, 133, 1222--1224).-A specimen of the amyl alcohol, obtained by repeated fractionation of commercial fuse1 oil, and repre- senting one-third of the quantity of the latter, boiled a t 131-131*5', has a sp. gr. 0.8065 a t 16" and [ a ] ? -0O55.5'. On oxidation with chromic acid, it yields an active valeric acid which boils a t 175' under 763 mm. pressure and has [.ID + 2O31.3'. The alcohol is probably a-methylbutyl alcohol, and the acid a-methylbutyric acid. I n the oxidation are also formed a valeraldehyde, which boils a t 92-93' under 761 mm. pressure and has [a], + 0°22*7', and an amyl valerate boiling a t 191-192" under 743 mm. pressure, and having [.ID 3'1 4.8'. I(. J. P. 0. Synthesis and Properties of I-Erythritol.By L ~ O N MAQUENNE (Ann. Chim. Phys., 1901, 24, [vii], 399-412).-A r&sumk of work already published (compare Abstr., 1900, i, 423, 472 ; 1901, i, 497). G. T. M. Eateriflcation of Phosphorous Acid by Glycerol and Glycol, B ~ P . C A R R ~ (Compt. rend., 1901,133,882-884).-A glycerophosphorous acid having the formula O:PH( OH)*O*CH,*CH(OH) *CH,*OH is obtained on warming glycerol with phosphorous acid ; the second hydroxyl group of the acid is not esterified even when the alcohol is in excess, The limits of esterification with molecular proportions, at 125' under the ordinary pressure, is reached in 20-30 hours, 60.6 per cent. of the acid being converted into ester ; prolonged heating lowers the percentage owing to the loss of glycerol by evaporation.The limit is reached more rapidly when the experiment is made a t 125" under 15 mm. pressure, the time required being 10 hours. Barium glyceg-ophosphite, Ba( C,H,O,P),, is amorphous and very soluble ; it is hydrolysed by boiling water and by cold solutions of the alkali hydroxides. The acid, O:PH(OH)*CH,*CH,*OH, results from the interaction of glycol and phosphorous acid ; it is monobasic, its deliquescent barium salt having the composition Ba(C,H,O,P),. GI. T. M. 1 2132 ABSTRACTS OF CHEMICAL PAPERS, New Volatile Beryllium Salt. By G. URBAIN and H. LACOMBE (Compt. rend., 1901, 133, 874-876).-The basic 6er@%zcm acetate, Be,O(OAc),, produced by dissolving the product of the action of dilute acetic acid on beryllium hydroxide in glacial acetic acid, separates from this solvent in needles or octahedral crystals insoluble in cold water and almost insoluble in alcohol or ether; it is decomposed by hot water.The salt crystallises best from chloroform, melts to a colourless liquid at 283-284', and boils without decomposition a t 330-331O under the ordinary pressure. The vapour may be superheated to 360' without undergoing any decomposition. The salt may even be heated at 150° in the presence of hydrochloric and glacial acetic acids without altera- tion. The vapour density of the compound determined by V. Meyer's method is additional evidence in favour of the bivalent character of beryllium. G. T. M. Action of higher Aliphatic Acids on Normal Alkali Car- bonates. By 3 . KLIMONT (J. p . Chem., 1901, [ii], 64, 493-495).-The higher fatty acids (stearic, oleic, arachic) which are insoluble in water react with aqueous sodium carbonate, giving sodium hydrogen carbonate and the sodium salt of the fatty acid. With lower acids, which are somewhat soluble (decoic, Stc.), the sodium hydrogen carbonate is also decomposed. K. J. P. 0. Action of Ethyl Sodiomalonate on Tribromides. By WLADIMIR N. IPATIEFF and SWIDERSKI (J. Euss. Phys. Chem. Soc., 1901, 33, 532-540).-By the action of bromine, dimethylethylcarbinol yields a mixture of two dibromo-compounds, CMe,Br*CHMeBr and CH2Br*CMeBr*CH2Me, which, when further brominated, give two isomeric tri bromoisopentanes of the constitution CMe,Br* CHBr*CH2Br and CH,Br*CMeBr*CHMeBr. On treating the mixed tribromo-deriv- atives (1 mol.) with three atomic proportions of sodium and ethyl malonate (3 mols.), the following compounds were obtained : (1) ethyl ethanetetracarboxylate ; (2) the ethyl ester of an unsaturated acid of the composition C,H,,O, and probably of the constitution CHMe:CMe*CH,-CH(CO,H), ; two fractions of the ethyl ester, boiling under 10 mm.pressure a t 115-120O and 120--124O, 'have respectively the sp. gr. 1.058 and 1,064 a t Oo/O'; (3) the ethyl ester of a n unsaturated homo-acid, CMeBr : CMe *C H;CH( ZO,H),, which, after crystaliisa t ion from benzene, melts a t 115-11'T0; (4) an ester isomeric with (3) and corre- sponding with an acid, CMe,:CBr*CH,*CH(C02H)2, melting at 157-158'. Both these bromo-acids form insoluble silver and calcium salts. T. €1. P. Isoprenic Acid.By WLADIMIR N. IPATIEFF (J. Russ. Phys. Chem, Soc., 1901, 33, 540-545).-The action of sodium ethoxide on dibromo- isoprene and ethyl malonate gives rise to an ethyl ester, C,,H,,O,, which in an impure condition boils a t 125-128' under 15 mm. pres- sure ; it is a transparent liquid having a faint odour and combines with bromine, and decolorises 1 per cent. permanganate solution ; it has a sp. gr. 1,0566 a t Oo[Oo and nD 1.45081, the molecular refraction calcurORGANIC CHEMISTRY. 133 lated from this number showing that the molecule contains one double linking. On hydrolysis, the ester yields isopropenyl~rimetl~ylenedicurb- oxylic m i d (isoprenic acid), CH,:CMe*CH< CH2 I which was ob- tained as an amorphous powder soluble in water or acetic acid; in freezing aqueous solution, the values 245, 233, and 314 were obtained for the molecular weight, so that the acid undergoes polymerisation ; the acid melts an4 decomposes a t about 115", decolorises permangannte solution, and combines with bromine and hydrogen bromide, giving com- pounds not readily purified.The salts of the acid are mostly insoluble i n water and amorphous; the culcium salt, C,H,04Ca,2H,0, is ob- tained as a white, amorphous precipitate. C(CO,H),' The composition of dibromoisoprene is probably Cystin. CH,:CMe*CHBr* CH,Br. T. H. P. By JULIUS MAUTHNER (Zeit. Biol., 1901,42,176-186).- Certain metallic compounds of cystin are described, particular atten- tion being directed to that with copper, which is crystalline and has the formula C,H,oO,N,S,Cu.Cystin also forms a crystalline com- pound with hydrogen chloride, C,H,204N,S,,2HCl. Compounds are also described of the formulze C,H804N2S2Hg2,HgCI, ; 2CGH,o0,N,S,Hg,HgC12, 7H2O ; 2C,H,04N,s,Hg,,Hg(No,), ; Baumann (Zeit. physiol. Chem., 8, 300) showed that cystin may be reduced to cystein by tin and hydrochloric acid and subsequent re- moval of the tin by hydrogen sulphide. It is now shown t h a t hydrogen sulphide alone will bring about the same reduction. W. D. H. Action of Fuming Sulphuric Acid on Acetaldehyde, Propalde- hyde, and Acetone, By MARCEL DEL~PINE (Compt. rend., 1901, 133, 876-S78).-The vapour of acetaldehyde, when passed into fuming sulphuric acid (50 per cent. SO,), yields acetaldehyde-&3- disulphonic acid, CHO*CH($O,H),, and methanedisulphonic acid.The former acid yields, mi th aniline, ptoluidine and the naphthylamines, compounds of the type CH(S03H),*CH:NR,2H,0. Propaldehyde, under these conditions, gives rise to propaldehyde- PP-disulphonic acid, CHO*Cl\le(SO,H),, the potassium salt of which, when heated with barium hydroxide solution, yields the corresponding salts of formic and ethylidenedisulphonic acids. Acetone also undergoes sulphonation, yielding cccetone-ayy-trisulphonk acid, S03H*CH,*CO*CH(S03H)2, and the products of its hydrolysis, namely, disulphoacetic and methanedisulphonic acids. These acids were identified as barium salts. Barium acetone-ayy-triadphonate, Ba3[C,H,0(S0,),]2,2H,0, when dried a t lOS", is an amorphous sub- stance resembling alumina or silica ; it yields the corresponding salts of disulphoacetic and methanedisulphonic acids when boiled with barium hydroxide solution.G. T. M. Electrolytic Production of Haloid Derivatives of Acetone. By A. RICHARD (Compt. rend., 1901, 133, 878-880).-Monochloro- acetone is produced by electrolysing a mixture of hydrochloric acid and acetone. The best yield is obtained when the acetone is in excess134 ABSTRACTS OF CHEMICAL PAPERS, and the electrolysis conducted in a well-cooled electrolytic cell fitted with an anode having a large surface. The hydrogen evolved at the cathode has no action on the product. Monobromoacetone is conveniently prepared by electrolysing a mix- ture of hydrobromic acid and acetone at 35-40', but in this case the hydrogen must be evolved in a separate cathode cell, owing to its re- ducing action on the product.G T.M. Action of Nitric Acid on Aliphatic Compounds containing the Group CH(0H). I. Action of Nitric Acid on Secondary Alcohols. 11. Action of Nitric Acid on Ketonic Alcohols, R*CO*CH(OH)*R. By GIACOMO PONZIO (Atti R. Accad. Xci. Torino, 1900-1901, 36, 721-'733).-The first part of this paper has been already abstracted (see Abstr., 1901, i, 477). The action of nitric acid of sp. gr. 1.37 on ketonic alcohols, R*CO*CHR*OH (a-ketoles or aliphatic benzoins), affords a convenient means of preparing symmetrical a-diketones of the aliphatic series. The following compounds have been obtained in this way. Dipropionyl, prepared from propioin, [CH,Me*CO*CH(OH)*CH,Me], was distilled in a current of steam and converted into its dioxinze, C6vI,0,N2 ; this crystallises from benzene in shining, white needles whlch melt and sublime a t 185O, and are soluble in water, alcohol, chloroform, ether, or light petroleum.BibutyryE, CH,Et*CO*CO-CH,Et, obtained together with dinitro- propane by the oxidation of butyroin, is a yellow oil. The dioxime, C8Hl6O2N2, separates from benzene in slender, shining needles melting a t 175', and dissolving in alcohol, ether, or chloroform. Diisobutyryl, CHMe,*CO*CO*CHMe,, obtained from isobutyroin, gives a dioxime, C,H,,O,N,., which crystallises from benzene in white needles melting and subliming a t 163-164' and dissolving in alcohol or ether. DiisouaZei*yZ, CHMe,*CH,*CO*CO*CH,*CHMe,, prepared from iso- valeroin, yields a dioxime, C10HP002N2, separating from benzene in shining, white needles which melt and sublime a t 195' ; it is soluble in alcohol, ether, or chloroform.T. H. P. Synthetical Experiments with Tetra-acetylchlorodextrose and Tetra-acetylchlorogalactose. By ZDENKO H. SKRAUP and R. KREMANN (Moncctsh., 1901, 22, 1037-1048).-Investigation of the action of phenylhydrazine on tetra-acetylchlorodextrose has resulted in the isolation of glucosazone only, in addition to acetylphenylhydrazine and phenylhydrazine hydrochloride. Attempts to synthesise a disaccharide by the action of tetra-acetyl- chlorodextrose on the sodium and lead derivatives of dextrose were unsuccessful. A. small amount of P-penta-acetyldextrose (m. p. 11 2') was formed from tetra-acetylchlorodextrose on boiling it with molecular silver in toluene.When heated with metallic sodium and finely divided silver nitrate in ether, tetra-acetylchlorodextrose was converted into tetra-acetylnitrodextrose which melted a t 92'. This, when heated with sodium acetate and glacial acetic acid, yielded a-penta-acetyl- dextrose (m. p. 132'). On recrystallisation from alcohol, the almostORGANIC CHEMISTRY, 135 inactive tetra-acetylnitrodextrose ([ .ID + 1.536') became active ([a], + 143.65' a t 25') and melted at 145'. This is probably the tetra-acetylnitrodextrose previously described by Colley and Konigs (m. p. 151'; [.ID + 149.16' at 18"). When boiled with metallic sodium and silver nitrate, in ether, tetra- acetylchlorogalactose exchanges the chlorine atom for hydroxyl, yielding tetra-acetylgalactose. This melts a t 145', and has [a],, + 137.17O a t 25'.When boiled with sodium acetate and acetic anhydride, it is converted into penta-acetylgalactose (m. p. 142'). By hydrolysis of the tetra-acetyl- galactose and subsequent treatment with phenylhydrazine, glucosazone was obtained. G. Y. Hepta-acetylmaltose N i t r a t e (Acetonitromalt om) and Hepta- acetyl-@-methylmaltoside. By WILHELM KOENIGS and EDUARD KNORR (Ber., 1901, 34, 4343-4348. Compare Abstr., 1901, i, 369). --Hepta-ucetylmaltose nitrate, C,,H,,O,(OAC)~*NO,, is prepared by treating octoacetylmal tose with an ice-cold mixture of chloroform and fuming nitric acid; i t crystallises in large prisms melting a t 93-95' and has [.ID + 149'18' a t 19'. On boiling the nitrate with methyl alcohol in the presence of barium carbonate and a few drops of pyr- idine, hepta-acetylmethylmaltoside is formed ; this melts a t 128-129', amd has [a], + 60O46' at 20' (compare Fischer and Armstrong, Abstr., 1901, i, 671).On hydrolysis with barium hydroxide, P-methyl- maltoside is obtained, forming colourless needles melting at 93--95O and decomposing a t 100' ; fermentation converted it into @-methyl- glucoside. Pure octoa.cetylsucrose can be quantitatively hydrolgsed when it is treated with a cold solution of sodium hydroxide in aqueous methyl alcohol for a few hours, K. J. P. 0. Cellobiose. By ZDENKO H. SERAUP and J. Koma (Monatsh., 1901, 22, 1011-1036. See Abstr., 1901, i, 370)-The name cellobiose is now used for the substance previously termed cellose. Cellobiose, on hydrolysis by dilute sulphuric acid, is shown to yield dextrose only.Cellobiose forms a phenylhydraxone which decomposes at 90' and an osaxone which melts at 198". Hepta-ucetylchlorocellobiose, C,H,,O,,CI, is formed by the action of hydrogen chloride on the solution ot heptacetylcellobiose in acetic anhydride. Hepta-acetylmetl~ylcellobioside is formed by shaking with silver carbonate hepta-acetylchlorocellobiose in methyl alcohol solution ; it crystallises from alcohol in white needles melting at 173', and on hydrolysis yields a substance which closely resembles cellobiose but may be methyl- cellobioside. Attempts to obtain cellobiose from sprouting beans were unsuccess- ful. G. Y. Acetylation of Soluble Starch. By FRITZ PREGL (illonatsh., 1901, 22, 1049--1066).-Soluble starch prepared by Znlkowsky's method yielded, on acetylation by acetic anhydride in presence of a small quantity of sulphuric acid in the cold, an amorphous triacetyl It forms small needles which melt a t 178".136 ABSTRACTS OF CITEMICAL PAPERS.derivative, C,H70,Ac,, which did not reduce copper or bismuth salts, and was not coloured by iodine. It sintered Cat 260°, decomposed a t 275', and had [a],, 163.6'. Molecular weight determinations showed the molecular weight to be from eight to nine times that corresponding with the empirical formula. The product obtained on hydrolysis of the acetyl derivative was identical with the soluble starch and had [ a ] , +191*73O at 20'. Soluble starch had rain +191*27' at 20'. On analysis, both gave the formula C,H1,O,L (&&pare Syniews ki, Abstr., 1898, i, 61).Acetylation with an increased amount of sulphuric acid yielded a product having the empirical formula C,H70,Ac, ; the molecular weight determinations showed, however, that this formula must be tripled. This acetyl compound is soluble in alcohol, melts a t 150-155', has [ alD 149*03', and reduces alkaline copper solutions. Hydrolysis yielded a dextrin which gave a red coloration with iodine, had [a],, + 187.0°, and could not be identified with any dextrin previously described, G. Y. Humic Substances. By FAUSTO SESTINI (L'O~osi, 1901, 24, 289--299).-The humic substances which have been previously de- scribed by various authors must not be considered as so many different modifications of one individual substance, since facts are riot lacking which indicate marked differences in properties between humic sub- stances from divers sources.Artificial humic matter prepared from non-nitrogenous compounds contains no trace of nitrogen, whilst that obtained from the humus of the soil retains tenaciously a certain quantity of nitrogenous material. The author applies Liebermann's theory of colour shade (Abstr., 1901, ii, 368) to the change of colour from black to red and afterwards t o yellow when humic substances are oxidised and nitrated; also to the case of sacculmic acid which changes from brown to yellow when a portion of its hydroxyl is replaced by bromine, whilst the black colour returns if the hydroxyl is restored to the compound. The influence of the methoxy-group on the colour of organic compounds, which was pointed out by Liebermann (Zoc.cit.), is probably exerted in the case of humic substances, the author having often detected an odour of chloroform, bromoform, or methyl esters on treating such substances with chlorine or bromine, By oxidation and nitration with concentrated nitric acid (sp. gr. 1.4), the molecule of humic substances is quickly destroyed with the forma- tion of a mixture of products among which are nitration products belonging to the aromatic series; the only aromatic group which has been identified is the benzene nucleus. Quinone readily undergoes change into a black mass, which is also formed a t the ordinary tempera- ture from an aqueous solution of quinone kept in the dark and in an atmosphere of carbon dioxide ; it is probable that an additive product of quinone with water is first formed, and that this is gradually decomposed between 15' and 95' into quinol and black matter by the action of the liberated oxygen.The author confirms the views previously put forward by him that ulmin and sacculmin cannot be regarded as merely mixtures of the potassium salts of humic acids. As regardsORGANIC CHEMISTRY. 137 the chemical functions of humic substances, it is probable that beside anhydride or ether-linkings they contain ketonic, hydroxyl, and alkyl groups, partly arranged in open, and partly in closed, chains. T. H. P. Birotation of Chitosamine (Glucosamine). By ERNST EDW. SUNDVIK (Zeit. physiol. Chem., 1901, 34, 157).-At a low temperature, a solution of glucosamine hydrochloride shows a rotation of 24*5O.After heating for a n hour and then cooling to the same temperature, the rotation is only 18'. By ERNST SCHULZE and ERNST WINTERSTEIN (Zeit. physiol. C?Lem., 1901, 33, 574-578. Compare Kossel and Kutscher, Abstr., 1901, i, 107). -A solution of pure phosphotungstic acid does not precipitate glycine, leucine, aminovaleric acid, or tyrosine from 5 per cent. solutions. Phenylaniline is, however, partially or wholly precipitated. It is probable that in the presence of other substances the amino-acids may be precipitated. The precipitates obtained in the investiga- tion on histone bases (this vol., i, 193) gave negative results when tested for amino-acids. Action of Dilute Mineral Acids on Ethyl Aminodimethyl Acrylate. By LOUIS BOUVEAULT and A.WAHL (Bull. SOC. Chim., 1901, [iii], 25, 1031--1040).-When heated with dilute mineral acids, ethyl aminodimethylacrylate, CMe,:C(NH,)*CO,Et, is converted into ethyl dimethylpywvate, CHMe,*CO*CO,Et, which forms a mobile, colourless, ethereal liquid and boils a t 64-69" under 35 mm. or a t 60' under 10 mm. pressure. CHMe,*C(CO,Et) :N*NH-CO*NH,, separates in needles from a mixture of ether and light petroleum and melts a t 95-96'. The oxinze, CHMe,*C(CO,Et):NOH, crystallises in needles from a mixture of ether and light petroleum and melts a t 57'. DimethyZpyruuic mid, CHMe,*CO*CO,H, distils at 65-67' under 10 mm. pressure, forms colourless leaflets, and melts at 31'; its oxime forms white crystals and melts and decomposes at 163-165'; the phenylhydraxone separates from aqueous methyl alcohol in yellow needles often several centimetres long, and melts at 156-157' with- out decomposition.The acid is reduced by sodium amalgam and alcohol to a-hydroxyisovaleric acid ; by the action of ammonia on the ester, dimethylpyruvamide (Moritz, Trans., 1880, 35, 14) is produced. Dimethylpyruvic acid has been prepared in an impure state by Moritz (Zoc. cit.), by Brunner (Abstr., 1895, i, 335), who describes a silver salt and a diphenylhydrazone melting a t 129', and by Kohn (Abstr., 1899, i, 328), who describes an oxime melting a t 202' and a phenyl- hydrazone melting at 137', but the products obtained differ substantially from those here described. Thiocyanogen, the so-called $-Thiocyanogen, and the Yellow Colouring M a t t e r obtained from Thiocyanates.By ALWIN GOLDBERG (J. p. Chem., 1901, [ii], 64, 439-470. Compare Abstr., 1901, i, 516, 677).---Analyses of commercial canarin show that it has W. D. H. Action of Monoamino-acids on Phosphotungstic Acid. J. J. S. The semicarbaxorte, T. M. L.138 ABSTRACTS OF CHEMICAL PAPERS. the formula C,H,0N,S7 (Zoc. cit.). The decomposition of canarin by water, alkalis, concentrated acids, and heat is studied, Metallic compounds with sodium, potassium, copper, zinc, silver, and magnesium are described. The yellow substance which is formed as a bye-product in the preparation of the dye canarin is contained in the mother liquors, from which the sodium salt of canarin has separated, and has the formula C3H,0N,S2 (2). The relation of the yellow substance to canarin is discussed, and constitutional formula? are suggested for both substances. K.J. P. 0. New Methods for the Preparation of Dithiocyano- chromium Salts. By PAUL PFEIFFER (Ber., 1901,34, 4303-4307. Compare Abstr., 1 9 00, i, 6 88) .-Dithiocyanodiethylenediamine- chromium thiocyanate (loc. cit.) may be obtained when potassium chromothiocyanate,K,CrS,C,N,,is heatedwith anhydrous ethylenediamine for three hours on the water-bath. The yield is small as part under- goes decomposition during purification by crystallisation from water. When this salt is heated with ethylenediamine, it is partially trans- formed into the luteo-salt, Cr(C,H,N,),(SCN),, as also is potassium chromothiocyanate. J. J. S. Chromammonium Compounds, 11. By PAUL PFEIFFER (Zeit. anorg. Chem., 1901, 29, 107-137.Compare Abstr., 1900, i, 559; 1901, ii, 659).-Dithiocyunodiethylenediami.nechromiu~ salts. Dithio- cyanodiethylenediaminechromium thiocyanate, [ Cr( C2H8N2> ,(SCN) ,]SCN, xH20, was obtained in prismatic needles from the salt cr(C,H,N,),]CI, by first preparing the luteothiocyanate ~~r~C,Hs~2)Jl(scN)3,H2~ ; then heating this a t 130') when it loses ethylenediamine and mater, and finally extracting with water and crystallising. The salt is easily soluble i n pyridine and in sulphuric acid, but is decomposed by heating with water. The chloride, [Cr(C,H,N,),(SCN),]Cl,H,O, is obtained in orange- yellow needles by treating the thiocyanate with concentrated hydro- chloric acid. By treatment with hydrobromic acid, nitric acid, and sulphuric acid, the bornide, with $H,O, the nitrate, with lH,O, and the hydrogen sulphute, with I&H,O, have been obtained, besides an acid chloride the composition of which appears to be variable.In the preparation of the luteochloride some rhodoso salt is also formed and is most easily isolated as ethylenediaminerhodosochromiam bromide, which is obtained in transparent, red crystals. It is soluble in water and with potassium thiocyanate gives the thiocyanate. The molecular weights of the luteoethylenediaminechromium salts, and the thiocyano-compounds described were determined by the cryoscopic method. J. McC. Formation of Carbamide from Nitrogenous Substancee. BY JOHANN PLOT (Chem. Centr., 1901, ii, 1335-1336 ; from Oesterr. Chern. Zeit., 4, 485-487. Compare Jolles, Abstr., 1900, ii, 636; 1901, i, 30, 262, 583; this vol., i, 86).-In opposition to Jolles, the Ethy1enediaminerhodosochromiu;m salts.[ Cr5!(C2H8N2),0 OH( H2°)21 Br3,ORGANIC CHEMISTRY. 139 author considers that in the oxidation of purine compounds it is not the group CO*NH, existing in these compounds which yields carbamide, but rather that the formation of carbamide results from the union of the decomposition products, ammonia and carbon dioxide, in presence of nascent carbonic acid (H,CO,). By LUIGI FRANCESCONI and A. PARROZZANI (Gaazetta, 1901, 31, ii, 334--347).-The action of hydroxylamine on potassium cyanate yields, in addition to the hydroxycarbamide described by Dresler and Stein (Annalen, 1869, E. W. W. Isomerism in the Hydroxyureas. 150, 242), an isomeric compound to which the authors give the name This com- isohydroxycarbamide and the constitution OH* 8 *NH2 WOH pound and hydroxycarbamide (which is probably first produced in its tautomeric form having the structure OH.N and then passes into the compound having the ordinary formula, NH,*CO*NH*OH), are supposed to owe their formation to the fact that cyanic acid takes part in the reaction with hydroxylamine in its two tautomeric forms.This explanation is borne out by the observation that in the condensation of cyanic acid or of esters of isocyanic acid with phenylhydroxylamine, no stereoisomerides are obtained, whilst in the action of esters of isocyanic acid on hydroxylamine, derivatives of isohydroxycarbamide seem to be produced although they have not as yet been isolated.is$3ydroxycarbarnidp,, CH,O,N,, crystallises from ether in iridescent plates melting at 70-72’ and completely decomposing into water, carbon dioxide, ammonia, and nitrogen, and is readily soluble in water, from which it is deposited unaltered; it is readily soluble in alcohol, moderately so in ether, and reduces Fehling’s solution in the cold. With ferric chloride, it gives a transitory red coloration quite different from the blue colour obtained with hydroxycarbamide, into which it is transformed on heating in alcoholic solution. By boiling water, it is decomposed, with evolution of ammonia, into hydroxycarbamide and a substance giving a cherry-red coloration with ferric chloride. It has the normal molecular weight in freezing aqueous solution. Its hydro- chloride separates in large, rectangular prisms which reduce Fehling’s solution in the cold, and give a transitory rose-red coloration with ferric chloride; it is stable in a vacuum at the ordinary temperature.The diacetyl derivative, C,H,O,N,, crystallises from ether in mam- millary masses, which melt at 105-106°, dissolve readily in alcohol, and give no reaction eitherwith ferric chloride orwithFehling’s solution ; it has the normal molecular weight in freezing water, and when its aqueous solution is evaporated to dryness in a vacuum, a viscous residue remains which colours ferric chloride an intense red. Potassium oxyfdminate, CO,NK, obtained by the action of potassium hydroxide on isohydroxycarbamide in absolute alcoholic solution, crystallises in needles which, with ferric chloride, give an intense blood- red coloration quickly changing to yellow ; it reduces Fehling’s solu- tion on heating, and its aqueous solution evolves carbon dioxide on addition of hydrochloric acid ; with silver nitrate, it gives a white, and with mercuric chloride a yellow, precipitate, both of which rapidly 0H.E *NH2140 ABSTRACTS OF CHEMICAL PAPERS, blacken.The electrical conductivity was determined, p varying from 141.7 for a dilution V=32 to 159.9 for P=1024. Met~,yl~~ydi.oxycarbamide, OH*NH*CO*NHMe, prepared from methyl- carbimide and hydroxylamine, crystallises from ethyl acetate in rhom- boidal plates melting and decomposing a t 127' and is very soluble in water, less so in methyl and ethyl alcohols, and slightly in ether ; it gives the characteristic bluish-violet coloration with ferric chloride and reduces Fehling's solution.No other compound could be isolated from the products of the reaction yielding methylhydroxpcarbamide, but after the separation of the latter a viscous substance remained which, with ferric chloride, gave a rose-red coloration. Eth ylhydi*oxyca~barnide, OH*NH* CO NHEt, melts and decomposes at 129", and is soluble in water and in methyl or ethyl alcohol. Phen yZhyd?*oxycur bamide, OH*NPh CO NH,, prepared by the action of hydrochloric acid on a mixture of phenglhydroxylaxnine and potassium cyanate, melts a t 95', is soluble in nearly all solvents, and gives with ferric chloride a dark bluish-violet coloration. Its hydrochloride is a white, cryst,alline, very deliquescent compound melting and decomposing at 90'.Phenylmethylhy~rozycarbff~~de, OH*NHPh*CO*NHMe, prepared from methyl carbimide and phenylhydroxylamine, crystallises from benzene in marnmillary aggregates of needles melting at 121'. Its hydrochloride separates in unstable acicular crystals which lose hydro- gen chloride a t 100'. Phenylet~~yMydroxyccrbami~e, OH*NHPh*CO*NHEt, crystallises from a mixture of benzene and ether in mammillary groups of needles melting at 93'. Its hydrochloride is unstable, and crystallises with difficulty. The authors give details of improvements on Erdmann's method for preparing potassium cyanate (Abstr., 1894, i, 2). T. H. P. New Oxidation Product of Uric Acid. By MAX SCROLTZ (Bev., 1901, 34, 4130-4132).-~etracccrbirnide, O C < ~ ~ , ~ ~ .~ ~ > C O , is NH*CO*NM produced by oxidising sodium urate, dissolved in water, with a 3 per cent. solution of hydrogen peroxide, the reaction being accelerated by gently warming; the yield of this compound is only about 10 per cent. of the uric acid taken. The new product has no definite melting point but when heated evolves a pungent vapour which reddens lacmoid paper ; it is insoluble in cold water and the ordinary organic solvents, but dissolves in hob water and sodium hydroxide solution. The sodium salt, C,H,O,N,Na, is very soluble in water but insoluble in alcohol. The bccrium salt, C4Ba204N4, is obtained as a crystalline precipiOate by mixing hot solutions of tetracarbimide and barium hydroxide. The ccclcium, silver, lead, and copper salts are insoluble, the first two being amorphous whilst the others are crystalline. G.T. M. Chloroimides. By JOSEPH TSCHERNIAC [with A. BRAUN] (Ber., 1901, 34, 4209--4214).--The chloroimides of phthalic anci succinic acids, when boiled with water, yield the imides and the acids together withORGANIC CHEMISTRY. 141 nitrogen and chlorine, but no hypochlorous acid ; neither is hypochlorous acid formed by the action of cold water on the chloroimides. The oxidising and bleaching properties of an aqueous solution of succinochloroimide are therefore due to the chlorine liberated. By LOUIS HENRY (Bull. Acad. Roy. BeZg., 1901, 7, 3 6 7-3 72. Compare Abst r., 1 S 8 6, 78 6, S 60).-AdiponitriZe (aa'-di- cyanobutane), C,H8(CN),, obtained by the action of potassium cyanide on tetramethylene dibromide or di-iodide, is a thick, colourless, odourless liquid having a bitter taste ; it boils a t 295' under 760 mm.pressure, has a sp. gr. 0.951 at 19'/19', and nD 1.4397; the molecular refraction is 29.85, the calculated value being 29.70. When strongly cooled, it solidifies to a mass of long, needle-shaped crystals which melt a t 0' to 1'. It readily combines with hydrogen bromide t o form a white, cryatalline mass, and on hydrolysis yields adipic acid. A review of the melting points of the dinitriles of the acids of the succinic series shows that those nitriles with an uneven number of carbon atoms melt at a lower temperature than those with an even number. R. H. P Adiponitrile. H. R. LE S. Hydraeide and Aeide [Azoimide] of Propionic and iso- Valerie Acids.By HERMANN HILLE (J. pr. Chena., 1901, [ii], 64, 40 1-41 S).-PropionyZhydraxide, CH,Me*CO *N,H,, prepared by boil- ing hydrazine hydrate with ethyl propionate and fractionating the product under reduced pressure, is an extremely hygroscopic solid melting at 40' and boiling a t 130' under 16 mm. pressure ; it reduces an ammoniacal solution of silver, and Fehling's solution ; t'he hydro- chloride forms a white, crystalline solid, melting and decomposing a t 15 0'. Propionylbenzylidenehydrazide, C H,Me* CO N,H :CHYh, pre- pared by the action of benzaldehyde on the hydrazide, crystallises in plates melting a t 1 15'. Propionyl-o-hydroxybenxylidenehydracxide, CH,Me*CO *N,H:CH* C,H,*OH, crystallises in prisms melting at 284' ; popion yLP-propylidenelqdrazide, CH,Me * CO *N,H: CMe,, forms prisms melting at 101'.s-Dipropionylhydracxide, N,H,(CO*CH,Me),, prepared by long boiling of propionic anhydride and hydrazine hydrate, or by heating propionylhydrazide and propionic anhydride under pressure at 120°, crystallises in plates melting a t 136' and boiling a t 215-217' under 25 mm. pressure. Propionykaxoimide (propionylazide), CH,Me*CO ON, prepared from propionylhydrazide hydrochloride and sodium nitrite, is an oil of dis- agreeable and irritating odour, readily volatile in ether vapour ; with absolute alcohol, it yields ethylurethane ; and with 50 per cent. alcohol, diethylcarbamide (m. p. 108'); from the latter, by heating with concentrated hydrochloric acid, ethylamine hydrochloride is obtained (m. p. 109').is0 Valerylhydraxide, CHMe,*CH,*CO*N,H,, prepared from ethyl isoval- erate and hydrazine hydrate, crystallises in hygroscopic scales or needles melting a t 68' and boils at 133' under 15 mm. pressure ; the hydro- chloride is crystalline, and melts and decomposes at 174' ; isovaZe?*yZ- berzxylidenehydracxide CHMe,*UH,*CO*N,H:CHPh, crystallises in small plates melting at 95'. is0 ValeryLo-h?jdroxybenxyZidenehydraxids crys- tallises in needles melting at 1 12'. is0 V~lery Z - P - ~ r o ~ y l i d e ~ e ~ ~ ~ r a ~142 ABSTRACTS OF CHEMICAL PAPERS, CHMe,*CH,*CO*N,H:CMe,, crystallises in small plates melting at 67'. s-Diualerylhydraxide, N,H,(CO*CH,- CHMe,),,. is prepared by treat- ing the monohydrazide in alcoholic solution with iodine and crystal- lises in long, prismatic plates melting a t 182'.is0 Edeqilaxoim~de, CHMe,*CH,*CO*N,, prepared by the action of sodium nitrite on valerylhydrazide hydrochloride, is an unstable, colourless solid which, on boiling with absolute alcohol, yields isobutyl- urethane (b. p. 99" under 19 mm. pressure), and with 50 per cent. alcohol, s-diisobutylcarbamide (m. p. 128'). H. J. P. 0. Hydrazide and Azide [Azoimide] of Palmitic Acid. By F. H. DELLSCHAFT ( J . p. Chenz., 1901, [ii], 64, 419--438).--PalmityZ- hydraxide, C15H3,C0 *N2-H5, prepared by adding ethyl palmitate to hydrazine hydrate, crystallises in needles melting at 11 1" ; the hydro- chloride forms small needles melting at 1 38-1 43'. I'almitylbenxyF idenehydraxide, Ci5H3,*CO*N2H:CHPh, prepared from the hydrazide and benzaldehyde, crystallises in microscopic needles melting at 78".Palmityl o-hydroxybenxylidenehydraxide is a crystalline solid melting a t 1 U 4 O , and the compound with ethyl acetoacetate, C,,H,,* CO *N,H:CMe*CH,* CO,Et, prepared from the hydrazide and ethyl acetoacetate, crystallises in small, white needles, which become soft and yellow at 79' and finally melt at 122'. Palmityl-/3-propylidenehy&axide, Ci5H3Ib CO *N,H:CMe,, prepared from the hydrazide and acetone, forms microscopic, crystal- line needles which melt a t 71'. C,,H,,* CO *N,H,Ac, prepared by hoiling the hydrazide with acetic anhydride, crystallises in small needles melting a t 129'. prepared by warming the hydrazide with benzoyl chloride, crystallises in microscopic needles which soften a t lOOOand melt at 108'.Palmityl- hydrindylhydraxide, C15H31* CO *N,H:CH* C,H,, prepared from hydrind- aldehyde and the hydrazide, crystallises in white needles melting a t 86'. s-Dipulmitylhydvazide, N,H,(CO*C,,H,,),, prepared by the action of iodine on an alcoholic solution of the hydrazide, crystallises in small, insoluble needles melting at 147". Pcclmitylaxoimide, C15H31. CO *N3, pFepared by the action of nitrous acid (nitrous fumes) on the hydrazide hydrochloride, forms crystals melting a t 49' and decomposing at 60'. With absolute alcohol, penta- decylethylurethane (m. p. 51') is formed ; with boiling water, s-di- pentadecylcarbamide (m. p. 110') ; with aniline, palmitylanilide (m. p. 87 9'), and with ammonia, pnlmitylamide. Pentadecylamine is obtained when the urethane is boiled with concentrated hydrochloric acid ; the amine yields insoluble compounds with mercuric and cadmium chlorides.K. J. P. 0. Acetylpalmitylhydraxide, Benzoy~almitylhydrax~~, C15H,,* CO*N,H,Br, Mixed Organo-magnesium Compounds and their Application to the Synthesis of Acids, Alcohols, and Hydrocarbons. By VICTOR GRIGNARD (Ann. China. Phys., 1901, 24, [vii], 433-490).--8ORGANIC CHEMISTRY. 143 r2sumi of work already published (compare Abstr., 1900, i, 382 ; 1901, i, 250, 316, 393, 679). C. T. M. By NICOLAI D. ZELINSKY and N. LEPESCHKIR (J. Buss. Phys. Chm. Xoc., 1901, 33, 549-565).-1t has been previously shown (J. Russ. Phys. Chem. Soc., 1899, 31, 407) by the authors that from isolaurolene a hydrocarbon, C8HI6, can be obtained which, from its physical properties, must be a hexamethylene derivative.This compound, to which the name dihydro- isolaurolene is given, the authors have now prepared by the following four methods : (1) By the action of concentrated hydriodic acid on iso- laurolene at 200'. (2) By the reduction of the liquid isolaurolene hydr- iodide (see below) by means of hydrogen in presence of a zinc-palladium couple (see Abstr., 1899, i, 181). (3) By the action of concentrated sulphuric acid on isolaurolene. (4) By the reduction of laurolene hydriodide by means of hydrogen in presence of a zinc-palladium couple. As obtained by these different methods, dihydroisolaurolene has slightly varying properties, due probably to small quantities of impurities difficult to remove. The product yielded by method( 1) is a pleasant smelling liquid boiling at 114O (corr.) and having the sp.gr. 0.7686 at 17'/43, O ~ J , 1.4223 at 17", and the molecular refraction (Lorentz and Lorenz' formula) 37.05, the number calculated from the structural formula given below being 36.82. The authors conclude that dihydroisolaurolene is a dimethylhexamethylene, and as the 0-, m-, and p-dimethylhexa- methylenes have been already prepared and characterised, it must be 1 : 1-dimethylhexamethylene, CH,< CH2'CH2>CMe2. CH2*CH, To isolaurolene the constitution Dimethylhexamethylene from Camphoric Acid. QMe2*yH*QH2 CH2-CH*CH, is given and to laurolene, CMe,*CH CH2<Cn,&>cJ32> which would explain theready conversionof its hydriodideinto dimethyl- hexamethylene by reduction ; the fact that the carbon-atom rings in laurolene and in its hydriodide are identical is shown by the action of dimethylaniline on the latter compound, by which means laurolene is reformed.It is probable that camphoric acid, which readily gives up carbon dioxide with the formation of laurolene, also contains a six carbon atom ring. When isolaurolene or its hydrobromide is heated with concentrated hydrobromic acid in a sealed tube, a colourless, liquid, isomeric hydro- bromide is obtained which boils a t 70-71" under 15 mm. pressure, and slowly decomposes on keeping. The liquid hydriodide obtained in a similar manner is faintly coloured, and boils at 75-80' under 15-17 mm. pressure, On heating isolaurolene hydriodide with diethylaniline, isolaurolene is obtained.The action of concentrated sulphuric acid on isolaurolene yields dihydroisolaurolene and a mobile liquid having the empirical com- position C8HlS, and boiling at 259-260' under the ordinary pressure. The laurolene obtained by the distillation of camphoric acid is prob- ably not an individual compound but a mixture of isomerides. Laur- olene as thus prepared was found to diminish in specific rotation ([a]=)144 ABSTRACTS OF CHEMICAL PAPERS . from 22.9' to 16.2' on treatment with permanganate. whilst the sp . gr . and refractive index also show slight changes . T . H . P . Heats of Combustion of Cyclic Compounds . I . By P . ZUBOBF (J . Buss . Phys . Chern . Xoc., 1901, 33. 708-722).-By means of n calorimetric bomb. the author has measured the heats of combustion of a large number of cyclic compounds prepared by Zelinsky ; the results.expressed in calories per gram-molecule on the basis of Regnault's determination of the specific heat of water at 20'. are as follows : Hydyocarbons . Normal hexane ............................................ cycloHexane ................................................... Methylcyclopentane ....................................... 1 : 3-Dimethylcyclopentane .............................. Methylcyclohexane .......................................... 1 : 1.DimethylcycZohexane ................................ 1 : 4.DimethylcycZohexane ................................. Methylcyclohexene (j3} .................................... qcZoHeptane ................................................1 : 3.Diniethylcyclohexane ................................. 1 : 3 : 3-TrimethylcycZohexane ........................... Methylcyclohexene (a) .................................... cycZoHeptene ................................................ Laurolene ..................................................... isolaurolene ................................................... c H, < ~ ~ ~ : ~ ~ > CH*CH<~~:-:~> CH, . Alcohols . p-Methylcyclopentanol ................................. cycZoHexano1 ............................................. 8- Methylcyclohexanol ................................. cycZoHeptano1 ........................................... 1 : 3-DimethylcycZopentanol (2) ..................... 1 : 3-Dimethylcyclohexnnol (2) ........................1 : 3-Dimethylcyclohexanol (5) ........................ C,H,, 'CHMe'OH .......................................... Ketones . Acetyltrimethylene ....................................... c ycZoHeptanone .......................................... 1 : 3-DimethylcycZohexanone (2) ..................... 1 : 4-MethylacetylcycZohexane ....................... C6H,, . COE t ................................................ C7H,,'COMe ................................................ 1 : 1 : 5-Trimethylcyclo-5-hexene-3-one j3.MethylcycZopentanone ................................. p-Methylcyclohexmone ................................. 1 : 3-DimethylcycZo-6-hexene-5-one .................. ........... Nitrogen compounds . C6H1,N . 1 : 1-Aminocyclopropylethane ........................C.HI9N . C.H...CHMe'NH. ...................................... C9HI7NO . C7Hl, *CMe.NOH ....................................... C,H..N . 3-Amino-l-methylcycZohexane ........................ Constant volume . 997.8 945.7 943'4 1099.5 1100.8 1096.3 1252.8 1248'1 1238.9 1406.0 1047'6 1053.2 1058.7 1202-8 1203.4 2123.5 895.1 897-3 1039'2 1047.2 1059.0 1206.0 1193.1 1353'4 697.5 840'7 1003'4 1005.1 1139.5 1278.8 1300.7 1289.4 1111.8 1259.2 830.2 1128.0 1440.1 137Eiq3 Constant pressure . 999-8 947'4 945'1 1101.5 1102'8 1098'3 1255.1 1250'4 1241.2 1408'6 1049'3 1054-9 1060'5 1204'8 1205'3 2127'3 896-6 898-8 1040.9 1048.9 1060.7 1208'0 1195'1 1355.7 698.4 841.9 1004.9 1006.6 1141.2 1280.8 1302.7 1291.4 1113-3 1260-9 831 '5 1129.9 1442.6 1377.2ORGANIC CHEMISTRY.145 I n some cases where only small quantities of isomeric cyclic com- pounds were available, the numbers differ to some extent, but, for such isomerides, the author is of opinion that the heats of combustion are either equal or very nearly so. T. H. P. Piperylene and Tropilidene. By JOHANNES THIELE ( A finalert, 1901, 319,226-230).-Piperylene, when oxidised with potassium per- manganate solution, yields formic and acetic acids, a result which indi- cates that its constitution is that of ay-pentadiene, CH,:UH*CH:CHMe. If the hydrocarbon were divinylmethane, it should yield malonic acid. The hydrocarbon obtained by Armstrong and Miller (Trans., 1886, 49, 74) from compressed oil gas is identical with piperylene. The piperylene tetrabromide (apy8-tetrabromopentane) employed in characterising the hydrocarbon may crystallise either in prisms or leaflets melting at 114-115'.Divinylmethane should be the first product of the decom- position of dimethylpiperidine ; the shifting of the double linkings may be due to the action of the trimethylamine ; a similar action is observed in the preparation of cycloheptadiene, these examples illustrating the attraction of double linkings. Piperylene and tropil- idene do not condense with benzophenone or ethyl oxalate in the pres- ence of an alkali ethoxide, and the latter hydrocarbon does not react with diazobenzenesulphonic acid. This result is all the more surprising because tropilidene is undoudtedly a cycloheptatriene. G. T. M. Thiosulphates of Aromatic Amines. By A. WAHL (Compt. rend., 1901, 133, 1215--1217).-0n mixing solutions of sodium thiosulphate and aniline hydrochloride, anililze tluiosuZplmte, (NPhH,),,H,S203, is formed as a crystalline precipitate.Other primary amines of the benzene and naphthalene series yield similar thiosulphates ; secondary and tertiary amines, on the 0the.r hand, do not give these salts, but re- act with the thiosulphate with formation of sulphur and sulphur dioxide. Such bases as dimethyl-p-phenylenediamine yield thiosul- phates of the type NMe,*C,H,*NH,,H,S,O,. When heated, these salts are decomposed, giving the base, sulphur dioxide, sulphur, and water. Nitrosodimethylaniline hydrochloride and sodium thiosulphate, when warmed together in aqueous solution, yield dimethyl-p-phenylene- diamine sulphonic acid, representing 12-15 per cent.of the nitroso- dimethylaniline used. K. J. P. 0. Derivatives of p-Tolyl-a-naphthylamine. By ROBERT GNEHM and ED. A. RUBEL (J. p r . Chern., 1901, [ii], 64, 497--517).--Acetyl-p- tolyl-a-naphthylamine, CISHl,ON, crystallises from ethyl acetate in small, white or pale flesh-coloured crystals, melts at 124', and dis- solves readily in organic solvents; it is not hydrolysed by dilute sulphuric acid at 120-140", or by dilute alcoholic potassium hydr- oxide, but is hydrolysed by a 20 per cent. solution. The benxoyZ derivative, C,,H,,ON, separates from ethyl acetate in yellow crystals, melts at 140°, and is hydrolysed much more readily than the acetyl derivative. The acetyl derivative is best sulphonated by leaving it with five times its weight of sulphuric monohydrate during two weeks ; by this method, a monoswlphonic acid is produced of which the barium VOL.LXXXII. i. n I/146 ABSTRACTS OF CHEMICAL PAPERS, salt was analysed. Barium p-toly I-a-naphtlh y luminesulphonwte was pre- pared by hydrolysing the acetyl derivative with alcoholic potassium hydroxide, but was not obtained pure; the hydrolysis could not be carried out by boiling the diluted sulphonation mixture as in the case of acetyldiphenylaminesulphonic acid or by using hydrogen chloride or iodide. p-Tolyl-a-naphthy Znitrosonmine, C17H140N2, separates from alcohol or ether in golden-yellow crystals, and melts a t 102'. Alcoholic hydrogen chloride convertcl it into the isomeric p-toZgE4-nitroso-a-nap~thgZa~ine which crystallises from alcohol in blood-red needles and melts at 161' ; the hydrochloride forms brownish-black flakes with a bronze-like lustre, and melts at 173'.The hydrochloride condenses with p- naphthol to form an oxazime-dye, and is reduced by zinc dust to a diamine. The nitroso-base condenses with p-nitrobenzoyl cyanide to form p-tolylamino-a-nup?~thyG4-cyanaxomethine-p-nitrophenyl, C,H,Me*NH*C!,H,*N :C(CN)*C,H,*NO,, which separates from benzene in violet flakes with a bronze-like lustre, and from alcobol in brown, bronzy flakes, melts at 218', and is hydro- lysed by dilute acids to a dinmine and nitrobenzoyl cyanide. Nitroacetytl-p-tolyl-a-mcL;uhthylamine, C19H1,03N2, prepared by the action of nitric acid on p-tolyl-a-naphthylamine dissolved in acetic acid, crystallises from acetic acid and ethyl acetate, melks a t 240°, and is not volatile with steam.When hydrolysed with alcoholic potassium hydroxide, it gives a yellow nitrotolylnaphthyla~~~n~, C17H140,N,, which melts at 1 1 4 O ; an isomeric nitro-derivative, melting at 188O, was obtained by direct nitration of p-tolylnaph t h y lamine. Frinitro-p-tolyl- nuphthylamine, C17Hl2O6N4, melts at 245', is insoluble in most solvents but dissolves in nitrobenzene and in aqueous alkalis. Monobromo-p-tolyl-a-naphthglanzine, Cl7HI4NBr, melts at 220', and is insoluble in all the ordinary solvents. Tetrabromo-p-tdyl-a-naphthylamine, C17H,,NBr,, separates from benz- ene in well-formed crystals, melts a t 162', and is only slightly soluble in alcohol. By using a larger quantity of bromine, an isomeric tetra- homo-derivative was obtained, which crystallises in tablets and melts at 2 1 Z', together with a hexubromo-derivative, C17H9NBr6, which crystallises in short, greenish-yellow prisms, melts a t 185O, and is slowly decomposed by heating a t 115'.p-Tolyl-a-naphthylamine condenses with nitrosodimethyl-m-amino- phenol to a quinoneimine-dye ; the colour-base, C,,H,,ON,, forms minute, brownish-red needles, and melts a t 193'; it can also be pre- pared from Meldola's blue and p-toluidine. The homologous liase, C27H250N3, prepared by condensation with nitrosodiethyl-m-amino- phenol, forms green needles, and melts a t 209.5'. A table is given showing the absorption spectra of this series of dyes. T. M. L. Pseudophenols. By KARL AUWERS (Ber., 1901,34,4256-4267).- A discussion of the results previously obtained (see Abstr., 1900, i, 96 and 161) and those detailed in the following three abstracts.The term pseudophenols is proposed for such as are insoluble in alkalis. With 0- or p-cresol derivatives which contain one of the following sub-ORGANIC CHEMISTRY. 147 stituents in the side chain-chlorine, bromine, iodine, -NO,, or an acyl group-the compounds are insoluble in alkalis. When the substituent is -OH, -OR, -CN, -CO,H, or a positive radicle, the compounds are true phenols. These results, however, are subject to variation when there are substituents in the nucleus. R. H. P. Nitro- and Thiocyano-pseudophenols and Cyanophenols. By KARL AUWERS, c. SCHUMANN [and, in part, BRoIcHER] (Bey., 1901, 34, 4267-4282. See preceding abstract).-The compound previously described (Abstr., 1896, i, 421) as dibromo-+-cumen01 nitrite is a nitro- compound, and is best obtained by the action of silver nitrite on the acetate of dibromo-$-cumenol bromide, I t s acetyl derivative crystal- lises in felted needles, melts at 155-156', and when warmed with sodium methoxide yields dibromo-p-hydroxy-+-cumyl methyl ether.The free nitro-derivative of the pseudophenol is obtained in two forms by the action of sodium methoxide at the ordinary temperature on its acetate, namely, a stable melting at 135O (loc. c d . ) and a labile one melting a t 110'. Silver nitrate reacts with acetyldibromo-$-cumen01 bromide, forming dibi*omo-p-acetoxy-$-cumyl nitrate, which crystallises from methyl alcohol in slender, yellowish-white needles, and melts at 137-1 38'.The bromide of the phenol does not react with silver nitrate in the same way, but yieldseither dibromo-p-hydroxy-+cumyl alcohol or the corresponding ether which melts a t 254-255'. Analogous results were obtained by the action of silver nitrite and nitrate on the acetate of dibromo-p- hydroxymesityl iodide ; the acetyl derivative of the nitro-compound crystallises in slender needles melting a t 141' and, when hydrolysed with a cold solution of sodium methoxide, yields the stable form of the nitro-compound which crystallises in needles melting at 127-128" ; the acetyl derivative of the nitrate crystallises in slender needles melting at 153-154'. Dibrorno-p-hydroxy-+-czcmyZ thiocyanate, S C N * C H , * C < ~ ~ ~ ~ ~ > C OH, obtained by the action of potassium thiocyanate on dibromo-$-cumen01 bromide, crystallises from light petroleum in needles, melts at 112-113', and is not dissolved by aqueous alkalis without decom- position; the acetyl derivative, which can only be obtained from the acetyl derivative of the bromide, crystallises in lustrous leaflets, melts at 145-146', and when hydrolysed with aqueous alkalis, yields the sulphide, S(CH2*C6Me,Br2*OH), (Abstr., 1897, i, 36).The diacetyl derivative of the sulphide crystallises in needles and melts a t 232-233'. The methyl ether of the thiocyanate is obtained when the reaction between potassium thiocyanate and the bromide is carried out in absolute alcoholic solution ; it crystallises in lustrous leaflets, melts at 107-108", and when treated with sodium methoxide yields the dimethyl ether of the disulphide, S,(CK,*C,h[e,Br,*OMe),, which crystal- lises in felted needles melting at 187-188", and the methyl ether of the mercaptan, OMe*CGMe,Br,*CH2*SH, which crystallises in needles melt- ing a t 94-95', When the acetyl derivative of dibromo-$-cumen01 bromide is treated with potassium cyanide, a mixture of d~bromo-p-acetoxy-~-cum~~ cyanide, OAc*C,Me,Br,*CH,*CN, and the dibromo-pacetoxy-$-curnyl ether of dibromo-p-hydroxy-+-cumyl cyanide is obtained; the former is the more m 2148 ABSTRACTS OF CHEMICAL PAPERS.soluble in alcohol and crystallises in lustrous leaflets melting at 159-161', the latter crystallises in slender, felted needles melting a t 242-243'. Dibromo-$-curnenol cyanide, OH*C,Me,Br,*CH,*CN, crystallises in slender, white needles melting at 171') is soluble in alkalis and sodium carbonate, and when hydrolysed yields dibromo-p- hydroxy-p-xylylacetic acid, which crystallises in slender, white needles and melts at 216-218'.R. H. P. Pseudophenols, By 0. STEPHANI (Ber., 1901,34,4283-4291. See preceding abstracts).-3 : 5-Dibromo-2-hydroxybenxyl thiocyanute, OH*C,H2Br2*CH,* SCN, obtained when dibromosaligenin dibromide is treated with potassium thiocyanate, crystallises in colourless clusters of neegles melting a t 111-112', is insoluble in alkalis, and forms an cicetyl derivative, which crystallises in thick, yellowish needles melting a t 148-150'. 2 : 3 : 6-(rribromo-3-hydroxybenzyZ thiocyanate crystallises in thick, yellowish needles melting a t 121-122', and is soluble in cold alkalis; its acetyl derivative crystallises in silky needles, and melts a t 115'.3 : 5-Dibromo-4-hydroxybenx~Z thiocyanate crystallises in lustrous laminae melting a t 108-log', and is decomposed by alkalis. The acetyl derivative of dibromosaligenin iodide crystallises from alcohol in needles, melts at 116-117', and when treated with silver nitrite yields 3 : 5-dibromo-2-acetoxyphenyl~itronaethane~ OAc*C,H,Br2*CH,*N02, which crystallises in lustrous, slender needles, and melts a t 132-1 33' ; the corresponding hydq-ocy-compound crystallises in yellowish needles melting at 92-93', and is decomposed by cold alkalis, 2 : 3 : 6-~r~bromo-3-cccetoxybe.nxyl iodide crystallises in yellowish needles melting at 11 9-1 20'.Z'ribromo-3-hydroxyphenylnitromethane crgs- tallises in thick needles melting a t 135-136') and is soluble in alkalis. I n the course of this and previous researches of Auwers (Zoc. cit.), it 'was shown that of the dibromo-$-cumen01 haloids the chloride is the least stable, and the author's attempt to prepare the fluoride failed. Ethyl dibromo-p-hydroxy-$-cumylntalonate, OH*C1,Br2Me2*CH2*CH( CO,Et),, obtained by the action of the $-cumyl chloride on ethyl malonate in the presence of sodiium, crystallises in plates melting a t 92-93'; the acid, when heated at 173', yields dibromo-p-hydroxycumylacetic acid, which crystallises in yellowish needles, melts a t 170-171', and is not altered when boiled with alkalis. The formate and amyl ether of dibromo-p-hydroxy-$-cumyl alcohol were found to be similar in properties to analogous compounds pre- viously described (loc.cit.) ; the formate crystallises in slender, white needles melting at 150--152O, and the amyl ether forms rhombic! crystals melting a t 84.5'. Nitroso-derivative of Methylphloroglucinol Dimethyl Ether, By JACQUES POLLAK and M. SOLOMONICA (Monatsh., 1901, 22, 1002--1010).--The constitution of the monomethyl ether of methyl- phloroglucinol having been shown by Konya (Abstr., 1900, i, 545) to be [OH : OH : Me : OMe = 1 : 3 : 2 : 61, that of the dimethyl ether must be [OH :QMe : Me: OMe- 1 : 3 : 2 :5]. R. H. P.ORGANIC CHEMISTRY. 149 The nitroso-derivative melts at 160°, and is reduced by stannous chloride to the corresponding amino-hydrochloride, which yields a triacetyl derivative melting a t 152-1 55'.When heated with carb- amide, the hydrochloride of the base is converted into 3 : 5-dirnethoxp2- rnethyZcarbonp?- 6 -aminophenol, C,HMe( OMe),<i,O,->CO, which crys tallises from alcohol in delicate, greyish-white needles melting a t 188-1 89O. On oxidation with ferric chloride, the base yields 3-hydroxy- 5-nzet~~oxy-2-methyZ2"inone; this crystallises in delicate red needles which melt a t 183-185". Etherification of the nitroso-derivative by sodium methoxide and methyl iodide leads to the formation of the methenyl compound, C,HMe(OMe),<~>CIT, which crystallises in yellow leaves melting at 72-74". These reactions show the nitrosomethyZphloro- gZucinoZ dimethyl ether to have the nitroso-group in the oytho-position relatively to the hydroxyl.G. Y. Chloromethyl Benzoate and Methylene Dibenzoate. By MARCEL UESCUD~ (Compt. rend., 1901, 133, 1213-1214. Compare Abstr., 1901, i, 504, 644).-ChZorornethyZ benzoate (Zoc. cit.) is a colour- less liquid which boils at 210' under 740 mm. pressure and a t 120-122O under 1 2 mm. pressure, and has a sp. gr. 1.236 at 20'. Methylene dibenzoate is formed when chloromethyl benzoate is heated with dried potassium benzoate at 150'; gaseous ammonia and the dibenzoate yield primarily benzamide and formaldehyde, which react together forming methylenedibenzamide (m. p. 218') ; a t the same time, ammonium benzoate and hexamethylenetetramine are produced. K. J. P. 0. 2-Chloro-3-naphthoic Acid, By ERICH STROHBACH (Ber., 1901, 34, 4158-41 62).-2-Cl~Zoro-3-nap~tho~Z chloride, C,,H,Cl*COCl, pre- pared by heating 2-hydroxy-3-naphthoic acid and phosphorus penta- chloride (3 mols.) a t 200-210°, is an almost colourless, highly refrac- tive oil boiling at 248' under 160 mm.pressure, which solidifies at 56-5O to a mass of lustrous needles. The acid chloride when warmed with water yields 2-chloro-3-naphthoic acid, this substance being ob- tained in snow-white crystals melting at 21 6.5' (compare Hosaeus, Abstr., 1893, i, 355). Ethyl 2-chloro-3-naphthoate, C,,H,Cl*CO,Et, produced by ethylating the acid with absolute alcohol and hydrogen chloride, crystallises from methyl alcohol in white leaflets ; it melts at 50" and boils at 218-222O under 160 mm. pressure. 2-CJ~Zo~o-3-naphthamide, C,,H6C1*CO*NH,, formed by adding 2-chloro- 3-naphthoyl chloride to concentrated ammonia solution, crystallises from glacial acetic acid in white needles melting a t 236-237'.1-Chloro-2-naphthoyl chloride, c,,H,Cl*CoCI, prepared from 1-hydr- oxy-2-naphthoic acid and phosphorus pentachloride, crystallises from ether in aggregates of needles and melts indefinitely between 48' and 6 0 . 5 O ; after solidifying, i t melts at 64-65'. When distilled under 160 mm. pressure, the chloride boils at 2 2 6 O ; it seems to contain traces of 1 -chloro-2-naphthoyl trichloride, G. T. M.150 ABSTRACTS OF CHEMICAL PAPERS, Chlorobromo-3-hydroxybenzoic Acids and their Ethyl Esters. By C. MARTINI (Gaxxetta, 1901, 31, ii, 363-37O).--EthyZ 6-chloro-2- bromo-3-hyd~oxybenaoccte, OH*C,H,ClBr*CO,Et, obtained by the action of bromine on ethyl 6-chloro-3-hydroxybenzoate in acetic acid solution, crystallises from aqueous alcohol in slender, white, anhydrous needles melting a t 101-102'.The corresponding acid, prepared either by hydrolysis of the ethyl ester or by the action of bromine on 6-chloro- 3-hydroxybenzoic acid, separates from aqueous alcohol in small, white needles containing lH20 and melting at 194-195'; in aqueous solution, the acid gives a brownish-violet coloration with ferric c h 1 or i d e . Ethyl 2-chZoro-6-bromo-3-hydroxybenxoate, obtained by the action of bromine on ethyl 2-chloro-3-hydroxybenzoate, separates from its ethereal solution, on cooling in ice and salt, as a pasty mass which liquefies a t the ordinary temperature (24') and is only slightly volatile in a current of steam.The corresponding acid, prepared either by hydrolysing the ethyl ester or by brominating 2-chloro-3-hydroxy- benzoic acid, separates from aqueous alcohol in small, dense crystals which contain 1H20 and melt with incipient decomposition at 116-1 18' ; with ferric chloride, i t gives a violet coloration. The two acids above described and the corresponding dichloro-acid [CO,H : C1: C1: OH = 1 : 2 : 6 : 31 all crystallise with lH,O, and their ethyl esters crystallise in an anhydrous state, and are only hydrolysed with difficulty, even by concentrated potassium hydroxide solutions. T. H. P. Some Derivatives of p-Cresotic Acid [2-Hydroxy-m-toluic Acid]. By MAX FORTNER (Monatsh., 1901, 22, 939-954).--Nitration of 2 -acetoxy-m-toluic acid and subsequent hydrolysis yields 5-nitro-2- hydroxy-m-toluic acid, which melts at 199'.Contrary to Einhorn's statement (Abstr., 1900, i, 439), esterification of the nitro-acid takes place with hydrochloric acid and alcohol. The position of the nitro- group was determined by reduction of the ester to the amino-com- pound, which melted a t 106', and conversion of this, by Sandmeyer's reaction, into Thiele and Eichwede's ethyl 5-bromo-2-hydroxy-rn-tolztate [Br : Me : OH : C02Et = 5 : 3 : 2 : 13, which melts a t 75' (Abstr., 1900, i, 501). Hydrolysis of the ester yielded the 5-bromo-acid melting at 236'. The position of the nitro-group is also shown by comparison of 5-amino-2-hydroxy-m-toluic acid with that of Nietzki and Ruppert. 5-Nitro-2-acetoxy-m-toZuic acid separates from alcohol in yellowish crystals which melt a t 142'.5-Nitro-2-hydroxy-m-toluoyl chloride, prepared by the action of thionyl chloride, forms small, yellowish crystals which melt at 86-83' and have a characteristic aromatic odour. From the chloride were prepared the amide, which forms small, yellow crystals melting at 231' ; the anilide, yellowish needles which melt at 208'; the piperidide, which separates from alcohol in small, yellowish, glistening needles melting at 125' ; the phenyihydraxide, N,HPh[CO*c,H2Me(OH)*N0,],, which separates slowly from alcohol or glacial acetic acid as a crystal- line powder melting a t 255'. The amide, anilide, and piperidide giveORGANIC CHEMISTRY. 151 deep red colorations with ferric chloride. Attempts to brominate 5-nitro-2-hydroxy-m-toluic acid were unsuccessful.The 5-bromo-acid may also be prepared almost quantitatively by bromination of 2-hydroxy-m-toluic acid in chloroform solution. 5-Bromo-2-acetoxy-m-toluic acid crystallises from alcohol in white needles which melt at 155". 5-Bromo-2-hydroxy-m-toluoy? chloride, formed by the action of thiony! chloride, is easily soluble in benzene, from which it crystallises in rhombic plates melting at 80-85" and having ti characteristic odour. From it were prepared the ethyl estev; the arnide, which crystallises from alcohol in small leaves melting a t 75-78'; the anilide, which melts at 125"; the piperidide, which melts at 82-84", The amide, anilide, and piperidide give red to violet colorations with ferric chloride. G. Y. Isomeric Dimethylcoumarones contained in Coal-tar.By JOHANNKS BOES (Chem. Centr., 1901, ii, 1226 ; from Pharm. Zeit., 46, 878).-Since the presence of as-o-xylenol and as-p-xylenol has been detected in the decomposition products of the cosl-tar fraction boiling a t 220-222' (Abstr., 1900, i, 31), this liquid, whilst consisting mainly of 4 : 6-dimethylcoumarone, must also contain a small quantity of 4 : 5-dimethylcoumarone, together, possibly, with traces of 3 : 6-dimethyl- coumarone. E. w. w. Organic Mercury Compounds. By JOHANNES BOES (Chem. Centr., 1901, ii, 1347-1348 ; from Pharrn. Zeit., 46,915).-Coumarone and indene combine with mercuric sulphate to form the compounds C,H',0,2HgS04,2Hg0,H20 and C,H8,2HgS0,,3Hg0,H,O respectively. These substances are best prepared by means of DenigBs' mercuric sulphate solution (Abstr., 1895, i, 411) and are well suited for the quantitative separation of coumarone or indene from benzene solutions ; they form yellow precipitates, are insoluble in water and the ordinary solvents, lose water a t 100-llOo, decompose above 200°, and when treated with hydrogen sulphide or warm hydrochloric acid regenerate the hydrocarbon. The compounds C,H,0,HgS04,2Hg0 and C,H,,HgSO,, 2Hg0! pre- pared by shaking solutions of coumarone or indene respectively, diluted with pure methyl alcohol with the calculated quantity of a solution of mercuric sulphate, are also suitable, under certain con- di tions, for analytical purposes.The Constitution of Unsaturated and Aromatic Compounds. By JOHANNES THIELE (AnnaZen, 1901, 319, 129-143.Compare E. Erlenmeyer, jun., Abstr., 1901, i, 357, 373).-The formation of a-benzyl-P- benzylidenepropionic acid, CHPh: CH CH( CH,Ph) CO,H, from up-dibenzylidenepropionic acid, CH'Ph:CH*C( CHPh) C02H, is no exception to the rule deduced from the author's theory that the hydrogen atoms should attach themselves to the ends of the system C:C*C:C, for the unreduced compound also contains the conjugate system G':C*C:O interlaced with the other chain in the following E. W. W.152 ABSTRACTS OF CHEMICAL PAPERS. manner, c:c*f?c:a. The hydrogen atoms may therefore be considered C t o attach themselves to the ends of the system containing oxygen, forming the labile compound CH,Ph*C(CH:CWPh):C(OH),, which is CH2Ph* UH( CH: CHPh) *C02H. This explanation applies equally well to the reduction of y-phenyl- a-benzylidene-A2-crotonolactone.The existence of free triphenylmethyl has a n important bearing on the theory of partial valency, and according to this hypothesis the fourth valency of the methyl carbon atom is almost entirely satisfied by the residual affinities of the carbon atoms of the aromatic nuclei. The space formula for benzene adopted by Erlenmeyer? jun., consists of six regular tetrahedra arranged so that their bases lie in the same plane, forming a hexagon, their apical angles being situated on the same side of this plane, The theoretical conclusions deduced from this formula as to the behaviour of aromatic compounds are, however, in- variably opposed to the facts of experiment. According to this hypothesis, the carboxyl groups in terephthalic, isophthalic, and succinic acids have the same spacial relationship to each other, and the formation of anhydride should in each case take place with equal readiness.On this assumption, phydroxymethyl- benzoic acid becomes a n analogue of y-hydroxybutyric acid and should readily furnish a lactone. These assumptions are directly opposed to the known behaviour of the compounds in question. Ethpleneglycol and catechol form monomolecular carbonates, but according to this hypothesis quinol is also an analogue of the glycol and should also accordingly yield a simple carbonate ; resorcinol and quiool, however, both form polymeric carbonates. The central carbon atoms of a naphthalene molecule produced by the conjugation of two such benzene nuclei would be united by a double linking, and this portion should accordingly be the one most susceptible to the attack of substituting agents.This conclusion is manifestly incorrect and a similar fallacy is detected on applying the same line of argument to the anthracene molecule. The employment of a modification of this space formula in which the apical angles of the tetrahedra are placed alternately on opposite sides of the plane of the nucleus is attended with similar disadvantages. mmediately transformed into the stable product G. T. M. Unsaturated 7-Lactones. By JOHANNES THIELE (Annulen, 1901, 319, 144-155. Compare following abstracts).-This theoretical communication contains a discussion of the four following memoirs. The saturated y-ketonic acids give rise to two series of crotono- CHR*fH these derivatives being indicated by the symbols Aa and AS respectively.Sometimes a third isomeride is possible, as, for example, when the substituent X is a benzyl radicle ; the isomerism of dihydrocornicularolactone and ;r.phenyl-y-benzyl-AQ-crotonolactone is explained in this manner, these CR:QH actones, "O<O-CHX and co<()-cx,ORGANIC CHEMISTRY. 153 isomerides containing extra- and intra-nucleal double linkings respectively. The ha-lactones, on oxidation with permanganate, yield dihydroxy- lactones, GO<, , which in turn give rise to trihydroxy- acids, OH*CHR*CH(OH)*CX(OH)*CO,B ; this reaction is not, however, perfectly general, for py-diphenyl-ha-crotonolactone is very slightly affected by the oxidising agent.The As-lactones, on oxidation, yield hydroxyketonic acids, R*CO*CH(OH)*CHX*CO,H, the intermediate dihydroxylactones, CX( OH)* CH*OH bHeR CHX'?H*oH being unstable. Co<O-C**OH' The lactones of this series containing in the a-position a methylene group between a carbonyl and an ethylene linking, readily condense with aldehydes in the presence of a weak base such as aniline ; the corresponding Aa-derivatives do not react under these conditions. The As-derivatives are usually labile and are converted into their stable ha-isomerides by the action of acetic anhydride or a strong base such as ammonia, tropine, piperidine, or the aliphatic amines. Bases with a neutral reaction (aniline, pyridine, or their derivatives) do not bring about this transformation.The Ad-compound, however, is not invariably the stable modification, for in the case of the 7-phenylcrotonolactones, the isomeride of this series is readily trans - formed into its As-isomeride. This characteristic action of the strong bases is analogous to that of alkaline reagents on the enolic forms of the esters of P-ketonic acids ; in the latter case, a double linking shifts from the *C:C* to the :C:O group, whilst in the former, the rearrangement occurs between two *C:C* residues, The transformation of A@-lactone into its ha-isomeride is reversed when the strong base reacts in the presence of an agent capable of condensing with the regenerated As-lactone, the substance commonly employed being an aldehyde. The reduction of ammoniacal silver nitrate by the Aa- and AP- crotonolactones varies in rapidity with the position -of the double linking, and it also seems to depend on the presence of hydrogen in the y-position of the lactone ring, for derivatives having the general formula CO<o-~xu are not affected by this reagent.Both series of unsaturated lactones develop an intense yellow color- ation with alcoholic potassium hydroxide, which is supposed to be due substances t o the formation of hydroxyfurfuranols, OH*& which could be produced by a simple transformation from both Aa- and Ab-derivatives. Lactones such as phenylbenzylidenebutyro- lactone and dihydrocornicularolactone, which contain a double linking outside the lactone ring, do not exhibit this property. The following communications furnish experimental evidence in favour of the hypothesis that the two series of crotonolactones are structurally diesimilar and not stereoisomerides as suggested by Erlenmeyer, jun? (compare Abstr., 1901, i, 357, 3731, CH:C*R CR*ER 0 -OR' G.T, M,154 ABSTRACTS OF CHEMICAL PAPERS. The Lgctones of Desylacetic Acid. By JOHANNES THIELE and FRITZ STRAUS (Annalen, 1901, 319, 155-180. Compare Abetr., 1899, i, 612 ; Klingemann, Abstr., 1892, 1002, and Erlenmeyer and Lux, CH,*EPh Abstr., 1898, i, 668).-~y-Diphenyl-A~-crotonolactone, CO< 0-CPh' readily reduces ammoniacal silver nitrate and potassium permanganate solutions, and is converted into its stable Aa-isomeride, CO< CH:$JPh 0-CHPh' when boiled with alcohol containing traces of a base or salt having an alkaline reaction ; the catalysts employed are potassium carbonate or hydroxide, sodium acetate, ammonia, piperidine, or an aliphatic amine.The aromatic bases do not promote this transformation. py-Diphenyl-a-6enxylicEene-~s-crotonolactone, CHPh:C<co-O CPh: YPh ) produced by boiling together its generators in alcohol containing a trace of aniline, crystallises from this solvent in yellow needles melt- ing a t 141-142'; it is also obtained by heating the stable lactone with benzaldehyde containing a few drops of piperidine. The latter mode of formation indicates that the transformation of the labile lactone with the Aa-isomeride by the aid of piperidine is a reversible process. Desylcinnamic acid, COPh* CHPh*C( CHPh) CO,H, results from the action of a methyl alcoholic solution of potassium hydroxide on the preceding compound ; it separates from benzene as a white, crystalline powder, and melts a t 187-188".The methyl ester, obtained from the silver salt and methyl iodide, crystallises from alcohol in lustrous, white needles and melts a t 113.5'. The acid and its ester develop a n intense yellow coloration with alcoholic potassium hydroxide, but it is destroyed by the addition of water. When treated with acetic anhydride and a trace of sulphuric acid, the acid yields y-acetoxy-py- diphen y I-a- benxylidene but ys.oIccctone, OAc C Ph< , a oub- stance crystallising from alcohol in colourless, iridescent plates melting at 128-128.5". C H P h 7 : CHP b. 0-co a-Bromo-py-diphenyI-Aa-crotonokcctone, GO< CBr:yPh , prepared by 0--CHPh treating thin layers of the powdered Aa-lactone with bromine vapour in the presence of light, crystallises from alcohol or carbon disulphide in colourless needles and melts a t 118-1 19' ; it is somewhat insoluble in the ordinary organic solvents, reduces ammoniacal silver nitrate, regenerates the Aa-lactone when treated with alcohol and a zinc-copper couple, but is not attacked by zinc dust and cold acetic acid, CH2*~phBr, produced by 0-CPhBr py-Di6s.omo-py-dipilen y I but yro Zactone, CO< adding the As-lactone dissolved in carbon disulphide to a cooled solu- tion of bromine in the same solvent, separates as a white, crystalline powder which decomposes at 64' evolving hydrogen bromide and yielding y-bromo-~~-di~?~enyl-~~-crotonolc~ctolze~ CO< a sub- CH:yPh 0-CPhBr'ORGANIC CHEMISTRY, 155 stance crystallising from light petroleum in well-defined, brownish prisms, melting at 107-108’ and decomposing a t 130’.The mono-bromolactone yields the labile A“-lactone on reduction with zinc dust and glacial acetic acid, and when warmed with methyl alcohol gives rise t o y-methoxy-py-diphenyl-Aa-crotonoZactoe, CH:QPh “<O-CPh*OMe’ which separates from this solvent in colourless crystals melting a t 102.5’. , produced CH:QPh 0-CPh-OAc y- Acetoxy-/ly-diphenyLAa-crotonolactone, CO< by shaking an ethereal solution of the bromo-lactone with silver acetate, crystallises from methyl alcohol or benzene, and melts a t 1 16’. Desyleneacetic acid, COPh*CPh:CH*CO,H, prepared from By-di- bromo-py-diphenylbutyrolactone by the action of a cold alcoholic solution of potassium hydroxide, is also obtained by oxidising the Ap-lactone with a potassium permanganate solution containing mag- nesium sulphate, and is produced in small quantities along with desyl- acetic acid when the dibromide is converted into y-bromo-py-diphenyl- ha-crotonolactone by the action of heat ; it crystallises from benzene and melts a t 139O; the solidified product, however, has a melting point of 167’.The two modifications, when mixed together, melt at 1 6 7 O . These two modifications of the acid seem to have a transforma- tion temperature which is below the melting point of the substance melting at 139O ; this form is distinguished as the a-, and the other as the P-compound. The a-acid, when heated a t 130-135°, changes into the p- compound, whilst this substance, when dissolved in ammonia and pre- cipitated by acid, regenerates the acid of lower melting point.The silver salts obtained from the two modifications yield the same methyl ester on treatment with’methyl iodide ; thisderivative forms lustrous needles melt- ing a t 89’, and is isomeric with y-methoxy-py-diphenyl-Aa-crotonolactone. Desyleneacetic acid may also be obtained from P-bromo-py-diphenyl- A‘-crotonolactone or y-me thoxy-by-diphenyl-Aa-crotonolact one by the action of alcoholic solutions of potassium hydroxide ; i t is identical with the product from desylenemalonic acid (Japp, Trans., 1895, 67, 138; 1897, 71, 133). Ethyl desylenemalonate, COPh*CPh:C(CO,Et),, when crystallised from alcohol, melts at 70-71O. Deoxybenzoin is readily prepared by treating chlorobenzil with granulated zinc and alcoholic hydrochloric acid.The Lactones of Angelic Acid. By JOHANNES THIELE, ROBERT TISCBBEIN and EMIL Lossow (Annalen, 1901, 319, 180-195)- Ap(a)-Angelicalactone, prepared from laevulic acid by Bredt’s method (Abstr., 1890, 863), yields a-anisylidene-Ap-angelicalactone, OMe* C , H , * C H : C < ~ ~ ~ M e , when condensed with anisaldehyde, and a-benzylidenelcevdic acid, COMe*CH,*C(CHPh)*CO,H ; when treated with benzaldehyde ; the former product crystallises from methyl alcohol in yellow needles melting at 98-5-99”, and the latter in white G. T. &I.156 ABSTRACTS OF CHEMICAL PAPERS. needles melting a t 121' (compare Erdmann, Abstr., 1900, 375, 1129). The condensations are carried out in the presence of a trace of piper- idine; when the reaction with benzaldehyde is performed in a methyl alcohol solution of potassium hydroxide, a dibenxylidelzs- Zavulic acid is obtained which forms colourless needles melting at 177-1 78', and differs from Erdmann's PG-dibenzylidenelmulic acid Benxylidenemalic acid, HO* CH(C0,H) *C(CHPh)*CO,H, and iodoform are obtained on treating a-benzylidenelaevulic acid with iodine and sodium hydroxide; the acid separates from water in white crusts (ZOC.C i t . ) CHPh:C-CO melting at 1 7 3 O and yields the anhydride, co,Bxe~~H,co>O, of L P-acetyl-a-benzylidenemalic acid, a substance crystallising from benzene and light petroleum in white needles melting at 116.5-117'. a-Anisyl- idenelcevulic acid, CH,Ac * C (CH.C6H4*OMe)*C02H, obtained from the corresponding lactone by treating it with crystallised sodium carbon- ate in dilute alcoholic solution and acidifying the product, crystal- lises from toluene in needles melting a t 119-119.5O ; the lactone is regenerated by the action of acetic anhydride and a trace of sulphuric acid. Anisylidenemalic acid, C02H*CH(OH)*C(C0,H):CH*C,H4*OMe, pro- duced together with iodoform by the action of iodine and sodium hydroxide on the preceding acid, forms white needles sintering a t 165' and decomposing at 177". The formation of condensation products from a-angelicalactone and the aldehydes shows that it has a constitution corresponding with the - CH,*gH formula CO<~-~~-. It is partially transformed into the p- or CH:$JH, Aa-angelicalactone, CO<O--CMe, by heating with diethylaniline hydrobromide, or triethylamine ; the converse transformation occurs to a limited extent on warming the purified ha-isomeride with the latter reagent. Aa-Angelicalactone does not combine with anisaldehyde, but when oxidised wifh potassium permanganate solution containing mag- CH(0H) * FH* OH CHMe ' nesium sulphate yields dihydroxyvaterolactone, which crystallises from water, alcohol, or ethyl acetate in colourless needles melting a t 100' ; its diacetyl derivative, obtained by the action of acetyl chloride, crystallises from alcohol in colourless needles melt- ing a t 94-95'.Barium trihydroxyvalerate, produced by dissolving the lactone in barium hydroxide solution, is an uncrystallisable salt ; the corresponding acid is unstable and regenerates the lactone. Alkal- ine solutions of the lactone do not reduce ammoniacal silver nitrate. The stability of the dihydroxylactone under these conditions is evidence in favour of its formula and also of that proposed for ha-angelica- lactone.The dihydroxglactones derived from ha-angelicalactone and i t s AY-isomeride, CO<O-c:CH,' should have the formulae, CH,*$JH,QRGANIC CHEMISTRY. 157 the corresponding acids of the salts produced from these by the action of alkali hydroxides would be the hydroxylavulic acids, CO,H*CH,*CH(OH)*COMe and C02H*CH2*CH,*CO*CH,*O13, both of which, being a-hydroxyketones, ought t o reduce the silver solution. G. T. M. [Phenyl Aa-Crotonolactone]. The Unsaturated Aa-Lactone of Bensoylpropionic Acid.By JOHANNES THIELE and N. SALZBERBER (Anncclen, 1901, 319, 196-21 l).-p-Bromo-a-cccetoxy-y-phenylbutyro- prepared from the corresponding Iactone, GO<, . hydroxylactone by the action of acetic anhydride, crystallises from alcohol in colourless, vitreous, monoclinic prisms, and melts at 64.5". obtained from the pre- ceding compound by the action of a copper-zinc couple suspended in cold water, is a yellowish-red oil which solidifies in a freezing mixture, and when warmed with acetic anhydride or an alcoholic solution of piper- idine or even on distillation a t 140' under 30 mm. pressure, changes into its solid isomeride phenyl-Ahxotonolnctone, CO<cH2*!?H 0-CPh ' melting a t 9l0 (compare Fittig, Abstr., 1898, i, 196, and Kugel, ibid., 198). A slow transformation occurs even when the labile Aa-com- pound is kept in the dark but the change is not complete even at the end of twelve months, The ha-lactone, when hydrolysed either with mineral acids or alkali hydroxides, yields p- benzoylpropionic acid (m.p. 115-116'), and on oxidation with potassium permanganate in the presence of magnesium sulphate gives rise to ap-dihydroxy-y-phenyl- butyrolactone (Fischer and Stewart, Abstr., 1892, 1447), whilst the As-isomeride furnishes the red compound obtained by Kugel (loc. cit.) by the action of ferric chloride. a-Acetoxy-y-phenylcrotonic acid, CHPh:CH*CH(OAc)*CO,H, a bye- product in the preparation of phenyl ha-crotonolactone, crystallises from water in colourless needles containing 1H,O, and melting a t 78-79' ; the anhydrous acid, obtained by drying the monohydrate over concen- trated sulphuric acid, melts a t 90-9lG, and rapidly regains its water of crystallisation on exposure to the atmosphere.The acid, when treated with a chloroform solution of bromine, yields the dibromide (m. p. 206'; compare Abstr., 1899, i, 611), and on boiling with hydrochloric acid gives rise t o P-benzoylpropionic acid ; it decomposes into acetic acid and phenyl As-crotonolactone on distillation in a vacuum, a small amount of the ha-isomeride being obtained by rapid heating. a-Chloro-py-dibromo-y-phenyZbutyronitde, CHPhBr*CHBr*CHCl*CN, produced by treating the dibromide of cinnamaldehyde cyanohydrin with phosphorus pentachloride, crystallises from alcohol in colourless needles which melt somewhat indefinitely at 110-120' ; when mixed with zinc dust and glacial acetic acid, it yields phenylcrotononitrile, CHPh:CH*CH,*CN or CH,Ph*CH:CH*CN, a substance crystallising from light petroleum in leaflets melting at 69-60' and rapidly reducing ammoniacal silver nitrate.CH(OAc)*FHBr CHPh' Phenyl A"-crotonolactone, CO< CH:(?H 0-CHPh'158 ABSTRACTS OF CHEMICAL PAPERS. fly-Bibrorno-a- acetoxy- y-PhenylbzLtyronitrile, CHPhBr*CHBr*CH(OAc) * CN, formed from the corresponding hydroxy-compound by t5e action of acetic anhydride, crystallises from alcohol in colourless, four-sided plates and melts at 166-167O. G. T. M. Unsaturated Lactones of Dihydrocornicularic Acid. By JOHANNES THIELE and FRITZ STRAUS (Annalen, 1901, 319, 211-225. Compare Abstr., 1899, i, 6 12,6 14).-/3y-Dibromo-a8-diphenylvaleric acid, CH,Ph*CHBr*CHBr-CHPh*CO,H, prepared from a8-diphenyl-Ap-pen- tenoic acid and an acetic acid solution of bromine, crystallises from carbon disulphide in white needles melting a t 172".The bromine atoms are readily removed by the action of zinc dust and glacial acetic acid. obtained by treating the preceding dibromide with cold dilute sodium hydroxide solution, crystallises from methyl alcohol in thick, white needles and melts at 91'. The lactone is not affected by hydrogen bromide dissolved in glacial acetic acid, alcoholic hydrochloric acid, or hot acetic anhydride ; it immediately reduces ammoniacal silver nitrate, and develops a deep yellow coloration with alcoholic potassium hydroxide solution. Dihydrocornicularic acid is obtained by boiling the lactone either with potassium hydroxide in methyl alcohol, or with a dilute alcoholic solution of sodium carbonate; by the former process, a small amount of a dimeric phenylbenzylcrotonolactone is simultaneously produced ; this compound crystallises in lustrous prisms melting a t 193'.Dihydrocornicularic acid is identical with the product obtained by Spiegel (Abstr., 1882, 1077). This substance, according to the authors' experiments, is reconverted into the original lactone when heated a t 200"; Spiegel, on the contrary, obtained a different compound, dihydro- cornicularolactone, to which he ascribed the formula CPh:YH 0-CH*CH,Ph ' a-Phenyl-y-benxyl-A"-crotonolactone, CO< CHPh. YH, Co<O-C:CHPh The polymeric lactone aIso yields the acid on treatment with potassium hydroxide in methyl alcohol ; it reduces ammoniacal silver nitrate, but is not oxidised by alkaline solutions of permanganate.a/3-Dihydroxy-a-pRenyL y- benxylbut yrolactone, CPh(OH)*FH*OH Co<o-CH* CH,Ph results from the oxidation of a-phen yl-y- benzyl-ha-crotonolactone with potassium permanganate solution ; it crystallises from chloroform in white needles and melts at 138'; its diacetyl derivative forms lustrous prisms and melts at 1 3 7 O . afly- Trihydroxy-as-dipheryhaleric acid, CH,Ph*CH(OH)*CH(OH)*CPh(OH)*CO,H, obtained in the form of its barium salt by hydrolysing the dihydroxy- lactone with barium hydroxide solution, is unstable and regenerates the lactone. The &her salt, C,7H,70,Ag, is a hygroscopic, amorphous, white precipitate,ORGANIC CHEMISTRY. 159 y- Acetoxy-a-phenyl-y-benzylbutyrolactone, CHPh*FH, Co<O-C(OAc\*CH,Ph' produced from dihydrocoroicularii acid b$ the action of acetic anhydride and sulphuric acid, melts a t 105-106° and not at 9S-99' as recorded by Spiegel. Dihydrocornicularolactone is formed during the crystallisation of the acetoxy-compound and is obtained in larger quantities by treating the acid with half its weight of acetic anhydride and a trace of an acid ; it is converted into its isomeride a-phengl-y-benzyl-Aa-crotonolactone by heating with a glacial acetic acid solution of hydrogen bromide, but this transformation is not affected by acetic anhydride.A Zactone, CI7Hl4O2, isomeric with dihydrocornicularolactone, is produced together with this lactone and its acetyl derivative by heating dihydrocornicularic acid with acetic anhydride, traces of phenylbenzyl-ha-crotonolactone are also obtained ; i t crystallises from alcohol in highly refractive leaflets and melts at 128.5'.The new lactone is probably a stereoisomeride of dihydrocornicularolactone, and resembles the latter in reducing ammoniacal silver nitrate rapidly, but not instantaneously, and in developing a yellow coloration with alcoholic potassium hydroxide ; it regenerates dihydrocornicularic acid by alkaline hydrolysis. G. T. M. Naphthaldehydic Acid. By JOSEF ZINK (Xonatsh., 1901, 22, 986- 990)-When naphthaldehydic acid is formed by fusing acenaph- thenequinone with potash, it is accompanied by naphthalic acid, the amount of the latter increasing with the duration of the fusion.Naphthalic acid is also formed on boiling naphthaldehydic acid with alkalis. The formation of a hydroxy-acid or lactone corresponding with phthalide could not be detected. Potassium cyanate in absolute alcohol has the same action as aqueous alkalis. Methyl naphthaldehydcte melts a t 105' (compare Wegscheider, Monatsh., 1882, 348). G. Y. New Glyceride : Glyceryl Phthalate. By WATSON SMITH(J. #oc. Chem. Ind., 1901, 20, 1075--1076).-When glycerol and phthalic anhydride are heated for a long time nearly to boiling, either alone or with zinc chloride, the product is a solid mass resembling glass slag in appearance, which is most probably diglyceryl triphthcdate. It is practically insoluble in all solvents, with the exception of acetone, in which it dissolves to a slight extent. On hydrolysis with sodium hydroxide, it yields glycerol and phthalic acid; with sulphuric acid, it gives sulphonated products, and it is nitrated by a mixture of ooncen- trated nitric and sulphuric acids.H. R. LE S. Derivatives of Nitrophthalic Acid. By HEINRICH SEIDEL (Bey., 1901, 34, 4351-4363. Compare Onnertz, this vol., i, 95).-P-Nitro- phthalic acid yields P-nitrophthalimide when heated in gaseous am- monia ; this crystallises in yellowish leaflets melting a t 202' ; a-nitro- phthalimide forms yellowish needles melting a t 216'. From the a-imide, by means of Hofmann's reaction, 6-mitro-2-amino6enxoic acid,160 ABSTRACTS OF CHEMICAL PAPERS. NO,.C,H,(NH,)*CO,H, is obtained as an ochre-yelIow, crystalline powder melting at 184"; the acid readily loses carbon dioxide, with formation of m-nitroaniline.The P-imide yields two isomerides, 4-nitro-2-aminobenxoic acid melting at 264' and 5-nitro-2-arninobenxoic mid melting at 280'. From the former, 4-nitrosalicylic acid (m. p. 235') and 4-aminosalicylic acid (m. p. 220" with decomposition) can be obtained. The two nitrophthalic acids are reduced by sodium sulphide t o aminophthalic acids; the a-amino-acid is a yellow powder melting at 226", whilst the P-amino-acid crystallises in needles, which lose their crystalline form on drying and melt at 2SO'. K. J. P. 0. a- Phenylglutaric Acid and y8-Diphenylallylacetic Acid [y6-Diphenyl-y-pentenoic Acid]. By FRITZ FICHTER and OTTO MERCKENS (Ber., 1901, 34, 41 74-4178).-EthyZ y-acetyZ-a-phenyL gkutarate, CO,Et*CHAc*CH,*CHPh*CO,E t, obtained by condensing ethyl chlorohydratropate (Spiegel, Abstr., 1881, 277) with ethyl sodioacetoacetate, boils at 189' under 11 mm.pressure, and, on hydrolysis with 25 per cent. alcoholic potassium hydroxide, yields a-phenylglutario acid; the latter is also obtained by heating with hydrochloric acid ethyl a-phenylpropune-aay-tricccrboxykate, which is formed by condensing ethyl P-iodopropionate with ethyl phenyl- malonate, and boils a t 219-221' under 13 mm. pressure. a-Phenylglutaric acid is best purified in the form of its calcium salt, which crystallises in white, microscopic needles with 4H20 ; the 6arium salt, with 2H,O, is ill-defined, the zinc salt, with 7H,O, forms sheaves of needles, and the silver salt is anhydrous.The pure acid separates from benzene or light petroleum in small crystals, melts at 82-83', and partially changes in dry air into the anhydride; the latter is obtained quantitatively on distilling the acid under reduced pressure and crystallises from ether in beautiful, small needles, melts at 95', and boils at 218-230' under 13 mm. pressure. On boiling the anhydride with water, a hydrated form (with 1H,O) of a-phenyl- glutaric acid is obtained in large, colourless needles, When dry sodium a-phenylglutarate is heated with benzaldehyde (1 mol.) and acetic anhydride for 50 hours at 155', considerable quantities of y6-dip~ertylallylacetic acid [y6-diphenyZ-y-pentenoic acid], CHPh:CPh*CH,*CH,*CO,H, are formed; it is best isolated in the form of the sparingly soluble, amorphous calcium salt (with 1 +-2H,O) ; the barium salt contains 2H,O.The pure acid crystallises from a mixture of ether and light petroleum in colourless needles, melts at 106O, and when treated with hydrogen bromide in glacial acetic acid a t the ordinary temperature, yields an oil which is readily transformed into y6-diphenyhalerolactone ; this separates from ether in beautiful crystals and melts a t 59-60". By GIROLAMO MAZZARA (Gaxxetta, 1901, 31, ii, 347--356).-Whilst ethyl gallate crystallises with 2&H,O, it has been stated by Bietrix (Abstr., 1893, i, 343) that the methyl compound contains 3H20. In this case, then, there appears to be no analogy similar to that existing between the methyl and ethyl esters of the dihalogenated gallic acids, which all crystallise with W.A. D. Anhydrous Methyl Gallate.ORGANIC CHEMISTRY. 161 l&K,O. The author finds, however, t h a t when the anhydrous methyl gallate described by Will (Abstr., 1888, 1059) is crystallised several times from water it contains l$H,O ; this hydrate, which he assumes t o be a compound of the anhydrous ester with the hydrate containing 24H20, readily reverts to the anhydrous form. Ethyl gallate melts at 158" if crystallised from benzene, or at 1 5 5 O if it is crystallised from water (with 2$H20) and dehydrated. Action of Bromine on Methyl and Ethyl Gallates and on their Chloro-derivatives. By P. GUARNIERI (Gaxxctta, 1901, 31, ii, 356-363).-Ethyl dibromogallate crystallises with 1+H20 and melts a t 137'. Methyl dibromogallate, which Bietrix (Abstr., 1893, i, 343) described as crystallising with 1H,O and melting at 139O, is found by the author to contain 1&H,O and to melt a t 169'.Ethyl Cl~Zo~~obronzogaZZate, C,H,BrC1(OH),*C02Et [Cl : Br : (OH), = 2 : 6 : 3 : 4 : 51, prepared by the action of bromine on ethyl chlorogallate in acetic acid solution, separates from water in leaflets containing 1 &H,O, and melting, after dehydration, a t 134-135'. Methyl chZorobromogaZZnte crystallises from water in yellow leaflets containing I&H,O, and melt- ing after dehydration at 162-1663'. All the halogenated methyl and ethyl esters of gallic acid melf a t lower temperatures than the esters from which they are derived ; the disub- stituted derivatives of methyl and ethyl gallates crystallise with l$H,O, whilst the monohaloid compounds contain only 1H,O.The methyl esters in all cases melt at higher temperatures than the corresponding ethyl compounds. T. H. P. By NICOLAI N. LJUBAVIN (J. Buss. Phys. Chem. Xoc., 1901, 33, 680-684).-The author has studied the action taking place when solutions of tannin and tartar emetic are mixed under different conditions of concentra- tion and in presence of ammonia and of sodium acetate. The action is found to depend on the order in which the two solutions are mixed ; thus, when a 1 per cent. solution of tannin (2-3 mols.) is added to 1 per cent, tartar emetic solution (1 mol.), a precipitate is obtained, whilst if the solutions are mixed in the inverse order, no precipitate is formed. The precipitate obtained is in every case white and gela- tinous, giving greyish lumps when dried in a desiccator.When dried at the ordinary temperature, the composition corresponds with the formula C,,H,(SbO)O,,H,O, but if dried at looo the formula ia C,,H,SbO,. The filtrate from the precipitate always gives the reactions for antimony and for tannin. Action of Benzenediazonium Chloride on Methylenedi-2- hydroxy-3-naphthoic Acid. By ERICH STROHBACH (Ber., 1901, 34, 4162-4165. Compare Mohlau and Strohbach, Abstr., 1900, i, 368).-The basic sodium salt, CH,[C,,H,(ONa) *C0,Na],,2H20, of methylenedi-2-hydroxy-3-naphthoic acid, obtained by treating the acid with an alcoholic solution of sodium ethoxide, crystallises in pale yellow needles. The methylene radicle of methylenedi-2-hydroxy-3-naphthoic acid is displaced by two azo-residues when benzenediazonium chloride is added VOL.LXXXII. i. I)& T. H. P. Interaction of Tannin and Tartar Emetic. T. H. P.162 ABSTRACTS OF CHEMICAL PAPERS. t o an alkaline solution of the acid, the product being identical with von Kostanecki's l-benzeneazo-2-hydroxy-3-naphthoic acid (Abstr., 1894, i, 91j. G. T. M. Chlorination of m-Hydroxybenzaldehyde. By HEINRICH BILTZ and OTTO KAMMANN (Ber., 1901, 34, 4118-4128. Compare Zincke and Walbaum, Absti., 1891, 708).-AZdehydotrichloroq.;ino- dichloyide, ~cI.Ccl,.~eCHO' prepared by saturating with chlorine an ccL*co-cc1 acetic acid solution& of m-hydroxybenzaldehyde slightly diluted with water, first a t the ordinary temperature and then on the water-bath, crystallises from glacial acetic acid in yellow plates, and melts at 137-1338'.It is decomposed by alkali hydroxides and carbonates, and also by phenylhydrazine and aniline. The oxime, C7H,0,NCl,, crystal- lises from dilute alcohol in brownish-yellow leaflets, melts at 169O, and is readily soluble in the ordinarv organic solvents. The semicarb- . I " axone separates in orange-coloured, cubical crystals, and melts at 202'. Dichlorornethyltl.ichloropzcinod~chloride, ~cl.ccl,. .CHCI; produced c c 1 * c o - ~ c l by treating the preceding aldehyde with phosphmus pehachloride, separates in colourless crystals and melts at 117'; a bye-product containing phosphorus and melting a t 224' is also formed in this reaction. T'etrachloro-m-hydroxybenxaldehyde, OH*C,Cl,*CHO, obtained in quantitative yield by reducing aldehydotrichloroquinodichloride in acetic acid solution with stannous chloride, crystallises from benzene in colourless needles melting a t 189-1909 The acetyl derivative, OAc*C,CI,*CHO, crystallises from glacial acetic acid in needles, and melts a t 11 2O.T'e trach lor o -m-h y dr ox y belzxalde h y dephen y lhy draxone, OH*C,CI,*CH:N*NHPh, produced by mixing its generators in acetic acid solution, separates from this solvent in felted, yellow needles and melts at 124-125'. Both the phenylhydrazone and the aldehyde dissolve in solutions of the alkali carbonates and hydroxides, developing yellow colorations. Acetyltetrachloro-m-hydroxybenzaldehyde, wheh treated with phenyl- hydrazine, yields the corresponding phenylhydrazone, a substance crystallising in yellow plates and melting at 188--189O, which, on warming with acetic anhydride, gives rise to the diacetate, OAc*C6~1,*CH:NPhAc ; this compound, also obtained by acetylating tetrachloro-m-hydroxybenzaldehydephenylhydrazone, crystallises in light brown leaflets, and melts at 148'.Tetvachloro-m-eihoxybenxaldehyde, OEt* C,Cl,*CHO, prepared by boil- ing together tetrachloro-m-hydroxybenzaldehyde, sodium ethoxide, and ethyl iodide in alcoholic solution, separates from glacial acetic acid in felted, colourless needles, and melts at 67-68' ; the phenylhydrazone crystallises from the ordinary organic solvents in yellow leaflets melting a t 111-112'. Tetruchloro-m-hydroxybengaZdoxime, OH*C6C1,*CH:NOH, produced OAc*C,Cl,*CH :N*NHPh,ORGANIC CHEMISTRY.163 from hydroxylamine hydrochloride, sodium hydroxide, and the come- sponding aldehyde in aqueous solution, crystallises from benzene in white needles and melts a t 194-195O. Acet?/ltetruchloro-m-hydroxybenzonitrile, OAc.C,Cl+.CN, obtained by heating the preceding oxime with acetic anhydride, crystallises in aggregates of lustrous? pale red needles and melts at 145-146' ; when hydrolysed with a boiling alcoholic solution of sodium ethoxide, i t yields the sodium derivative of tetrct~?doro-m-h~droxybenxonitr~~e. The latter nitrile forms yellowish-white needles and melts at 219-220'. I'etyuchloro-m-hydroxybenaamide, OH*C,~l,*CO*NH,, produced by hydrolysing tetrachloro-m-hydroxybenzonitrile with 10 per cent. hydrochloric acid a t 200°, crystallises from glacial acetic acid in needles melting at 260-261'; on further treatment with boiling 50 per cent.sulphuric acid, the amide yields tetrachloro-m-hydroxybenzoic acid (m. p. 172'), this acid being also obtained by the direct oxidation of tetrschlorom-hydroxybenzaldehyde. Tetrachloro-m-hydroxybenxylidene chloride, OH*C,Cl,* CHCl,, prepared by the action of phosphorus pentachloride on tetrachloro-m-hydroxy- benzaldehy de, crystallises from glacial acetic acid in prisms with truncated, pyramidal ends, and melts at 86-87' ; it separates from t h e dilute acid in a.ggregates of needles containing 3H,O and melting a t 66-68', This chloride is also obtained by reducing dichloromethyl- trichloroquinodichloride with stannous chloride, and justifies the constitution given to this quinone derivative.Tetruchloyo-m-ucetoxybenxylidene chloride, OAc* C,Cl,*CNCl,, produced by warming the preceding compound with acetic anhydride, crystal- lises from glacial acetic acid in colourless, double pyramids. G. T. M, Halogen Derivatives of Phenols. By W. RICHTER (Bet.. ,1901, 34, 4292-4296. Compare Auwers, Abstr., 1899, i, 36 ; 1900, i, 164, 165). -p-Acetoxybenxylidene bromide, CHBr,*C,H,*OAc, obtained by the action of phosphorus pentabromide on p-acetoxybenzaldehyde (b. p. 264-265O), crystallises from light petroleum in colourless prisms, melts at 97-98', and is readily soluble in most organic solvents. It turns dark on exposure to light, and on treatment with an acetic acid solution of hydrogen bromide, even in the entire absence of moisture, yields p-hydroxybenzaldehyde.By the action of bromine in chloroform solution, it is converted into dibromo-p-hydroxybenzaldehyde. m-Acetoxybenzylidene 6romide, obtained by the action of phosphorus pentabromide on a chloroform solution of m-acetoxybenzaldehyde (b. p. 263O), is a yellow oil, which on treatment with hydrogen bromide yields m-hydroxybenzaldehyde ; bromine transforms it into tribromo- m-h ydroxybenzaldehy de. The constitution of Auwers and Hamye's tetrabromotoluquinol (Abstr., 1899, i, 96) has been confirmed by the preparation of a dincetyl derivative melting a t 282-283' and by its reduction to t ribromo t oluquinone me1 ting a t 2 0 3-2 0 4'. Tetrachlorotoluquinone (Gorup, Annalen, 1867, 143, 159) melts at 266-270', and on reduction with sulphurous acid yields the corre- sponding quinol, CH,Cl*C,CI,(OH), ; this crystallises from acetic acid in glistening plates, melts at 228O, and is readily soluble in dilute alkalis.n 2164 ABSTRACTS OF CHEMICAL PAPERS, The chlorine of the side chain is not readily replaceable. The diacetate crystallises in glistening needles melting at 232' and readily soluble in acetone. J. J. S. Synthesis of Ketones, By EDMOND E. BLAISE (Compt. ?*end., 1901, 133, 1217-1218. Compare Abstr., 1901, i, 252,317,363).-The crystalline compounds of the type CRR:N*MgI,Et,O (loc. cit.), which are formed when nitriles interact with the compounds of magnesium alkyl iodides and ether, react with water yielding ketones. To prepare the ketones, it is not necessary to isolate the intermediate compounds; the nitrile (1 mol.) is added to a solution in dry ether of magnesium alkyl iodide (1.5 mols.); the mixture is heated a t looo, and then, after addition of water and the distillation of the ether, the ketone is distilled in a current of steam, The best yields are obtained with aromatic nitriles, in which the cyano-group is in the nucleus.0-Tolyl ethyl ketone, C6H,Me*COEt, is a liquid boiling at 219-221'; its semicarbaxone melts a t 173'. Benzyl n-popyl ketone, prepared from butyronitrile and benzyl chloride, is a liquid, having the odour of aniseed, and boiling a t 238-241'; its semicarbaxone melts at 84'. Benxyl iso- amyl ketone boils a t 267' ; its semicarhazone melts a t 133'. o-Methyldeoxy- benzoin boilsat 317-320' under theordinarypressure and a t 191' under 21 mm.pressure ; its semicarbaxone melts a t 19So, p-Tolyl bzctyl ketone melts at 22' and boils a t 266-267'; its semicarbaxone melts at 212'. p-Tolylpopyl ketone boils at 248-250' ; its semicurbaxone melts a t 232'. n-Propyl isoarnyl ketone boils a t 176-1 78' ; its semicarbaxone melts a t 102'. Ethyl prop91 ketone and phenyl ethyl ketone have also been prepared by this method ; their semica~bccxones melt at 110' and 182' respectively. K. J. P. 0. Condensation of Acetylene Hydrocarbons with Alkyl Esters. Synthesis of Acetylenic Ketones and p-Ketonic Esters. By CHARLES MOUREIT and RAYXOND DELANGE (Compt. rend., 1902, 134, 45--47).-Rutyryl'phenyZacetylene, COPr*CICPh, a liquid of sp. gr. 0.998 at 0' and boiling at 135-137' under 9 mm. pressure, is obtained by the action of amyl butyrate on the sodium derivative of ghenylacetylene in presence of ether, and treatment of the product by water.When hydrolysed with sulphuric acid, it yields the P-diketone, 6enxoyZbu~yryZrnethune (phenyl pro& methylens diketone), the copper derivative of which crystallises from alcohol in prisms melting at 132-1334 Benxoylphenylacetylene, COPhGiCPh, which melts at 49.5" and boils at about 200' under 15 mm. pressure, is obtained similarly from ethyl bsnzoate and phenyl acetylene ; when hydrolysed, it yields dibenzoylmethane, melting at 81'. The alkyl esters of P-ketonic acids are readily obtained by the action of ethyl, isopropyl, isobutyl, and amyl acetates and amyl butyrate on the sodium derivative of heptylidene. isoProp3Z ncetoacetate boils at 75" under 15 mm. pressure, and its copper derivative melts at 175"; amyl butyrylbutyrate boils at 125-127' under 9 mm.pressure. According to the author, a complex sodium derivative such as OEt*CPh(ONa)*CiCPh is first formed, and this, in contact with water, yields the acetylenic ketone, alcohol, and sodium hydroxide. I n the New Reactions of Organo-metallic Compounds.ORGANIC CHEMISTRY. 165 case of P-ketonic esters a still more complex disodio-derivative is the first product (compare Abstr., 1901, i, 581 and 442). By JACQUES POLLAK (Moncctsh., 1901, 22, 996-lOOl).- Cotoin yields a mononitroso-derivative and has therefore the constitu- tion COPh*C,H,(OH),*OMe [COPh : OM: : OH : OMe= 1 : 2 : 6 : 41, and not [l : 2 : 4 : 61, since, according to the observations of Kostanecki (Ber., 1887, 20, 3133), a substance with the latter formula should yield a dinitroso-derivative. Nitrosocotoin crystallises from acetic acid in dark red leaves and in glistening, orange-yellow needles, both forms melting at 153-154’.The needles, which lose weight over sulphuric acid, probably contain acetic acid of crystallisation. Special Case of Steric Hindrance. By ERNST BORNSTEIN (Bey., 1901, 34, 4348--4351).-0n treating p-toluidino-p-toluquinone- monotolylimide, C,H,*NH*C,H,O:N*C,H, (Abstr., 1901, i, 375), with hydroxylamine hydrochloride and sodium carbonate in the presence of alcohol, a reaction takes place in which the group (NOH) replaces the group C,H,N:, and p-toluidine and the mono-oxime of p-toluidino- p-toluquinone, C,H,*NH*C,H,O:NOH, are formed.The oxime crystallises in yellowish-red, lustrous leaflets melting a t 1 90°, soluble in alkali hydroxides and carbonates. Concentrated hydrochloric acid dissolves it with a bluish-violet coloration, and concentrated sulphuric acid with a green coloration which becomes violet on the addition of- water. K. J. P. 0. Borneol- and Menthol-glycuronic Acids. By A. BONANNI (Beitr. &em. Physiol. Path., 1901, 1, 304--309).-See this vol., ii, 160. Colophony. By WILHELM FAHRION (Zeit. angew. Chem., 1901, 14, 1197-1208, 1221-1233, 1252--1253).-The colophony used was of American origin. The acid number obtained was 170.2, the saponifica- tion number 177.9, the difference (7.7) being the ether number. Colophony is partially soluble in light petroleum, and the author understands by “ inner acid or saponification number ” the quantity of potassium hydroxide, expressed in milligrams, required for the neutralisation or saponification of 1 gram of the soluble portion.The numbers obtained were 162.7 and 164.3 respectively ; whilst in another series, the ‘( inner saponification number ” was 165.2. The inconstancy of this leads to the conclusion that the portion of colophony soluble in light petroleum does not contain an ester, but another neutral saponifiable substance. The part insoluble in light petroleum consists essentially of an acid, which, however, in presence of excess of alkali unites with more of this than is necessary for the saturation of the carboxyl group. The amount of insoluble residue (in light petroleum) depends on the extent to which the colophony has suffered autoxidation.The colophony also contains unsaponifiable matter, so that the molecular weight of the acid cannot be calculated directly from the “inner acid number ” ; the quantity of unsaponifiable matter increases with the length of time that the colophony is exposed to the air. After C. H. B. Cotoin. G. Y.166 ABSTRACTS OF CHEMICAL PAPERS. determining the percentage of acid in the portion soluble in light petroleum, the molecular weight calculated from the I‘ inner acid number” is about 313. This agrees with the formula C2,H3002 for sylvic acid. It is proved that crystallised sylvic acid is identical with abietic acid, and Mach’s formula, C,,H,,O,, is incorrect. The melting point of crystallised sylvic acid varies considerably (148’ to 164’) according to the method of heating.The constitution suggested CH:C( CO,H)* 7 EX*?”* CMe=yH by Eischoff and Nastvogel, namely, I CH2-CHPr-CH*CH*CHPr*CH2’ seems to satisfactorily express its reactions towards alkali and iodine respectively. The sylvic acid contained in the colophony is in an amorphous condition, and from the fact that crystallised sylvic acid gives an ethyl ester, it is probable that the above constitution represents the amorphous variety, and in the crystallised the carboxyl group lies further away from the doubly linked carbon atoms. From the amorphous sylvic acid, the crystallised modification can be obtained by treatment with aqueous alcohol or by the action of hydrochloric acid on the alcoholic solution.The melting point of the amorphous acid is not very definite, but lies considerably below that of the crystallised. By prolonged heating of the crystallised acid, it is converted into the amorphous variety, and at the same time the molecular weight (calculated from tho acid value) is increased because some other products are formed; in fact, colophony is produced, and this leads to the view that the turpentine contains sylvic acid, and as the terpenes only distil at a comparatively high temperature, this serves t o convert the acid into colophony. Sylvic acid is autoxidisable ; a peroxide, C,,H,,O,, is formed, and this is transformed by intramolecular rearrangement into tetrccoxy- sylvic acid, C,,H,,(OH),O,. The autoxidation, however, takes place in stages, and a peroxide of the formula C,,H,,O, is first produced, which is transformed into dioxysylvic acid, C,o.H,,(OH)O,.The part of the colophony insoluble in light petroleum contains these peroxides. When oxidised with permanganate in alkaline solution, sylvic acid gives an acid which is probably tetrahydroxysylvic acid, C20H32(OH)402. Incidentally, the author has investigated the iodine value of certain phenols, quinones, and peroxides, and concludes that for these it is quite worthless, and for substances in general containing hydroxyl groups its value is always doubtful, By [ALEXANDER TSCHIRCH and] EDUARD KETO (Arch. Phrm., 1901, 239, 548-581).-Copaiva balsams from Maracaibo and Para were examined; also an African variety, illurin balsam, obtained from Hardwickia M a d i in the Niger basin.The balsam was diluted with ether, and extracted completely with 5 per cent. aqueous sodium carbonate, and then a few times with 1 per cent. aqueous potassium hydroxide. From the residue, the ether was distilled off, and the essential oil distilled over with steam ; there remained a mixture of indifferent resens, mostly, but not wholly, soluble in alcohol. These are present in but small amount, whereas the oil forms the chief constituent of the balsam, J. McC. The Resins of Copaiva Balsams.ORGANIC CHEMISTRY. 167 The resin acids were liberated from the sodium carbonate solution with hydrochloric acid, and redissolved in ether; the solution was extracted first with 5 per cent. aqueous ammonium carbonate, then with 5 per cent.aqueous sodium carbonate. I n the case of the Para balsam, there were obtained : from the ammonium carbonate solution, para- copaiwic acid, C,,H3,03, melting a t 145-148", and from the sodium carbonate solution, homoparacopuiwic acid, C,,H,,O,, melting a t 11 1-1 12'. From samples of Maracai bo balsam, p-metacopaiwic acid, c11HI6o2 (or C16H2403 or C,,H,,O,), melting at 89-90', and illwic acid, C,,H,,O,, melting at 128-129', were obtained. From illurin balsam, illuric acid was obtained. The amount of the resin acids varies from 1 0 per cent, of the balsam in the case of the Para variety to 30-40 per cent. in the case of that from Maracaibo. In the case of the Para balsam, about equal amounts of the acids dissolve in the ammonium and sodium carbonate solutions; in the other cases but little dissolved in the aminonium carbonate.Only a small part of the acids could be obtained crystalline, the bulk being amorphous and not entirely soluble in light petroleum. One sample of illuria balsam contained a crystalline sediment con- sisting of illuric acid; in consequence, this acid could be isolated in comparatively large amount and its properties studied. It crystallises in the hexagonal system and has [a], - 58-9" in 5 per cent. alcoholic solution at 189 It is a monobasic acid; its crystalline barium (with 4H,O'?), sodium (with 6H20?), and lead salts and its amorphous silver salt were analysed. It does not contain a methoxyl or ethoxyl group; it will not form an acetyl or benzoyl derivative, or a methyl or ethyl derivative ; it will not react with hydroxylamine or phenylhydrazine ; with phosphorus pentachloride or triiodide, it does not yield a well defined product ; with alcoholic hydrochloric acid, it does not yield an ester, but is transformed into an isomeric acid, C20H2803, melting a t 108-109" ; it reacts with nitric acid, and also with sulphuric acid, but the respective products do not contain nitrogen or sulphur.The acid has an iodine number corresponding with the presence of two double linkings, and in alcoholicsolution it takes up 4 atoms of bromine. It gives thecholesterol reactionsand is not affected by fusion with potassium hydroxide ; in these and other respects it resembles the resin acids of the Conifera?, especially pimaric acid, but it differs from them in that it reduces silver salts in alkaline solution.It resists the action of reducing agents, but it can be oxidised ; excess of alkaline perman- ganate converts i t into carbonic, oxalic, formic, acetic, and other fatty acids, together with a small quantity of an acid which melts at 194'. Illuric acid is probably identical with the acid obtained by Umney and by Peinemann from illurin balsam ; possibly, also with Fehling's oxycopaivic acid. Schweitzer-Rose's copaivic and Strauss's meta- copaivic acids could not be obtained from the balsam. A commercial specimen of ([ copaivic acid" appeared to be identical with metacholestol (Mach, Abstr., 1895, i, 384). C. F. B. Constituents of Koso Flowers. By [RUDOLF BOEHM and] ARTHUR LOBECK (Arch. Pharm., 1901, 239, 672-696.Compare Leichsenring, Abstr., 1894, i, 424 ; Daccomo and Malagnini, Abstr., 1899, i, 158).-By repeated crystallisation from alcohol, commercial16s ABSTRACTS OF CHEMICAL PAPERS. kosin was separated into less soluble a-kosin melting a t 160°, and a little P-kosin, more soluble in alcohol, and melting a t 120'; both have the constitution C,1H2,05(OMe), or C2,H,,05(OMe),. a-Kosin forms a tribenzoyl derivative, C2,H1,0,( OBZ)~( OMe), or C,1N,1~02( OBz)& OMe), ; when heated with 10 per cent. aqueous sodium hydroxide and zinc dust, it is attacked, but only slightly, some methylphloroglucinol methyl ether (compare Boehm, Abstr., 1899, i, 32) being formed ; when it is heated for a few minutes with strong sulphuric acid, the same product is obtained in 14 per cent.yield, together with butyric acid. A commercial ethereal extract; of J'Zores Koso was examined by pounding it with calcined magnesia, extracting the mixture with water, and precipitating the extract with dilute sulphuric acid. .From a solution of the crude product in methyl alcohol, a little anhydro- protokosin, C58H7a0,7, crystallised slowly ; this melts a t 182Oand, when crystallised from alcohol containing a little water, is converted into Leichsenring's protokosin, C,,H,,O,, which contains two methoxyl groups and is thus C,7H,,0,(0Me),. From the mother liquor, by evaporation and treatment with light petroleum, small quantities of kosidin, C,,H,,O,(OMe),, melting at 178", were obtained. The main constituent, however, was kosotoxin, which melted at 6 2 O , and probably has the formula C,,H,,018(OMe)2, rather than half this, since all the other constituents of the drug contain 2 methoxyl groups in the molecule.When heated with aqueous sodium hydroxide and zinc dust, kosotoxin is, to a large extent, converted into kosin, but 'some trimethylphloro- glucinol and dimethylphloroglucinol are formed also. When heated with strong sulphuric acid for a little while, it yields some trimethyl- phloroglucinol and methylphloroglucinol methyl ether. Different samples and extracts of the flowers were found to differ greatly. From one sample of the flowers, a little of a poisonous substance, a-kosotoxiu, was obtained, which melts at 68-69O and seems to have the constitution C2,H,P0,(OMe)2' From a sample of ethereal extract, a microcrystalline 6u bstance was obtained which burns on platinum foil without melting, contains methoxyl, and has the composition ~I,*l,*l,* C, F.B. A Blue Pigment from Crenilabrus Pavo. B~RICHARD VON ZEYNEK (Zeit. physiol. Chem., 1901, 34, 148--152).-A deep blue pigment can be extracted by means of glycerol from the floats of Cvedabrzcs pavo. Its solubilities and optical properties are described ; it is not yet identified chemically. W. D. H. Guaiacum Blue and Aloin Red. By EDUARD SCHAER (Ye&. Natzcr.-GeselE. Basel, 1901, 13, 287-307. Compare Abstr., 1900, i, 512; ii, 583).-Schonbein has suggested that the blue substance formed by oxidising ' guaiaconic acid ' from guaiacum resin is a peroxide similar to ozone. I n accordance with this view, it is now shown that the blue colour is very readily destroyed by a number of chemical agents and is also sensitive to the action of light.The influence of acids is determined by their strength ; sulphuric, hydrochloric, and salicylic acids act the mosh powerfully, then tartaric, citric, and formic acids, whilst benzoic and acetic acids have only a feeble action ; whenORGANIC CHEMISTRY. 1G9 dissolved in solvents not miscible with water, the blue colour is only very slightly sensitive to the action of acids. Alkali hydroxides and carbonates and alkaline salts act much more vigorously than acids; they quickly destroy the blue colour when formed, and entirely pre- vent its formation by the oxidation of guaiacum resin or guaiaconic acid. The action of light greatly facilitates the formation of guaiacum blue by the atmospheric oxidation of guaiacum resin or of the acid pre- pared from it, but it is also very active in bringing about the subsequent spontaneous bleaching of the blue colour; both these processes are regarded as oxidations in which the oxygen of the air is rendered active by the resin and other constituents of the solution.It is pointed out that the formation of ' aloin-red ' from ' barbaloin ' proceeds in a manner very similar to that of 'guaiacum-blue ' from guaiacum resin, and five methods of producing this red compound are described, including two in which peroxides are probably the active agents ; its formation may be used as a very sensitive test, for aloe preparations, f o r cyanogen and halogen compounds (especially hydro- cyanic acid), for free ammonia, for copper, and for peroxides.T. M. L. Basic Properties of Oxygen. By PAUL WALDEN (Ber., 1901, 34, 4185-4202. Compare Collie and Tickle, Trans., 1899, 75, 710 ; Kehrmann, Abstr., 1900, i, 61 ; 1901, i, 484; von Baeyer and Villiger, Abstr., 1901, i, 658, and this vol., i, 112 ; Werner, this vol., i, 50).-The early part of this paper consists of an historical summary ; the latter part is a physico-chemical study of dimethylpyrone. This substance has no appreciable influence on the speed of mutarotation of sucrose ; if a base, i t is a very much weaker one than aniline. The values for the distribution ratios between benzene and water, of picric acid alone, and of picric acid along with dimethylpyrone (1 mol.) shorn that in concentrated solutions (v = 32) a dimethylpyrone picrate is formed which is decomposed into its constituents by dilution.From the difference in the depression of the freezing point of dilute solutions of hydrochloric acid caused by the addition of dimethylpyrone, the affinityconstant, kh, of the latter as a base is found to be approxi- mately 3 x 10-14. Dimethylpyrone comports itself as a relatively good electrolyte in liquid sulphur dioxide at 0' ; the conductivity increases on dilution, owing, probably, to dissociation of the salt formed. into the ions SO, and C7H80,. Both dimethylpyrone and tribromoacetic acid are very feeble conductors when dissolved separately in acetonitrile, but the com- bination of the two in molecular proportions in concentrated solution has a considerable conductivity. Formation of a salt obviously occurs, but the rapid diminution of conductivity with dilution indicates that it has little stability.The conductivity of dimethylpyrone in aqueous solution is very slight ; pD = 202 at 25' approximately, and k = 7.5 x From measurements of the conductivity of aqueous solutions of picric acid a t 2 5 O Y and of aqueous solutions of picric acid (1 mol.) + dimethylpyrone (1 rnol.) diluted (1) with water, (2) with an N/64 - - + + 10-9.170 ABSTRACTS OF CHEMICAL PAPERS, solution of dimethylpyrone, the affinity constant, i&,, of dimethylpyrone, as a base was found to be 2.4 x a value agreeing closely with that obtained by the freezing point method (supra). Dimethylpyrone is thus stronger bthan carbamide and much weaker than aniline. The influence of dirnethylpyrone on the conductivity of aqueous solu- tions of sodium hydroxide shows that it is not only a base but also an acid with an affinity constant k8 = 0.88 x loA1* ; it is therefore of an amphoteric character, and capable of forming both hydrogen and hydroxyl ions.The high value of E obtained with aqueous solutions of dimethylpyrone corresponds in reality to the formation of an '' internal salt." W. A. D. Oxygen Bases. By J~MES WALKER (Ber., 1901, 34,4115-4118. Compare Baeyer and Yilliger, Abstr., 1901, i, 65S).-In order to ascertain the strength of the oxygen bases, dimethylpyrone and tetra- methylpyrone, each of these compounds was dissolved in the equivalent amount of N/lO hydrochloric acid, and 20 C.C.of the solution were mixed with 1 C.C. of methyl acetate in a thermostat at 35". The course of the hydrolysis was followed by titrations with standard barium hydroxide solution, and a comparative experiment was made with carbamide. The calculated velocity coefficient showed that these bases have approximately the same strength, the vahes of the constant for carbnmide, dimethylpyrone, and tetramethylpyrone being 0.00066, 0*00065, and 0.00068 respectively. The hydrolytic experiments carried out in dilute solutions of varying concentration show that the hydrochlorides of carbamide and dimethylpyrone are dissociated to approximately the same extent, in isotonic solutions. Ethylene oxide is often stated to be a strong base, because it is capable of displacing metallic radicles from their salts when dissolved in water.This reaction takes place, however, only when the hydr- oxide thereby produced is insoluble. The first phase of the action is the hydrolytic dissociation of the dissolved metallic salt into free acid and free basic hydroxide, The equilibrium is destroyed by the addi- tion of ethylene oxide, which absorbs some of the acid, and causes further hydrolysis of the salt, the reaction taking place in accordance with the equation C2H,(OH)Cl + M*OH=C2H,0 + H20 + MCl. A certain amount of the hydroxide must be present in solution to main- tain the equilibrium, and if the substance is very insoluble the required proportion is not attained and the decomposition continues until the whole of the metallic radicle is precipitated.If the salt is only slightly hydrolysed, the precipitation is very slow, as in the case of magnesium chloride ; alumina, however, is rapidly thrown down, because its salts are almost completely dissociated in aqueous solution. G. T. M. Double Compounds of the Oximes of Tetrahydropyrone Derivatives. By A. POSNIAKOFF ( J . Buss. Phys. Chm. SOC., 1901, 33, 6 6 7-6 6 9) .-o-DipopoxydiphenyZtetrahyd~opy~one, OH,*CK( C,H,*OPr) C0<CH2 CH(C,R,* OPr) prepared by a method analogous to that employed by Petrenko- Kritschenko for obtaining the corresponding o-diethoxy-compound >o,ORGANIC CHEMISTRY. 171 (see Abstr., 1899, i, 440), separates from alcohol in crystals melting at 112-113'. Its oxime is deposited in white crystals which melt at 170' and dissolve in alcohol but do not combine with it ; with acetic acid, it yields a crystalline compound melting and decomposing a t about 165O ; the oxime also combines with chloroform and with ethylene glycol, giving well-formed crystals, but none of these compounds gives concordant results on analysis. Pyridine and quinoline also dissolve the oxime, but do not combine with it. Petrenko-Kritschenko's supposition, that an increase in the size of the alkoxy-groups present in these derivatives heightens their capacity for combining with solvents, is thus seen to be erroneous (compare also Petrenko-Kritschenko, Abstr., 1900, i, 306).The melting points of the dimethoxy-, diethoxy-, and dipropoxy- compounds are 202O, 133O, and 170" respectively. T. H. P. New Transformation of the two Xanthhydrols into Xan- thenes.By T1oBERT Eoss~ (Compt. rend., 1901,133, 880--882).--Di- nnphthoxanthhydrol, O<CIOH6>CH*OH, C H obtained by treating bromo- dinaphthoxanthene, O<C10H6>CH Br, with an alcdholic solution of potassium hydroxide, crystallises in colourless needles and melts a t 144'. When fused, this substance yields the corresponding ether, (C2,H,,0)20, a compound melting at 2 5 0 O . Dinaphthoxanthhydrol and xanthhydrol, O<CGH4>CH*OH, CH when treated with fuming hydrochloric or hydrobromic acid, regenerate the corresponding chloro- or bromo-xanthen. These xanthen derivatives containing a haIogen behave like the salts of amines, giving rise t o double salts with mercuric and platinic chlorides (compare Collie, Trans., 1900, 76, 1114).The haloid xanthen derivatives, when boiled with absolute alcohol, behave like diazonium salts, exchanging their halogen for hydrogen with formation of acetaldehyde and the corresponding halogen acid. C10H6 10 6 6 4 G. T. M. Basic Properties and Quadrivalence of Oxygen in the Xanthone Series. By ROBERT FOSSE (Compt. vend., 1901, 133, 1218-1220. Compare Abstr., 1901, i, 604, 643 ; and this vol., i, 51). -From a solution of dinaphthoxanthone in acetic acid and platinic chloride, a platinichloride, CH,:(CloH,),:O,P tC1,, is obtained as a bright red, crystalline precipitate. The opinion is expressed that in the mono-halogenated naphthoxanthones previously described (Zoc. cit.) the oxygen atom is quadrivalent, and that the monochloro-deriva tive is represented by the formula C,H,< CH*C I 11 H R .The fact that this compound behaves as a hypochlorite is thus accounted for. 0-c1 K. J. P. 0. Xanthones from 2-Hydroxy-3-naphthoic Acid. Formation of Xanthones. By ERICH STROHBACH (Bev., 1901,34,4136-4146). -Phenyl 2-hydroxy-3-naphthoale, O~*CI,H6*C02Ph, prepared by heat-172 ABSTRACTS OF CHEMICAL PAPERS. ing a mixture of phenol, 2-hydroxy-3-naphthoic acid, and phosphorus oxychloride at 130', crystallises from dilute alcohol in leaflets melting at 128-129' and boiling a t 257-261' under 160 mm. pressure. The acetyl derivative, OAc*C,oH,*C02Ph, obtained from the preceding compound by Liebermann's method, melts at 186.5'. p- ToZyZ 2-hydroxy-3-rtaphthoate, OH* C, ,H,*C02*C,H4Me, crys t allises in pale yellow needles, and melts a t 90-90-5'; it is readily soluble in the ordinary organic solvents.The phenyl ester, when heated a t its boiling point, evolves phenol and yields y-dinaphthoxanthone ; the p-tolyl derivative under these conditions condenses without elimination of p-cresol to form 2-methyl- y-phenonaphthoxanthone, a substance separating from glacial acetic acid in pale yellow crystals and melting a t 158-159'. The communicat>ion also contains a discussion of syntheses in the xanthone series which is not suitable for abstraction. G. T. 31. Heterocyclic Compounds. By ARTHUR KOTZ and OTTO SEVIN (J. pr. Chem., 1901, [ii], 64, 518-529).-A summary is given of the methods which have been employed in the preparation of ring- compounds containing carbon and sulphur. rn-Xylylene disulphide, C,H4< CH2'? is a white, amorphous sub- CH,*S' stance which melts at 115-116'. p-Xplybne disulphide is a white, amorphous substance, and melts a t 168-169'. o-Xylylenethiol condenses with methylene iodide to form the o-me?*- cGptaZ, C,H4<CHi.S>CH2, CH *S which separates from chloroform in thick, transparent, odourless crystals and melts a t 152-153'.The rn-wzev- captal is a white, amorphous, odourless powder, melts a t 73', and is soluble in chloroform. The p-mercaptal is a white, amorphous, odour- less powder, and melts a t 149-150'. p-Xylylenethiol condenses with ethylene bromide to a white, amor- phous compound, C H < CH2*s*(?H2 which melts at 113-114', and ' CH;S*CH,' is insoluble in most solveLts. bu; dissolves readily in chloroform. The compound C,H4<cH2.S.CHi>CH2 CH,*S CH is a white, amorphous com- pound.and melts at 55-56'. The compound from p-xylylenethiol and p-xylyfene br&nide, melts a t 192-193' and is insoluble in all solvents ; molecular weight determinations in nitro- benzene and chloroform solutions gave values corresponding with the formula (CI6Hl4SJ3. T. M. L, Gaze's "Pure Berberine." By HARRY M. GORDIN and C. G. MERRELL (Arch. Pharrn., 1901, 239, 626-637).-The substance ob- tained by boiling acetoneberberine with chloroform and alcohol is not berberine, as Gaze supposed (Abstr., 1890, l o l l ) , but berberine hydro- chloride, C,,,Hl7O4N,HC1,2H,O. Berberine appears to act on chloro- form as alkaline mineral baaes do, converting it into hydrochloric andORGANIC CHEMISTRY.173 formic acids. Piperidine, which resembles berberine in absorbing carbon dioxide from the air, has the same action on chloroform; hydrastine, quinine, and morphine have not (for strychnine, compare Trowbridge, Abstr., 1900, i, 187). Relationship of Canadine to Berberine. By JOHANNES GADAMER (Arch. Pharm., 1901, 239, 648-663).-When the hydrochloride of hydroberberine, which is optically inactive, is treated with half the equivalent amount of ammonium d-o-bromocamphorsulphonate, the salt of a laevorotatory base is precipitated along with hydroberberine, whilst a dextrorotatory base remains in solution. The former melts at 132' and has [a]. - 298.2' in 1 per cent. chloroform solution ; the second melts a t 159-140°, although occasionally, when still impure, it melted a t 132-1333', and has [ a ] D 297.4'.A specimen of canadine melted a t 132-133' and had [a], - 298.0' ; canadine seems, however, also to have been obtained with the melting point 140'. Evidently canadine is identical with the lzvorotatory base obtained from hydro- berberine, and hydroberberine must be either r - or dl-canadine. It has been assumed generally that berberine is a tertiary base. Its compound with methyl iodide, however, is not a true ammonium iodide derivative, but is rather of the same nature as the compounds with chloroform, acetone, alcohol, &c. Moreover, berberine is a strong base, very different from hydroberberine and canadine. On these grounds, the author regards berberine as a quaternary ammonium base, and modifies Perkin's formula accordingly, regarding the alkaloid as C,,HlSO,N*OH, and not C20Hl,04N.C. F. B. C , ~ ~ , 0 , < ~ ~ > c 1 ~ H ~ 0 2 N g c S H , O ~ < ~ ~ ~ C 1 ~ H , O ~ N O O H * Perkin. Gadamer. C. F. B. Bydroxycinchotine. By W. WIDMAR (Monatsh., 1901, 22 976-982).-When boiled with moderately dilute snlphuric acid, the so-called cinchoninesulphonic acid yields a small quantity of /3-iso- cinchonine and a base, C1,H2,02N2, which the author considers to be hydroxycinchotine (hydroxydih~dq~ocirnchonine). The base melts a t 2 68' and has [.ID +200*79' at 15", measured in an alcohol-chloroform solution. The sulphate, (C,,H2,0,N,),,H2S04,8H20, forms white, thick prisms which melt at 233-234'. The hydrochloride, ClQH,,0,N2,HCI, melts at 227-229'. The platinichloride, (Cl,H,,O,N,),,H,PtCI,, crystallises in well-defined, rhombic plates.The base is quite distinct from Jungfleisch and Ldger's hydroxy- cinchonines, and from the isomeric compound obtained by Schmid on fusing cinchotinesulphonic acid. The results agree with Skraup's suggestion (Abstr., 1901, i, 404) that the substance described as cinchoninesulphonic acid is an additive compound of cinchonine and sulphuric acid. G. Y. By JOHANNES GADAMER (J. pr. Chew., 1901, [ii], 64, 566--568).-Controversial; a reply to 0. Hesse (this vol,, i, 51). Hyoscine and Atroscine. T, M. L.174 ABSTRACTS OF CHEMICAL PAPERS, Change of Atroscine into &Scopolamine. By HERMANN KUNZ- KRAUSE (L pr. Chem., 1901, [ii], 64, 569-571).-Confirmation is given by melting point determinations of Gadamer's statement that dry atroscine passes spontaneously into i-scopolamine (A bstr., 1898, i, 92).T. M. L. Ibogine. The Active Principle of a Plant of the Tabernze- montana Genus growing in the Congo. By ALBIN HALLER and EDOUARDHECKEL (Compt. rend., 1901,133,850-853. CompareDgbowski and Landrin, this vol., i, 114).-1bogine, C,6H,20,N2, the active prin- ciple of various species of Iboga (Aboua) growing in the Congo, is extracted from the bark of the stems and roots and also from the leaves of these plants by alcohol, the macerated material having been first digested with hot light petroleum and with chloroform ; it crystal- lises in orthorhombic forms, melts a t 152', and has [ a ] I , --12*88O. The alkaloid has a bitter taste and is alkaline to litmus; it is insoluble in water but dissolves in the ordinary organic solvents.The salts of t healkaloidareamorphous, and the substance is nothgdrolysedon boiling i t with dilute sulphuric acid. Its alcoholic solutions do not reduce Feh- ling's solution or ammoniacal silver nitrate. The product, when de- rived from the stems of the plants, is accompanied by another sub- stance melting at 206-207'. G. T. M. Tropic Acids and the Optical Function of the Asymmetric Carbon Atoms in Tropine and Ecgonine. By JOHANKES GADAMER (Avch. Yharm., 1901, 239, 663--671).--It is known that tropine yields an optically inactive tropic acid when oxidised, whereas both d- and Z- ecgonine (these are not optical antipodes) yield an active d-tropic acid. CH,-CH-CH, CH,* CH*CO,H CH,*CH-OH* C0,H I &Me I kMe bH*OH , I NMe dH*OH I I I I CH,~H--CH, CH~~H*CH,*CO,H CH,.CH-CH, Tropine.Tropic acid. Ecgonine. As even tropine from hyoscyamine is optically inactive, and as naturally occurring compounds with asymmetric carbon atoms are usually active and not mixtures of optical antipodes, i t is probable that tropine is in- active by internal compensation, its two similar asymmetric carbon atoms (printed in thicker type in the formula) being respectively d and 1. By oxidation to tropic acid, the symmetry of the molecule is destroyed, and the two asymmetric carbon atoms are no longer similar, The in- active tropic acid thus obtained is therefore probably susceptible of resolution into active components. The author has effected this resolution by crystallisation of the cinchonine salt from a mixture of alcohol and acetone.From the less soluble portion, 1-tropic acid was prepared with [a], - 14.8' to - 15.2' in 2-6-5 per cent. aqueous solution at ZOO, and melting point 243'; the ammonium salt had [a] + 16.5' in 3 per cent. aqueous solution at 20'. From the mother liquor of the insoluble cinchonine salt d-tropic acid was obtained, but only in the impure state, with [ u ] ~ + 7 * 4 O in 14 per cent. aqueousORGANIC CHEMISTRY, 176 solution at209 As tropic acid from ecgonine has [ u],, + 14*9O to + 15.1° (Liebermann, Abstr., 1891, 749), it is presumably identical with d-tropic acid from tropine, and consequently the two left-hand asym- metric carbon atoms in ecgonine must be respectively d- and 1-, as in tropine and the tropic acid obtained from it, The author also discusses the nature of the two other asymmetric carbon atoms in ecgonine.Ferrous Chloride Pyridine. By PAUL PFEIFFER (Zed. anorg. Chem., 1901, 29, 138--139).-Chromium chloride pyridine (Abstr., 1900, i, 559), when heated with iron, gives large, greenish, transparent crystals, which become yellowish when pulverised. The substance is probably identical with the compound, FeC1,,3C,NH5,2H,0, de- scribed by l-teitzenstein (Abstr., 1900, i, 162), as the ratio of Fe :Cl :C,NH, has been found to be nearly 1 : 2 : 3. 2- and 4Benzoylpyridines and their Derivatives. By A. E. TSCHITSCHIBABIN (J. Russ. Phys. Chem. Soc., 1901, 33, 700-707). -The oxidation of 2 - and 4-benzylpyridines to the corresponding benzoylpyridines is best effected by means of potassium permanganate in neutral solution, the yields obtained reaching about 90 per cent.2-BenxoyZpyridine, COPh*C,H,N, obtained as a liquid boiling a t 317" under 763 mm. pressure, dissolves in water, alcohol, or ether, does not solidify when cooled in ice and salt, and has the sp. gr. 1.1558 at 20°/00 and 1*1710 a t Oo/Oo. It bas feeble basic properties, and dissolves in mineral acids, but all its salts are hydrolysed by large proportions of water with the separation of the base as an oil. ThepZatinichloride, (C,,H,ON),,H,PtCl,, crystallises from water, by which it is partially decomposed, in the form of aggregates of yellow crystals. The picrate, Ci,H,ON,C6~H3O7N3, separates from alcohol or acetone in short prisms with rhombic bases melting a t about 130° with slight decomposition.The phenylhydraxone, Cl8Nl5N3, is deposited from alcohol in faintly yellow crystals melting at 136-1 37'. 2-Benzoylpyridine yields two isomeric oximes, which are formed simultaneously but can be readily separated by crystallisation, since one form is deposited in cubes melting at 150-152' whilst the other isomeride is obtained as tetra- hedra melting at 165-167O. If a large excess of hydroxylamine is employed, the cubic modification is obtained in predominating propor- tion. The configurations of the two forms were not determined. 4-Benxoylpyridine crystallises from light petroleum in thin plates melting at 72' and boils a t 315' under 762 mm. pressure ; it is soluble in water, alcohol, or ether, and also in mineral acids, yielding salts which are readily decomposed by water.The plaatinichloride separates in needles and is completely decomposed by water ; the picrate crystal- lises from alcohol in feathery aggregates, which melt and slightly de- compose at 160' and are soluble in acetone. The phenylhydyaxone separates from alcohol in faintly yellow crystals melting at 181-182'. Two oximes were also obtained in this case, the one obtained in the larger quantity separating from alcohol in prisms melting at 176-177', whilst the other forms small crystals melting a t 152-155'. No trace could be found of the oxime melting at 163-165, described by Freund (Abstr., 1898, i, 43) and by Fulda (Abstr., 1900, i, 53). C. F. B. J. McC. T. H. P.176 ABSTRACTS OF CHEMICAL PAPERS. Ester& of Pyridoylacetic Acids. By ADOLF PINNER [and Db.DONCHI, PAUL DREXLER, and B. BAY] (Ber., 1901, 34, 4234-4253).- A detailed description of the pyridoylacetates (see Abstr., 1900, i, 409). These, when treated with hydrochloric acids, yield the ketones C,NH,* COMe, which, like the ketonic acids, easily form oximes, hydr- azones, and pyrazolones. The cyanohydrins of the ketones decompose when treated with hydrochloric acid, yielding carbinols, C,NH,* CHMeOOH, which reduce Fehling's solution in the cold, Ethyl 2-pyridoylacetate decomposes when distilled, but forms stable salts ; the sodium derivative crystallises in needles and melts and de- composes at 234' ; the potassium and copper derivatives also crystallise in needles, the hydrochloride, subhate, and Izitcr*ate are unstable, but the pkctinichloride crystallises in thick, red plates and melts a t 175".The phenylhydraxone crystallises from methyl alcohol in long, lustrous, yellowish needles, melts a t 122', and forms a picrate which crystallises in yellow, felted needles melting at 197'. 3-a-Pyridoyl-1-phenybyr- ccxolone, N < ~ ~ . ~ - ~ > C H p , crystallises from benzene in small nodules and melts at 179'; the potassium derivative of ethyl 2-pyridoyl- acetate, when oxidised by iodine, yields ethyl di-2-pyridoylsuccinate, C2H2(CO*C,NH,),(C02Et)2, which crystallises in colourless, rhom bic prisms, melts at 137', and forms a platinichloride crystallising in red plates and melting and decomposing a t 217" ; the ester, when treated with ammonia, yields ethyl 2-p~ridoylaminocrotonate, which crystallises from alcohol, melts at 63', and is immediately decom- posed by acids into ammonia and the acetate ; the salts of the acetate react with alkyl haloids forming the alkyl esters, but these are all un- stable liquids ; 2-pyridyl methyl ketone forms a hygroscopic hydro- chloride melting a t 183-185', a platinichloride crystallising in prisms and melting at 220°, and an amorphous nitrute melting and decompos- ing a t 125'.The corresponding cnrbinol was not obtained in the pure state, as the melting point of the recrystallised product varied, probably owing to the formation of its pinacone ; it forms, however, a stable hydrochloride melting at 205', and platinichloride which crystallises, with 1&H20, in yellow prisms and melts at 218' when anhydrous.The unstable ethyl /3-2-pyridoyZpropionate, obtained either by the con- densation of ethyl a-pyridinecarboxylate and ethyl propionate or by the methylation of ethyl 2-pyridoylacetate, forms an amorphous platini- chloride melting a t 175', and when warmed with hydrochloric acid, yields 2-pyridyl ethyl ketone ; the latter forms a hydrochloride which crystallises in small, deliquescent prisms melting at 148-150', and a platinichloride which crystallises in reddish, lustrous prisms melting a t 188'. The analogous 2yyridoylethylacetate easily yields 2-pyridy 1 propyl ketone, which forms a crystalline picrate melting a t 759 2-Pyridyl phenethyl ketone, obtained by treating the sodium salt of ethyl 2-pyridoylacetate with benzyl chloride, is an unstable oil and forms a crystallineplatinichloride melting at 188" and a picrate melting at 129".The pyridoylacetates easily condense with amidine8 forming hydroxy- C,NH,* C(NH,):CH* CO,Et,ORGANIC CHEMISTRY. 177 pyrimidines , 4-a-Pyridyl-6-h ydroxy-2-methy Zpyrimidine, N<CMe-N- > c C5N q, C(OK): CH from acetamidino and ethyl 2-pyridoylacetate, crystallises from alcohol in needles, melts a t 270°, and forms an amorphous, insoluble silver salt. 4-a-Pyridyl-6-hyd~oxy-2-p?~enyZpy~irnidine crystallises in needles, melts at 268', is soluble in alkalis and mineral acids, and forms apkatini- chloride which crystallises in needles melting at 268"; the ethyl ether crystallises in prisms, melts a t 1 20°, and forms a platinichloride melting a t 205' ; the acetyl derivative crystallises in needles melting at 150°, and, when heated, yields the anhydride of the hydroxypyrimidine, (C15H1,N,),0, which crystallises from alcohol in needles, and melts a t 208'.This reaction seems to be a general one for the acetyl derivatives of hydroxypyrimidines. 4-a- Py&@- 6 4 y dr ox y-2-pl8en y I- 5-met?& y l'y r imidine, CPh- from ethyl P-2-pyridoylpr~ponate and benzamidine, crystallises from alcohol in prisms melting at 230" ; it forms an amorphousplatinichloyide melting a t 238', and an acetyl derivative which crystallises in prisms, melts at !04', and yields a n anhydride when heated. Ethyl 3-pyridoylacetate forms a potassium salt which crystallises from acetone in needles, an amorphous copper salt, an amorphous silver salt, and a plcctinichloride.Ethyl 4-pyriclineca?.boxyZate is a colourless liquid which boils a t 1 I 0" under 15 mm., and a t 219-220' under atmospheric pressure, and has a sp. gr. 1.0091 a t 15'; its hydrochloi-ide crystallises in hygroscopic, lustrous needles and melts at 165' ; its platinichloi*ide is an amorphous, orange-yellow precipitate, Ethyl 4-pyridoylacetate crystallises in thick bundles of prisms melting at 54' ; the sodium and potassium derivatives crystallise in needles ; the copper derivative is crystalline, and melts at lS3--184", and the silver derivative is amorphous ; the platinichloride crystallises in orange- red leaflets, and melts a t 156'. The phenylhydraxone crystallises in small needles, and, when heated, is converted into 3-y-py~idyl-1-phenyl- pyraaolone, which crystallises from methyl alcohol, and melts a t 215O ; ethyl di-4-pyridoylsuccinute crystallises in small needles melting at 197". 4-Pyridyl methyl ketone is an oil which boils at 212-214"and is easily soluble in alcohol, ether, or acids ; its hydrochkclride is deliquescent ; the platinichloride crystallises in lustrous leaflets melting at 205", the mercurichloride in needles melting at 183-184", the picrate in leaflets melting at 130°, the phenylhydraxone in yellow needles melting at 150°, and the oxime in lustrous needles melting at 142'.When treated with methyl iodide, the sodium derivative of ethyl 4-pyridoylacetate yields the methiodide of 4-pyridyl ethyl ketone, which, when treated with silver chloride, is converted into the methochloride ; the latter crystal- lises in very deliquescent needles, and forms aplatinichloride which crys- tallises in needles, melt'iag and decomposing a t 205", and an nurichloride which crystallises in yellow, lustrous plates and melts a t 163-1 64".4-Pyridyl propyl ketone is an oil boiling a t 229-231", and forms a piwate which crystallises in long, yellow needles melting a t 96". VOL. LXXXII. i. 0178 ABSTRACTS OF CHEMICAL PAPERS. 4.Pyridyl butyl ketone boils a t 239--240', and its picrate crgstallises in needles melting at 101'. The ethyl ester of 2-methylpyridine-6-carboxylic acid (Abstr., 1900, i, 409) boils a t 133' under 35 mm. pressure, and when treated with ethyl acetate and sodium ethoxide yields sodium 2-methyl-6-pyridoyl- acetate which crystallises in yellow nodules from alcohol ; the acid is an oil which cannot be distilled, the potassium salt crystallises from acetone in long needles.2-Methyl-6-pyridyl methyl ketone is a colour- less oil boili~ng a t 198-200' ; it forms aplatinichloride melting a t 162'. R. H. P. Ethyl Dihydroxycinchomeronate. By SIEGFRIED RUREMANN (Ber., 1901, 34, 4165).-A claim for priority (compare Trans., 1900, 67, 250, and Errera and Perciabosco, this vol., i, 116). W. A. D. Synthesis of 2- and 4-Hydroxyquinolines. By RUDOLF CAMPS (Arch. Pharrn., 1901, 239, 591-610. Compare Abstr., 1900, i, 115, 310).-When o4sobutyrylaminoacetophenone (Bischler, Abstr., 1893, i, 531), CH,*CO*C,H,*NH*CO*CHMe,, is boiled with a dilute solution of sodium hydroxide in alcohol and water, 4-hydroxy-2-isopropyl- quinoline, C 6 H 4 N-- 3 : 3 : 4-trimethyl-2-quinolone, --C*CHMe,' c6H4<$yz&F2, and isobutyryl-o:flavaniline, <CMe:FH N=C*C,H,*NH* CO*C€€Me,' 6 4 are obtained, melting respectively at 196', 143-1 44") and 11 7'.o-Benzoylaminoacetophenone (Bischler, Zoc, cit.), under similar cir- cumstances, yields 4-hydroxy-2-phenylquinoline (Knorr, Abstr., 1888, 1113), together with a little benxoyl-o;fEavaniline, which melts a t 150'. That Bischler could not effect a similar condensation was due to the fact that the alcohol he employed was free from water. A minoacetophenone condenses with ethyl chloroformate, in anhydr- ous ethereal solution, to form ethyl o-acetylphenylcarbamate, CH,*c@C,H,*NH* CO,Et. This melts at 91' and yields a little 2 : 4-dihydroxyquinoline (Fried- lander and Weinberg, Abstr., 1883, 351) when it is boiled with dilute aqueous alcoholic sodium hydroxide, although for the most part it is decomposed into carbon dioxide and aminoacetophenone.With phenylacetyl chloride in anhydrous ethereal solution, amino- acet ophenone condenses to form phen ylacet yLo-urninoacetophenone, CH,*CO*C,H,*NH*CO*CH,Ph. This melts a t 79-80' ; when boiled with dilute aqueous alcoholic sodium hydroxide, it is converted almost quantitatively into 2-?iyd~oxy, 3-phenyL4-methylquino line, CMe: YPh 'GH4<N =C. OH, which melts at 275O, no isomeric 4-hydroxy-2-benzylquinoline being formed. The other results described in the paper have been published already (Abstr., 1901, i, 751). C. F. B.ORGANIC CHEMISTRY. 179 Condensations of Formaldehyde with Pyridine and Quinoline Derivatives.By WILHELM KOENIGS (Be?.., 1901, 34, 4322-4326. Compare Abstr., 1899, i, 74, 389; 1900, i, 189).-The number of hydrogen atoms in a 2- or 4-derivative of pyridine or quinoline which can be replaced by methylol, *CH,*OH, groups by the action of formaldehyde is always lessened by one when the 3- or 5-position contains as a substituent an alkyl group or a benzene nucleus. The same generalisation holds when both 3- and 5-positions are substi- tuted. If, however, the 3- or 5-position is occupied by a carboxyl group, the introduction of methylol is facilitated rather than retarded. Neither 2-methylpyridine nor 2-methylquinoline forms condensa- tion products with paraldehyde, chloral, or benzaldehyde. J. J.S. Condensation of Formaldehyde with 2-Ethylquinoline and with 3 -Methyl-2-ethylquinoline. Ey WILHELM KOENIGS and EDUARD BISCHKOPF (Ber., 1901, 34, 4327-4330. Compare preceding abstract).-2-a-DimethyZoZethyZpuinoline, C,NH,*CMe(CH,*OH),, is formed when 2-ethylquinoline is heated with excess of a solution of formaldehyde under pressure for 48 hours ; it crystallises from petrol- eum in colourless needles melting at 95-96'; the hydrochloride crystallises in colourless needles melting at 178-1 '79" ; the auri- chloride forms pale yellow granules, and the mercurichloride greyish- white flakes. 2-a-MethyloZethyl-3-rnethyZquinolioze, C,,H,,ON, prepared from 3-methyl-2-ethylquinoline and formaldehyde, is a crystalline solid melting at 87-88" ; the platinichloride crystallises in reddish- yellow needles melting and decomposing a t 200-205' ; the mercuri- chloride forms white crystals, the aurichloride pale yellow needles, and the cadmioiodide pale yellow crystals melting and decomposing a t 157-1 60'.Attempts to prepare 2-a-dimethylolethyl-3-methylquinol- ine failed. 3-Methylquinoline does not condense with aldehydes, and thus resembles /3-picoline. K. J. P. 0. Condensation of P-Methylquinaldine [2 : 3-Dimethyl- quinoline] and of 2-Methylquinoline-3-carboxylic Acid with Formaldehyde. By WILHELM KOENIGS and FERDINAND STOCKHAUSEN (Ber., 1901, 34, 4330-4336. Compare preceding abstracts).-Bimethylol-P-methylquinaldine [2-dimethylolmethyl-3- methylquinoline], C,NH,Me*CH(CH,*OH), is prepared by heating 2 : 3- dimethylquinoline with formaldehyde under pressure a t 1 OO', and crystallises with H,O in long needles melting at 85-86'; when anhydrous, it melts a t 106-1 08'.The phtinichloride crystallises in small, yellow needles melting and decomposing at 193O ; the hydro- chloride forms needles melting and decomposing at 200-201° ; the ccuvi- chloride, yellow needles melting at 145' ; the cadmiochloride crystal- lises in white needle8 melting and decomposinglat 207-20907 the rnercuri- chloride in white needles melting at 136O ; thepicrate crystallises in long, yellow, silky needles melting a t 170'. On oxidation with nitric acid, the base yields 3-methylquinoline-2-carboxylic acid (m. p. 144"). The Zactone of 2-trime~hylolmethylquinoline-3-carboxylic acid, C,NH,<C(CH,.OH),>CH', co--0 is formed when 2-methylquinoline-3- 0 2180 ABSTRACTS OF CHEMICAL PAPERS.carboxylic acid is heated a t 100' for many hours with great excess of formaldehyde under pressure, and crystallises from water with K20 in white needles melting a t 167-168O; the hydrochloride crystallises in long, white needles melting and decomposing a t 189-19 1' ; the plutinichloride crystallises, with SH,O, in red needles, plates, or leaflets, which darken a t lS0' and finally melt and decom- pose at 21 6-21 7' ; t.he uurichloride crystallises in long, thin, golden- yellow needles, melting and decomposing at 209--210' ; the picrute forms tufts of yellow, lustrous needles, melting and decomposing a t 142-143'. When oxidised with nitric acid, acridinic acid (Graebe and Caro, Abstr., 1880, 398) is obtained, The lactone is insoluble in sodium carbonate, but immediately dissolves in sodium or barium hydroxide ; carbon dioxide reprecipitates the lactone from these solu- tions.K, J. P. 0. Condensation Products of Homonicotinic Acid [4-Methyl- pyridinecarboxylic Acid] with Formaldehyde and Acet- aldehyde. By WrLHELfif XOENIGS (Ber., 1901, 34, 4336-4342. Compare preceding abstracts).-When homonicotinic acid is heated with formaldehyde solution under pressure a t loo', the lactone of 4-trimethylolmethylpyridine-3-carboxylic acid, 8 H*CH:F*C(CH,*OH),*?H, N-CH: C*CO 0 ' is formed; it crystallises from ethyl acetate in colcurless needles melting at 148'; the LydrochZoride is very soluble in water; the tcurichloride crystallises in yellow, flattened needles or plates, the platinichlovide in orange-red, four-sided plates melting and decompos- ing a t 230' ; the picrate crystallises in pale yellow needles or scales, which melt and decompose at 204'.A rnonoucet?jZ derivative is obtained by boiling the crude lactone with excess of acetic anhydride, and crystallises in colourless prisms which melt at 153-154', and volatilise undecomposed. When heated with aqiieous sodium hydroxide, an amorphous sodium salt is formed. Oxidising agents, especially nitric acid, convert the lactone into cinchomeronic acid. When acetaldehyde (or paraldehyde) and homonicotinic acid are heated at 140-150' under pressure, two substances are formed which can be separated by fractional crystallisation of their picrates from water. From the more soluble picrate (m.p. l43'), the plchhi- chloride of the lactone of ethylol-homonicotinic acid, $ H*CH: ?*CH2* y HMe is obtained in reddish-yellow crystals, which darken a t 240' but do not melt at 278'. From the less soluble picrate (m. p. 186'), a plctinichloride, (C,,H,,O,N),,H,PtCI,, is obtained in yellowish-red crystals melting and decomposing a t 238'. The author believes the base t o be the lactone of crotonylol-homonicotinic acid, fiH*CH:F*CH,* FH*CH:CHMe N-GH : C-CO --0 the base exhibits a blue fluorescence in solution in ethyl acetate; with N-CH : C CO--0 ' 9ORGANIC CHEMISTRY. 181 cadmium chloride, the hydrochloride of the base gives a double salt crystallising in yellow needles, melting and decomp6sing at 230-231'. K. J. P. 0. Acridine. 11. By ALBERT EDINGER and W.ARNOLD (J. p. Chem., 1901, [ii], 64, 471-492. Compare Abstr., 1901, i, 753)-When heated with phosphorus pentachloride and phosphmus oxychloride a t 120-130°, 5-thioacridone yields 5-chloroacridine (m. p. 11 9'). With red phosphorus and bromine, 5-bromocccridine, C13H8NBr, is mainly obtained ; it crystallises in brownish-yellow needles melting at 116', and in the presence of acids is very readily converted into acridone ; the platinichloride forms small, brown, quadratic crystals ; the picrate crystallises in small, yellow needles melting at 212-213" ; the hydro- chloride forms needles decomposing a t 238', and the suZphate yellow needles decomposing at 170'. 5-lodoac~idine, C,,H,NI, cannot be obtained by the action of phos- phorus and iodine on thioacridone, but is prepared by the action of sodium iodide on 5-bromoacridine in the presence of alcohol ; it crystal- lises in bro wnish-yellow needles melting at 169' ; the sulphate crystal- lises in yellow needles ; the platinichloride crystallises in brownish- yellow needles, and the picrate in lemon-yellow needles melting at 204'.5-Benxo~Zthioacridol, C,,H,NBzS, obtained by benzoylating thio- acridone by the Schotten-Baumann method, crystallises in yellowish- green leaflets melting at 209' ; the picrate crystallises in yellowish- green needles melting at 190'. - - C(S*CH Ph) 5-Benx~lthiocccridoZ, C,H,<& >C,H,, prepared by the action of sodium ethoxide on a mixture of benzyl chloride and thio- acridol dissolved in alcohol, crystallises in large, greenish-yellow needles melting a t 109' ; the hydrochloride and nitrate both crystallise in yellow leaflets, the former decomposing at, 140-141', the latter at 106-107' ; the platinichloride is a brownish-yellow solid ; the picrate crystallises in yellowish-brown, lustrous needles melting a t 189-1 go', whilst the suZphate forms yellowish-brown crystals melting and de- composing at 179-180'.5-MethylthioacridoI, C,,H,N*SMe, prepared by treating thioacridol and methyl iodide with sodium ethoxide in alcoholic solution, crystallises in greenish-yellow needles melting at 113-114' ; the hydrochloride forms yellow needles melting at 198' ; the sulphate melts at 156-157'; the nitrate melts and decomposes a t 117-118'; the platinichloride is an ochre-yellow, crystalline powder, and the picrate forms lustrous needles melting at 205'.Alcoholic hydrochloric acid converts it into acridone and methylmercaptan. When thioacridol and methyl iodide are heated under pressure at 75-80', the methyl ether just mentioned is formed; a t 150°, a substance containing no sulphur, but much iodine, is obtained, which, with sodium carbonate, yields mainly acridone ; at 250', acridine hydriodide and iodine are produced. A tetranitroacridone, C13H,0N(N0,),, is formed when thioacridol is heated with concentrated nitric acid under pressure ; it forms insoluble lemon-yellow crystals melting above 350', and dissolves in alkalis with a cherry-red coloration. H. J. P. 0.182 ABSTRACTS OF CHEMICAL PAPERS. Diaminoacridinium Compounds. By FRITZ ULLMANN and A.MARIB (Bey*., 1901, 34, 4307-4316. Compare Abstr., 1900, i, 689).- 2 : 8-Diamino-3 : 7-dimethylacridine (D.R.-P. 52324) crystallises from aniline in yellow needles, dissolves in concentrated sulphuric acid to a yellowish-green solution with a blue-green fluorescence, but is not readily soluble in organic solvents. The hydrochloride, C1,13,6N3cI, forms a microcrystalline, red powder and is only sparingly soluble in alcohol ; the platinichloride is an insoluble, orange powder, and the diacetyl derivative crystallises from aniline in yellow needles. When dissolved in nitrobenzene and treated with methyl sulphate, the diacetyl derivative is converted into 2 : 8-diacetylamino-3 : 7 : 10-tri- methylacridinium methosuZphute, NHAc*CGH2Me<? H- >C,H,Me*NHAc, NMe( O*SO,* OMe) in the form of a reddish-yellow, crystalline precipitate readily soluble in water and also in concentrated sulphuric acid.The chloride, C20H2,O$?,CI7 crystallises from alcohol, in which it is only sparingly soluble, in small, yellow needles. The rzitrccte is an orange-yellow, crystalline powder, and the dichromute, (C20H220,N,)2Cr,07, separates from acetic acid in yellow crystals, Most of the salts are decomposed by ammonia, yielding a pale-coloured, crystalline substance insoluble in the usual solvents, 2 : 8-Bianaino-3 : 7 : 10-trimethylacridi~ium chloride, obtained from the acetyl derivative by the action of hydrochloric acid, or from 2 : 8- diamino-3 : 7-dimethylacridine by transformation into the methosul- phate and then into the chloride, crystallises in large, red needles which are readily soluble in water, yielding an orange-coloured solution with green fluorescence, The nitrute crystallises in red needles, spar- ingly soluble in alcohol, and the dichromate is an orange-red powder, insoluble in alcohol.2-Nitro-4 : 4 -tetramethyldiaminodiphenylmethane (D.R.-P. 79250) crystallises in brick-red needles melting at 95" and readily soluble in most organic solvents. On reduction with stannous chloride, it yields the 2-umino-derivative, which crystallises from a mixture of ether and light petroleum in pale rose-coloured plates melting at 96'. Dinitro- tetramethyldiaminodiphenylmethane (Pinnow, Abstr., 1901, i, 98) melts a t 195" (cow.), not 1 9 1 ~ 5 ~ . Tetramethyldiaminoacridine (Biehringer, Abstr., 1897, i, 73) is readily alkylated by the action of methyl sulphate in toluene solution, and when the product is treated with nitric acid, it yields 2 :%tetra- methyldiamino-l 0-methylacridinium nitrate, NMe,* C , H , < g E a O H 3 * N M e 2 , in the form of long, dark-red needles with a steely lustre.I t dissolves in concentrated sulphuric acid, but is practically insoluble in alcohol. All these acridinium compounds dye tannined cotton with great readi- ness; the coIours obtained are fast to alkalis, and vary from pure yellow t o orange-red. When the acridine derivatives are alkylated with halogen alkyls, they yield, even in neutral solutions, alkylated amino-derivatives and not acridinium compounds.ORGANIC CHEMISTRY. 183 The dye known as patent phosphin (D.R.-P.79703) contains no acridinium salt, but is an alkylated aminoacridine. 3’-Dimethylamino-[Pheno]l: 2-naphthacridine. By FRITZ ULLMANN and A. MARIB (Ber., 1901, 34, 4317-4322. Compare Abstr., 1 900, i, 360, 36 1)-2- Dim?t?~yZaminopheno-l : 2-naphthacridine, J. J. 8. flu NMe2* C,H,<$~C,,H,, or its leuco-derivative may be obtained by the action of P-naphthol on tetramethyltetra-aminodiphenylmethane or on the anhydroformaldehyde derivative of m-aminodimethylaniline, also by the action of dihydroxydinaphthylmethane on m-aminodi- methylaniline and the action of /?-naphthol on m-aminodimethylaniline and paraformaldehyde ; the yields are good. It crystallises from a mixture of benzene and light petroleum in stellate groups of large, yellowish-red needles or in thick, quadratic plates melting a t 185.5’, and dissolves in concentrated sulphuric acid and in alcohol, yielding fluorescent solutions.The hydrochloride forms dark-brown needles soluble in water or alcohol; the nityate forms red needles sparingly soluble in water ; the dichyomate is insoluble in water, and the picrate crystallises in red plates insoluble in alcohol, ether, or benzene. The Zeuco-compound, Ci9Hl8N2, crystallises from benzene in plates melting a t 202-207’ and insoluble in alcohol or ether. 2-Dimethylamino-1 2-methyZpheno- 1 : 2-nc6phthacridinkm chloride, crystallises in red needles, soluble in water or alcohol to duorescent solutions which do not change on the addition of ammonium or sodium hydroxide solutions. The dichromate is a red, crystalline powder in- soluble in alcohol, but readily soluble in acetic acid.Naphthacridones and Naphthacridines. By ERICH STROH- BACH (Ber., 1901, 34, 4146-4158. Compare Mahlau, Abstr., 1896, i, 242).-Naphthacridone is produced by heating 2-hydroxy-3-naphthoic acid with P-naphthylamine at 260-280’ for 10-12 h w r s ; it is ac- companied by smaller quantities of P/?-dinaph t h ylamine, 2-hydroxy-3- nap?~tho-P-nc6phthalide, OH* C,,H,* CO *NH*CloH7, and traces of P-naph- IhyZamino- 3-naph thoic acid, CloH7 *NH*C,,H,* CO,H. When the heat- ing is carried out in the presence of phosphorus oxychloride, the yield of the bye-products is increased. 2-Hydroxy-3-naphtho-P-naphthalide is more conveniently prepared by heating a mixture of methyl 2-hydroxy-3-naphthoate and P-naphthylamine with phosphorus oxy- chloride a t 180-200’; it crystallises from pyridine or water in lustrous, yellowish-white leaflets and melts at 243-244’.P-Naphthyl- amino-3-naphthoic acid crystallises from alcohol or water in yellow needles and melts a t 222-225’. J. J. s. 14-EthyZ-Pl~,a,’/3,’-naphtlzacridone, C , o H 6 < ~ O > ~ l o ~ 6 , NEt obtained by heating the potassium derivative of /?lP,al’~l’-naphthacridone with excess of ethyl iodide at 130-150’, crystallises from acetone in lustrous, yellow needles melting at 204.5-205O. The ethyl compound dissolves in the ordinary organic solvents, its solutions having a green fluor-184 ABSTRACTS OF CHEMICAL PAPERS. escence. The solution of the substance in concentrated sulphuric acid has a reddish-orange colour, and develops a yellowish-green fluorescence on warming.The unsymmetrical constitution is given t o naph thacridone and its ethyl derivative, in view of the fact that it is the a-hydrogen atom contiguous to the P-amino-group which is displaced in condensations with /3-naphthylamine (compare Lellmann and Schmidt, Abstr., 1888, 289, and Morgan, Trans., 1900, 77, 814). 14-lodo-/3,~,aif/31'-napl~thac~idine hydriodide, CiOHG<b I>CloHG, results from the action of hydriodic acid of sp. gr. 1.70 on @?pul'&'- naphthacridone at 160-180' ; it is a reddish-orange, crystalline sub- stance darkening on exposure to light, and decomposing at 180-190'. When heated with acetone or alcohol, it reverts to naphthacridone. NHI N- P1P,u,f/3~-~rapJ~thccc~~di~2e, CloH,<b H>CioHG, produced by heating a mixture of the corresponding acridone and zinc dust in a stream of hydrogen, dissolves in pyridine and less readily in the other organic solvents; it is, however, insoluble in water.The base melts at 205.5-206' ; its solutions in all solvents except concentrated sulphuric acid have a yellowish-green fluorescencs. The preceding base is termed by the author (( /3-naphthacridine," whilst Reed's isomeride melting a t 216' (Abstr., 1886, 1037) is indi- cated by the index leter '' a-." G. T. M. Action of Nitrous and Nitric Acids on Mesityloxideoxime. By CARL D. HARRIES (AnmuZen, 1901, 319, 230--256).-Mesityl- nitrimine, the product of the action of nitrous acid on the stereoiso- meric mesityloxideoximes (compare Abstr., 1898, i, 400, 568 ; 1899, i, 566), when reduced with zinc dust and water, yields trimethyldihydro- pyrazoline boiling a t 63-64' under 23 mm.pressure (compare Curtius and Wirsing, Abstr., 1894, i, 248). This base is also obtained by reduc- ing the hydrogen chloride compound of the nitrimine ; the nitrimine CMe*r>o CMe,N may have one or other of the following formuls, CH< or CMe,:CH*CMe:N<& 0 isoMesitylnitrimine (ketotrimetJyZdihydroisooxazoZeoxime), X C M e 0 'CMe,>c:NOH, produced by heating mesitylnitrimine with water a t 1 20', crystallises from chloroform in white leaflets and melts at 156-157'; it has the properties of an oxime, forms a sodium derivative, does not reduce Fehling's solution until after hydrolysis with dilute sulphuric acid, and is not affected by bromine or by zinc dust and water.Its cccetyl derivative crystallises from light petroleum or alcohol, and melts at 68-69'. ? *CMe, Ketotrime thyzdihydvoisooxaxole, N-cMe>CO, - obtained by mixingORGANIC CHEMISTRY. 185 the oxime with cold concentrated nitric acid and heating the oily product, C6H905N3, either by itself or with acetic anhydride, is a colourless, refractive oil boiling a t 50-51' under 16 mm., and at 151' at the ordinary, pressure; it has a pleasant odour, and a sp. gr. 1.020 at 37'. On treatment with hydroxylamine, it regenerates iso- mesitylnitrimine and with phenylhydrazine, the phenyliqdraxone, 0 *CMe, N-CMe>C:N*NHPh, - is obtained, which crystallises from alcohol or light petroleum in yellow needles melting at 140-141'.isoMesitylnitrimine, when boiled with dilute acids, is completely broken down, and nothing but a small amount of acetoxime is obtained. Mesitylglyoximpeyoxide nitrite, O < ~ ~ ~ > C * C H , * C M e , * 0 *NO, pro- duced by gently warming mesityloxideoxime in dilute nitric acid of sp. gr. 1.1, crystallises from methyl alcohol, acetone, glacial acetic acid, or acetic anhydride in golden-yellow leaflets or needles, and melts at 12s-129'. a-NitvomesityZ-P-aniZ, N02*CH,*C(NPh)*CH:CMe2, prepared by add- ing aniline to the preceding nitrite suspended in dry ether, crystal- lises from the ordinary organic solvents in yellow leaflets melting a t 84-85' ; it yields a-nitromesityloxide, CMe,:CK*CO*CH,*NO,, and aniline on hydrolysis with dilute mineral acids, this product being a yellow oil boiling a t 95-96' under 23 mm.pressure and having a sp. gr. 1.212 at 27.3". The nitro-group in this compound is attached to a primary carbon atom, the substance giving a well-defined sodium derivative, The nitro-compound decolorises bromine, and when treated with semicarbazide and aniline gives rise t o the semicarbazone and anil derivatives of nitroacetone respectively ; the former of these crystallises in needles melting at 163-1664', and the latter, which is also obtained by the action of aniline on mesitylglyoximeperoxide nitrite in glacial acetic acid, crystallises from alcohol or light petroleum in amber- coloured needles or prisms sintering a t SO' and melting a t 87". The anil derivative is quantitatively hydrolysed into nitroacetone by heat- ing with 25 per cent.sulphuric acid. The foregoing reactions constitute a ready method of preparing nitroacetone (compare Lucas, Abstr., 1900, i, SZ), 100 grams of mesityloxide furnishing 35 grams of the product. Nitroacetone boils a t 103-104' under 24 mm., and a t 185-190' under the ordinary, pressure, When distilled in large quantities, it decomposes at 165' into acetic acid and a substance having a n odour of prussic acid, probably cyanic acid. The sodium derivative, COMe*CH: NO,Na, separates in colourless crystals, and the silver derivative in yellow needles. The nitro-com- pound neither reduces ammoniacal silver nitrate nor forms an oxide with nitrous acid ; it yields acetylmethylnitrolic acid (compare Behrend and Tryller, Abstr., 1895, i, 201).a-Nitro-y-benzylideneacetone, CHPh:CH*CO*CH,*NO,, produced by condensing nitroacetone with benzaldehyde in a 5 per cent. solution of sodium hydroxide, crystallises from alcohol in yellow plates, sinteru at S3', and melts at 87-88O. G. T. M.186 ABSTRACTS OF CHEMICAL PAPERS. Azothionium Compounds. By FRIEDHICR KEHRMANN ( Ber., 1901, 34, 4170-4174).-Azothionium salts of the type C,H4<ix>c6H49 analogous to the azoxonium salts (compare Abstr., 1900, i, 61 ; 1901, i, 484; Werner, Abstr., 1901, i, 50) are obtained by oxidising thiodiphenylamine derivatives with acid oxidising agents. [With V. V~s~~~.]-P?henazothioniurn ferrochloride, (C,,H,NSCl),,FeCI,, obtained by adding a cold alcoholic solution of thiodiphenylamine t o ice-cold alcoholic ferric chloride, forms brownish-green crystals.Phenaxothioniurn hromide, C~H~<:B>C~E*, obtained by mixing cold alcoholic solutions of thiodiphenylamine and of bromine, is a coarsely crystalline, olive-green powder. Yhenaxothionium picrute is a greyish- green, sandy, crystalline powder. By WALTHER BORSCHE (Bey., 1901, 34, 4297-4302. Compare Kipping, Proc., 1900, 6 3 ; Young, ibid ., 73) .-When salicylsemicarbazone is heated a t 250-300', it yields o-hydroxybenzylideneazine ; when boiled with aniline for some time, the products are the same azine and s-diphenylcarbamide, or when the boiling is continued for only a short time, a third product, phen y 1-o-h ydroxybenzy lidenesemicarbazone (Curtius and Hof mann, Abstr., 1896, i, 647), is also formed. Acetophenonesernicurbcczone crystallises in colourless plates melting and decomposing at 198-199'; when boiled with aniline, i t yields acetophenonephenylcavhamic acidhydrcczone melting a t 187-1 88'.Aceto- phenonesemicarbazone and o-toluidine yield di-o-tolylcarbamide and ucetophenone-o-tolylcarbamic acid hydrazone, W. A. D. A New Reaction of Semicarbazones. CMePh: N*NH*CO*NH*C6H4Me. The latter crystallises from alcohol in long, colourless needles, melts at 211-212', and is not readily converted into the corresponding mine. Acetonesemicarbazone and P-naphthylamine yield acetone- P-naphthylcarbamic acid hydrazone in the form of pale red needles melting at 192-1 93' and di-P-naphthylcarbamide. The reaction is best carried out in the presence of dimethylaniline. Tertiary bases do not react with semicarbazones in the same manner as aniline.J. J. S. Pyridazines. By ALFRED OPPENHEIN (Ber., 1901,34,4227-4234. Compare Abstr., 1899, i, 390)-Disubstituted pyridazines have been synthesised by the action of hydrazine on y-ketonic acids of the formula X*CO*CH,*CHR*CO,H. BenxoyZdimetl~ylmuZonic acid, CH2Bz*CMe(C02H),, obtained when the sodium compound of ethyl isosuccinate suspended in ether i s treated with bromoacetophenone, is a yellow, crystalline substance which melts a t 145' with the evolution of carbon dioxide, yielding an acid which is identical with the P-benzoyl-a-methylpropionic acid obtained by Klobb (Abstr., 1900, i, 498) by the condensation of pyrotartaric anhydride with benzene. p-Benzoyl-a-methylpropionic acid condenses with hydrazine, formingORGANIC CHEMISTRY.187 N-CPh 3-phenyZ-5-methyZpyridaxinone, NH<Co.CHMe>CH2, which crystal- lises in rhombohedra, melts at 1575', is soluble in most organic solvents except light petroleum, and when treated with bromine yields the corresponding pyridaxone, which crystallises from alcohol in small, colourless needles and melts at 189-190'. On treating the latter with phosphorus oxychloride, it yields 6-chZoro-3-phenyZ-5-methyZpyrid- axine, which crystallises from alcohol in slender needles, and melts at 141-142', and, when treated with hydriodic acid, yields 3-phenyl- 5-methyZpyridaxine, which crystallises in long, silky needles and melts at 95'; the hydriodide of the latter crystallises in yellowish-brown needles, sinters a t 90°, and is completely molten at 140°, and the chromate crystallises in slender, felted needles, The chloropyridazine, when treated with sodium e t hoxide, yields 6 -ethoxy-3-phen yZ-5 -methyl- pyridazine, which crystallises in slender needles, melts at 103-104', and forms an insoluble azcrichloride, a chromate, and a picrate melting at 150" ; the analogous 6-methoxy-compound crystallises from alcohol in slender, felted needles, and melts at 60-61' ; 6-uniZino-3-phenyl- 5-methylpyridaxine, obtained when the chloro-compound is treated with aniline, is a white, crystalline substance which melts at 173-174', atid forms an insoluble chromate.Derivatives of Pyrimidine. By WILLIAM 0. EMERY (Ber., 1901, 34, 417S-41Sl).-When dinluric acid is heated with phosphorus pentachloride, initially on the water-bath, and finally in a sealed tube for half an hour at 120', it is converted into the same tetrachloropyrimidine as was formerly obtained in the same way from alloxan (Ciamician and Magnaghi, Abstr., 1886, 226); the latter melts at n temperature slightly higher (70") than formerly given (67-68'), and is not changed by distilling with zinc dust or by sodium amalgam.When heated with sodium iodide in alcoholic solution for 10 hours, it is converted into a mixture of IrichZo?.oiodopyrisnidi~e, C,N,Cl,I, and dichlorodi- iodopyrirnidine, C4N2C1,T2 ; these are separated on recrystallisation from methyl alcohol, the latter being obtained in needles melting at 159', and the former in yellowish nodules melting a t 93-94'. (retrabromopyriiidine, C,N,Br,, obtained from dialuric acid and phos- phorus pentabromide, is volatile with steam, and forms snom-mhite crystals melting a t 165-166".When tetrachloropyrimidine is boiled with zinc dust and water for a long period, the whole of the halogen is removed and pyrimidine formed (compare Gabriel and Colman, Abstr., 1899, i, 638). R, H. P. W. A. D. Nitroprusside, Ferrocyanide, and Ferricyanide of Antipyrine. By M. C. SCHUYTEN (Chem. Centr., 1901, ii, 1362 ; from Hundel. van het vGfde VZaamsch Natuur Geneeskundig C'ongres, Bvugge, 190 1 ).-These antipyrine salts are readily prepared by processes of double decomposition. The nitroprusside, (CllH,20N2)2,H,Fe(NO)(CN),,H,0, is a pale brown, amorphous substance, melts a t 77-78", is soluble in water, and has an acidreaction. Aqueous solutions become blue on exposure to air and solutious in acetone green.Antipyrine ferrocyunide, (C,,H120N2),,H4Fe(CN),'188 ABSTRACTS OF CHEMICAL PAPERS. is a white substance. forms yellow, needle-shaped crystals, and is readily soluble in water. E. w. w. Antipyrine ferricyanlde, (C,lHl,ON,) ,H,Fe(CN)v Compounds of Antipyrine with Ferric Haloids. By M. C. SCHUYTEN (Chern. Centy., 1901, ii, 1362-1363; from IZundel van het @fde Vlaarnsch Natuw Geneeskzcndig Congres, Brugge, 1901).- Antipyrine ferric chloride (Hasse's ferropyrine, Pharm. Cent?-.-H., 36, 59), ( Cl1H1~0N2),FeCl,, prepared by mixing aqueous or ethereal solutions of ferric chloride and antipyrine, is an orange-yellow powder, which becomes brown at 150°, melts a t 2 0 5 O , and is readily soluble in water.The aqueous solution has an acid reaction, and when warmed gives a brown precipitate which partially redissolves on cooling. The action of many reagents on the aqueous solution of antipyrine ferric chloride is described in the original paper. Antipyrine ferric bromide and antipyrine ferric iodide cannot be prepared by mixing the components or by double decomposition, and are doubtless unstable under ordinary conditions. E. W. W. Synthesis of Uracil, Thymin, and Phenyluracil. By EMIL FTSCHER and GEORG ROEDER (Bey., 1901, 34, 4129. Compare this vol., i, 124).-4-Phenyluracil, prepared by the authors from its hydro- compound, was first obtained by Warmington from ethyl benzoylacetate and carbamide (Abstr., 1893, i, 369). Weidel and Roithner had already obtained 4-methylhydrouracil in an impure form.and hvdrouracil has been described under the name of P-lactilcarbamide by Cengfeld and Stieglitz (Abstr., 1893, i, 632). G. T. M. Benziminazoles. By OTTO FISCHER and MORITZ RIGAUD (Bey., 1901,34,4202-4209).-s-Dimethylphenylenediarnine combinesreadily with aromatic aldehydes a t the ordinary temperature with elimination of lH,O ; the products are easily hydrolysed into their components, however, by dilute acids and alkalis, The compound, C,,H,,N2, obtained from benzaldehyde, crystallises from methyl alcohol and melts a t 102-1 03' ; the derivative, Cl,H1,0N2, obtained from salicylaldehyde forms short, colourless prisms and melts a t 155'. [With W. K~~~.]-l-PhenyZbenximinazoZe, C,,H,,N,, obtained by boiling o-aminodiphenylamine with formic acid for several hours, crystallises from light petroleum in concentrically grouped needles and melts at 97' ; the platinichloride forms reddish-yellow prisms or leaf- lets, the mevcurichloride long,.pike-shaped crystals, and the picrate, slender needles which change into prisms. The meihiodide, C,, H,,N,I, crystallises from water in colourless leaflets, melts a t ZOO', and with warm aqueous sodium hydroxide yields the carbinol-base, 1-pheny1-3-metZiylbenximinaxoZeoZ, C , H , < ~ ~ ~ > C H * O H ; this crystallises from dilute alcohol in colourless, flat prisms, melts a t 168', and is only very slowly hydrolysed by boiling aqueous sodium hydroxide. Ultimately, small quantities of an oily o-nzetlhylamino-ORGANIC CHEMISTRY. 189 diphenylamim are obtained, the hydrochloride oE which forms beautiful, colourless needles.4 : 5-Diamino-m-xylene condenses readily with formic acid, giving 4 : 6-dimethylbenximinuxole, which crystallises from chloroform, on adding light petroleum, in silvery leaflets, melts a t 1 7 5 O , and yields a crystalline hydrochloride, platinichloyide, and picrate. When heated a t 130°, with methyl iodide dissolved in methyl alcohol, it yields the 1 : 3 : 4 : 5-tetrumethylbenximinaxole methiodide, CllH15N21, which crystallises in white needles and melts a t 278-279'; the derived carbinol base, C,H,Dle,<~~~>CH*OH, crystallises from light petroleum in colourless, acutely truncated prisms, melts a t 135", and is not affected by boiling aqueous alkaline hydroxides, 1 : 4 : 6-Trimethylbenximinuxole iodide is formed as an easily soluble substance along with the foregoing less soluble, higher methylated derivative, when the parent benziminazole is simply warmed with methyl alcoholic methyl iodide ; with potassium hydroxide, it yields a base which crystallises from light petroleum in colourless prisms and melts at 70" ; the platinfchloride forms reddish-yellow needles.p-Nitro-m-tolyl ethyl ether crystallises from light petroleum in colourless prisms, melts a t 55" (Staedel and Kolb, Abstr., 1891, 186, give 51"), and when heated for 10 hours with alcoholic ethylamine, is converted quantitatively into p-nitro-m-eth y It oluidine, which crystal- lises from dilute alcohol in yellowish-red needles and melts a t 60". m-Ethyl-o-tolylenediamine, obtained by reduction of the nitro-compound with tin and hydrochloric acid, crystallises from light petroleum in long, colourless needles, melts at 59") and on boiling with acetic acid yields HLi bner's 2 : 6-dimethyl-1-ethylbenziminazole (compare 0.Fischer and Schilling, Abstr., 1893, 283), which thus has the structure vMe:CH* $NEt CH=CH*C--N >CMe. The isomeric 2 : 5-dimethyl-1-ethylbenz- C Me : C H C-N, iminazole is shown to have the structure /-,H=CH,-)NEt>CMe by its formation from 4-ethyl-3 : 4-tolylenediamine and glacial acetic acid ; it crystallises from light petroleum in long, thin needles, is very hygro- scopic and melts a t 86-87', not at 165-166' as stated by Schilling, whose compound probably contained, or consisted of, 3 : 4-diacetyl-bethyl- tolylenediamine, which melts, when pure, at 177".The platinichloride of the p-azole crystallises in reddish-yellow prisms decomposing at 25 10, the aurichloride in yellow tufts melting at 129-130", and the nitrate melts a t 133'; the rnercurichloride melts at 190°, whilst the picrate forms small, bright yellow prisms, melts at 260-261", and is very characteristic. The picrate of the a-azole melts at 233-233", and the mercurichloride a t 149-150'. On heating the hydrochloride of either the a- or /3-azole on the sand- bath, ethyl chlorideis evolved, and the same ethenyl-3 : 4-tolylenediamine (m. p. 198') is obtained in both cases ; the latter is thus tautomeric according to von Pechmann's views. W. A. D. Aminolophine. By JULIUS TROEGER (J. pr. Chem., 1901, [ii], 64, 530-546) .-m-Nitrolophine, CPh-N EPh*NH>CG6H,-N0,, produced to-190 ABSTRACTS OF CHEMICAL PAPERS.gether with benzilam from m-nitrobenzaldehyde and benzil in presence of ammonia, is a crystalline powder almost insoluble in the ordinary organic solvents, and does not melt a t 295'. m-Aminolophine, @ ~ ~ ~ ~ > C , H 4 * N H 2 , forms minute, thread-like crystals, becomes brown at about 280', and blackens and melts a t 290' ; it gives a dirty-white precipitate with phosphotungstic acid, a red- brown precipitate with potassium bismuthoiodide, and a white precipitate with potassium mercuric iodide, a dark yellow precipitate with potassium zinc iodide, a white precipitate with lead acetate, and a dark-brown, crystalline precipitate with iodine in potassium iodide ; the hydrochloride, C2,H17N3,2HC1,separates in needles on adding concen- trated hydrochloric acid to a solution of the base in the dilute acid; the plutinichloride, ~~C2,H17N,)2,H2PtC16, forms a pale flesh-coloured precipitate ; the nitrate, C2,H17N2,HN03, crystallises in needles ; the sulphate, is only slightly soluble in water, and separates in clusters of crystals ; the picrate, C2,H,7N3,C6H3O7N3, forms brownish-yellow needles, and melts and decomposes at 200'; the aurichloride forms a brown precipitate.m-Aminolophine tetraiodide, C2,H7N,H14, forms brown needles, and decomposes when heated above 200'. The product of the action of methyl iodide on m-aminolophine appears to contain loosely combined hydrogen iodide, and the formula is provisionally assigned to it.p-Aminolophine crgstallises in minute needles and becomes brown and decomposes gradually above 180' ; the hgdrochlorida, C2,Hl7N,,2HC1, forms small, compact crystals ; the nitrate forms white needles, the platinichlovide is a dirty brown-yellow precipitate, and the aurichloride a dark brown precipitate. o-Aminolophine is a white, crystalline substance ; the hydrochloride, C,,H17N,,2HC1, forms minute, white needles. C21H15N3Me31,H1,H20 T. M. L. Ketone Reactions of y-Lutidone. By PAVEL Iw. PETRENKO- KRITSCRENKO and S. MOSSESCHWILI (J. pr. C'hem., 1901, [ii], 64, 496). -With phenylhydrazine, y-lutidone yields a hydraxoize, C13H15N3, as crystals melting at 125'. With hydroxylamine, an oxime is not formed, but a crystalline substance, C7H,,0,N, which melts a t 249O.K. J. P. 0. Partial Hydrolysis of Triaminomesitylene. By FRA NZ WENZEL (Monatsh., 1901,22,983-985).-Triaminomesitylene trihydro- chloride, when boiled with glacial acetic acid, yields the hydrochloride of diaminohydroxymesitylene ; the base forms yellow needles, melts at 94-96', and with acetic anhydride yields the triacetyl derivative which has been previously obtained in the endeavour to acetylise tri- aminomesitylene (Abstr., 1898, i, 580). G. Y. Oxidation of Hydrazoximes. VI. By GIACOMO PONZIO (Gazzetta, 1901, 31, ii, 413-416. Compare Abstr., 1898, i, 386; 1899, i, 717, 827 ; 1900, i, 588 ; 1901, i, 169).-Diacetyl-p-tolylhgdr- awxime, NOH:CMe*CMe:N,H*C,H,Me, prepared from isonitroso-ORGANIC CHEMISTRY. 191 methyl ethyl ketone (diacetylmonoxime) and p-tolylhydrazine, crystal- lises from alcohol in yellowish prisms melting at 169O, and is soluble in chloroform, benzene, or ether.4 : 5-Oxy-1-p-tolyl-3 ; 4-dimethyl-1 : 2 ; 5-osotriasole, RMe C Me-- *<h*N(C,H,Ble)*N ' obtained by treating a chloroform solution of diacetyl-p-tolylhydraz- oxime with yellow mercuric oxide under the conditions previously given (loc. cit.), crystallises from ether in pale yellow, shining prisms melting at 92-93O, and is soluble in water, light petroleum, alcohol, or chloro- form. It is a mono-acid base, and has a weak basic reaction, its hydrochloride being instantly decomposed into its components in con- tact with water. Diacetyl-o-tolylhydrazoxime, C11Hl,0N3, separates from alcohol in faintly yellow, flattened prisms melting a t 175" and is soluble in chloroform or ether.Diacetyl-P-naphthylhydrazoxime, CI,Hl,ON,, crystallises from chloro- form in rose-red lamina melting at 1 8 4 O , and is soluble in acetone. T. H. P. A Solid Diazonium Cyanide ; Diazoiodides. By HANS EULER and ARTHUR HANTZSCH (Bey., 1901, 34, 4166-4169).-On adding concentrated potassium cyanide solution to a solution of anisole- diazonium chloride cooled to - 80' and prevented from solidifying by the addition of alcohol, the syn-cyanide alone is formed, the low tempera- ture apparently failing to influence the equilibrium between the syn- diazocyanide and diazonium cyanide ; if, however, a solution of anisole- diazonium hydroxide, prepared by precipitating a solution of the bromide with moist silver oxide at Oo, be saturated with hydrogen cyanide and concentrated by freezing out and evaporating in a vacuum at O--SO, crystals of the diaxonium cyanide, OMe* C6H,*N,*CN, HCN,BH,O,.separate. With a dilution vlo0, the mol. conductivity is 88, the salt thus electro-chemically resembling potassium cyanide ; as it combines instantaneously with @naphthol, a diazonium group is present. All three possible diazo-forms have thus been realised in the anisole series. The soliddiazo-haloids are to be regarded as solid solutions of colourless diazonium haloids and coloured syn-diazo-salts ; the explosiveness is proportional to the depth of colour. The chlorides are colourless and not explosive, the bromides slightly, and the iodides strongly, coloured and explosive. The colour of the iodides depends on the temperature of formation, as shown in the case of the following salts precipitated from aqueous methyl alcoholic solutions by lithium iodide.Anisolediazoiodide.. . , . . . . . . . . . , . . . , p-Bromobenzenediazoiodide . . . . . . 2 : 4-Dibromobenzenediazoiodide . At the ordinary At - 60". temperature. Yellowish-white. Golden-yellow. Lemon-yellow. Orange. Golden-yellow. Dark orange, W. A. D.192 ABSTRACTS OF CHEMICAL PAPERS, New Method of Producing the Azobenzoic Acids. By JOHANN MAIER (Bey., 1901, 34, 4132-4134).-The\ three nitrobenzaldehydes, when heated with excess of aqueous sodium hydroxide solution (40' Be.), are first transformed into molecular proportions of nitrobenzoic acid and nitrobenzyl alcohol, but these products subsequently interact, yielding the corresponding azobenzoic acid, CO,H*C,H,*N,*CGH,*CO,H. G.T. M. The Influence of the Medium, especially of Inorganic Substances, on the Properties of Proteids. By JOHANNES STARKE (Zeit. Biol., 1901, 42, 187--227).-The influence of the medium (milieu) on the properties of proteids, especially that of heat coagula- tion, is discussed at length. Another point discussed is the influence of the medium on the solubilities and precipitability of acid and alkali-albumin. The conclusion arrived a t is that there is no such influence exercised, but that the proteid molecule is as constant in its properties as other chemically defined substances. Proteids. 11. By ADOLF JOLLES (Uonatsh., 1901, 22, 991-995. Compare Abstr., 19Ol', i, 490).-The author suggests that the greater the proportion of the total nitrogen of a proteid which, on oxidation, is separated as carbamide, the greater the value of the proteid as a food- stuff.The absorption of nitrogen by the human organism being taken as a guide, i t is shown that casein (which yields 73 per cent. of its total nitrogen as carbamide) is ntilised t o a greater extent than is fibrin (which yields only 45 per cent.). W. D. H. G. Y. The Aromatic Group of the Proteid Molecule. B~VIRGILIO DUCCESCHI (Beitr. chem. Physiol. Path., 1901, 1, 339-346. Compare Fischer, Abstr., 1901, i, 745, 7SO).-When proteid is decomposed in hydrochloric acid solution by nitrous acid, cinnamic acid is a constant product. This points to the presence of a phenylalanine group in the proteid molecule, By KARL SPIRO (Beit?*.chem. Physiol. Path., 1901, 1, 347--356).-Cinnamic acid is obtainable from gelatin as well as from various forms of proteid (see preceding abstract). Nencki has previously shown that phenyletbylamine is a product of t'he putrefaction of gelatin. By CARL NEUBERG (Bey., 1901, 34, 3963-3967. Compare Blumenthal, Abstr., 1899, i, 465, 968).-The albumin from yolk of egg contains a group yielding glucosamine, since, when hydrolysed with hydrobromic acid and the products then oxidised with nitric acid, norisosaccharic acid is formed. This is best isolated in the form of its cinchonine salt (this vol., i, S4). A salt isomeric with cinchonine norisosacchnrate is also formed, This is more readily soluble in alcohol, burns brown at 190°, decomposes a t 230°, and has [aJD + 150' ; it is probably iden- tical with cinchonine d-saccharate.Quinine d-succharate melts a t 1 7 4 O , and closely resembles the cinchonine salt, W. D. H. The Aromatic Group in Gelatin. W. D. H. Carbohydrate Groups in Albumin from Yolk of Egg. J. J. S.ORGANIC CHEMISTRY. 193 Serum-albumin of Ox Blood. By A. HOUGARDY (Frau. du lab. de L. Predericq, Jigye, 1901, 6, 213-223 ; from Arch. de Biol., 18)- According to Halliburton, the albumin of ox blood can be differentiated into two fractions by heat coagulation. The main fact is confirmed, but the author doubts whether this is sufficient proof of two different proteids. No other difference between the proteids is alleged to exist. Moreover, a single and total coagulation is obtainable a t 65’ if tlmt temperature is maintained for 5 or 6 hours.By PROSPER VAN DE KERCKR~F. (Frau. du lab. de L. Tredericq, Ligge, 1901, 6, 21-25; from Arch. cle Biol., 15, 640). -The serum-globulin of mammalian blood can be separated by frac- tional heat coagulation into three (in the dog into four) parts. No other differences are shown to demonstrate that these are separate pro- teids. No reference is* made to recent work, which has shown that sorum-globulin can be differentiated by dialysis into euglobulin and pseudcglo bulin. W. D. H. Proteid Chemistry. Part I. A hitherto undescribed Pro- duct of Tryptic Digestion. By F. GOWLAND HOPKINS and SYDNEY w. COLE (J. Physiol., 1901, 27, 418-428).-The Adamkiewics reaction depends on the presence of glyoxylic acid in the acetic acid used.During tryptic digestion, a, crystalline product is produced which gives the reaction in a typical manner. The substance has the formula CllH1202N2; it yields skatole and indole when heated, and gives the pine-splinter reaction directly. The formula corresponds either with an indoleaminopropionic acid, or a scatoleaminoacetic acid, but this requires further investigation. The substance yields also a red deriv- ative with bromine, and is in fact the hitherto unisoIated tryptophan, W. D. H. Serum-globulin. W. D. H. Amounts of Hexone Bases obtained from Vegetable Proteids. By ERNST SCHULZE and ERNST WINTERSTEIN (Zeit. physiol. Chena., 1901, 33, 54’7-573. Compare Kossel and Kutscher, Abstr., 1901, i, 107).- The yields of histidine, arginine, and lysine obtained by the action of hydrochloric acid on the proteids from the following seeds, have been determined :-Picea excelsa, Pilaus silvestris, P.maritima, Cucurbita Pepo. Conglutin from the seeds of Lupinus Zuteus and other lupins, legumin from Pisum sativum, and edestin have also been hydrolysed and the percentages of bases determined. Except in the case of legu- min, the amount of arginine is much greater than that of histidine or lysine, and is a t a maximum in the proteid from Pinus silvestris and P. maritima and in edestin. The histidine was estimated as its hydrochloride, C,H,O,N,,HCl,H,O ; the arginine as the copper derivative, (C6H1,0,N,),,Cu(N0,),,3H20, and the lysine as its platinichloride, C,H,,O,N,,H,PtCl,. The sum of the percentage of nitrogen present (1) as ammonia, (2) RS hexone bases, is always far short of the total percentage of nitrogen present in the phosphotungstic acid precipitate.One source of loss lies in the retention of a certain amount of nitrogen compounds in the precipitate obtained on treating the phosphotungstic acid precipitate with baryta water. VOL. LXXXII. i. 23184 ABSTRACTS OF CHEMICAL PAPERS. If i t is assumed t h a t the amount of arginine produced by the hydrolysis of conglutin with acid is the same as is produced by the action of enzymes on the proteids of the seeds of Lupinus Zuteus during germinatiob, then this amount is greater than that which has been actually found in the germinating plant. Caseinogen and its Salts. By W. A. OSBORNE (J. Physiol., 1901, 27, 398-406).-Caseinogen is an insoluble acid which forms soluble salts not only with potassium, sodium, and calcium, but also with other metallic and organic bases.The calcium salt is the chief proteid in- gredient of milk; the ammonium salt is sold as eucasin, the sodium salt as nutrose and plasmon. All the salts are precipitated unchanged by half saturation with ammonium sulphate, full saturation with mag- nesium sulphate, or excess of alcohol. They liberate free caseinogen on treatment with an acid. They may be divided into two chief groups. Group I contains the calcium, magnesium, barium, and strontium salts; these are precipitated by any finely divided, insoluble substance, and will not pass through the pores of a clay filter. Their solutions are markedly opalescent ; they become turbid on warming to 35-45' ; this turbidity disappears on cooling. On prolonged heating, they form a film or 'skin ' on the surface. They react with the rennin ferment. The caseinogenates of caffeine, strychnine, and other alkaloids belong t o this group also, although they do not appear t o react with rennin. Group I1 contains the salts of potassium, sodium, and ammonium. These are not precipitated by finely divided substances, pass easily through a clay filter, form comparatively clear solutions, do not show the reversible change on warming, do not react with rennin, and no surface film is formed on warming. Lithium caseinogenate belongs t o the same group, although it shows a faint turbidity on warming. Calcium caseinogenate + potassium oxalate gives rise to calcium oxalate + potassium caseinogenate. Potassium caseinogenate + calcium chloride gives rise to calcium caseinogenate + potassium chloride. Certain caseinogenates show hydrolytic dissociation in a marked degree ; this increases on warming, and explains the occurrence of the turbidity previously referred to. A Derivative of Casein containing Sulphur and Chlorine. By THEODOR PANZER (Zeit. physiol. Chern., 1901, 33, 595-608).- When casein is treated with hydrochloric acid and potassium chlorate, freed from excess of chlorine, treated with hydrogen sulphide, air dried, and then extracted for a month with carbon disulphide, the residue is a derivative of casein containing chlorine and sulphur. I t s composition is C, 43.14 ; H, 5.10 j N, 10.08 ; S, 8.86 ; P, 0.46 ; CI, 8.36, and 0,24.04 per cent. It has decided acid properties,. yielding potassium, copper, and silver compounds. It dissolves in dilute alkalis, alkali carbonate solutions, also in glacial acetic acid, or in alcohol containing acetic acid, and gives none of the usual proteid reactions. Part of the sulphur is removed on boiling with alkali, and the compound 1s com- pletely decomposed when boiled with hydrochloric acid. J. J. s. Separation of Proteoses by Metallic Salts. By ZDENKO CERNY (P'iiger's Archiu, 1901, 87, 614-633).-The propel ties of J. J. S. W. D. H.ORGANIC CHEMISTRY. 195 proteoses precipitated by various salts of heavy metals (silver, copper, uranium) are described and compared. The differences observed are believed to be due t o the great lability of these substances, and the conclusion is drawn that the different known proteoses as separated by fractional precipitation with neutral salts do not really represent different substances present in the mixture. By FRIEDRICH MULLER (Zeit. Biol., 1901, 42, 468-564).-A lengthy account of several mucins and mucoids. The question to which most attention is directed is the nature of the carbohydrate radicle, the so-called ' animal gum.' It is regarded as probable that it is an acetyl derivative of glucosamine. Crystallised Cyanohmemoglobin. By RICHARD VON ZEYNEK (Zeit. physiol. Chern., 1901, 33, 426-450. Compare Abstr., 1900, i, 318).-CrystalIised methzemoglobin (Abstr., 1900, i, 196) dissolves in 0.5 per cent. hydrocyanic acid, yielding a reddish solution resembling oxyhaemoglo bin and having a characteristic, broad absorption band in the green part, of the spectrum. When diluted and mixed with alcohol at - loo, microscopic crystals are obtained; as a rule, these have the shape of long prisms terminated by pyramids, but occasionally are rhomboid in shape. The same compound is obtained by the addition of potassium cyanide t o alkaline methamoglobin solution. It is stable, and may be heated a t 40' in a stream of an indifferent gas, or its solution may be boiled at 40' under reduced pressure, with- out loss of hydrogen cyanide. When heated at 105-110° in a current of dry hydrogen, it loses water and a small amount of hydrogen cyanide ; the same gas is evolved when it is boiled with water or acids under atmospheric pressure. The compound contains 0.158 per cent. of cyanogen, a result which indicates the presence of only one cyanogen group in the molecule (mol. wt. of hzemoglobin =16669). The crystals are not affected by light, and bacteria cause only slow putrefication. Treatment with hydrogen sulphide transforms the cyanogen derivative into haemoglobin. Back's (Skand. Awh. Physiol., 6, 299) photomethamoglobin appears to be identical with cyanohamoglobin [this has been shown by Haldane, Abstr., 1900, i, 3181 and is produced by the action of hydrogen cyanide liberated by the action of sunlight on potassium f erricyanide. Reduced hzemoglobin does not combine with hydrogen cyanide, but oxyhmnoglobin reacts with hydrocyanic acid solution at 40°, yielding the same cyanohamoglobin. Action of Sunlight on Enzymes. By OSKAR EMMERLING (Ber., 1901, 34, 3811--3814).-The action of sunlight on 1 per cent. solu- tions of the following enzymes : invertase, yeast-maltase, maize-glucase, lactase, emulsin, and diastase, has been studied. The solutions were exposed f o r 6 hours and their fermenting properties then tested. With the exception of yeast-maltase, the enzymes suffered but very little deterioration owing to this exposure. Toxins, on the other hand, appear t o be very susceptible to light. W. D. H. Mucin and Mucoids. W. D. H. J. J. S. J. J. S.196 ABSTRACTS OF CHEMICAL PAPERS, The Action of Enzymes on each other. By AUGUSTIN WR~BLEWSKI, B. BEDNARSKI and M. WOJCZY~SKI (Beitr. chem. Physiol. Puth., 1901, 1, 289--303).-Pepsin destroys trypsin and hastens the destructive influence of acids ; trypsin weakens the action of pepsin, especially in the presence of alkalis ; pepsin has no action on rennet ; pepsin, trypsin, and diastase have no action on invertin ; trypsin and in- vertin have no action on, but pepsin slightly lessens the action of, diastase; pepsin and trypsin have no action on emulsin. Emulsin is completely ' salted out ' by ammonium sulphate, and so differs from invertin. The statement of E. Fischer that emulsir? hydrolyses lactose is confirmed. Zymase of yeast is rapidly destroyed by the proteolytic enzyme of the yeast cells. W. D. H. Tyrosinase. By C. GESSARD (Ann. Inst. Pastew, 1901,15,593-614. Compare Abstr., 1900, i, 468).-A further study of the colour changes induced by tyrosinase in tyrosine solutions containing various metallic salts shows that the compounds of iron (ferrous sulphate and lactate and ferric chloride) have a specific action, causing the development of a green coloration which changes to blue before the production of the bluish-black precipitate already noticed. This reaction takes place even when the solution has acquired the rose coloration produced in the presence of other metallic salts. Zinc salts, the lactate, for example, give rise to the blue coloration without the production of the intermediate green stage. The time required for the development of the rose coloration in- creases very rapidly as the tyrosinase extract is diluted. When the extract is maintained a t 65", the chromogenic property diminishes, until after 30 minutes the tyrosinase is almost wholly destroyed. Although the metallic salts promote the coagulation of the black precipitate, they hinder the development of the initial coloration, the retardatiqn being proportional to the amount of salt introduced. The neutral salts produce a retardation varying from 23 minutes to 9 days, whilst the addition of an alkali carbonate prevents the develop- ment of the coloration for a period of 17 days. Albumin from the egg of the fowl also produces a very notable retardation. The serum of different animals (calf, sheep, pig, horse, mare, and rabbit) exhibits this inhibitive action, but to a less extent; calf serum has the greatest effect, whilst that of the mbbit is least efficacious. The inhibitive action of the rabbit serum is, however, very appreciably increased by repeatedly injecting the animal with an aqueous extrack of tyrosinase. G. T. 31. Synthetical Action of Yeast Maltase. By OSKAR EMNERLING (Ber., 1901, 34, 3810-3811).-A small amount of amygdalin is ob- tained when a mixture of Fischer's mandelonitrile glucoside (Abstr., 1895, i, 554) and pure dextrose is left in contact with a solution of yeast maltase (Abst,r., 1901, i, 258) in sealed tubes for 3 months at 35'. J. J. S .

ISSN:0368-1769    

DOI:10.1039/CA9028200129

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

130 ABSTRACTS OF CHEMICAL PAPERS. In or g an i c C h em i s t r y. Reaction between Nitric Acid and Hydrogen Iodide. By ADOLF ECKSTADT (Zeit. anorg. Chem., 1901, 29, 51-94).--50 long as air is free from dust, it has no influence on the action between nitric and hydriodic acids. Scratches on the flask in which the reaction takes place accelerate the reaction to a n enormous extent. The order of the reaction between nitrous acid and hydriodic acid could not be determined; the reaction takes place very rapidly a t first, but soon slackens. Reaction takes place directly (NO,' + 2H* + 2I' = NO,' + H,O+I,) between nitric acid and hydriodic acid, for when carb- amide is added in order to destroy any nitrous acid present, the action has a normal course. Hydrogen ions exert a catalytical influence on the reaction.Ferric ions, as well as sixteen other cations examined, have no catalytic influence whatever on the reaction. Ferrous ions enormously accelerate the reaction, the influence being independent of the anicn present. It was observed that when about two-thirds of the hydriodic acid had been decomposed, a great acceleration took place, so that the reaction thereafter quickly completed itself, and this is -attributed to the influence of the iodine produced. Tri-iodine ions can only be formed so long as iodine ions are present, that is, until about two-thirds of the hydriodic acid is used up. Then the action of the oxidiser ceases, or iodine is separated in the colloidal state or as a solid, and this, giving rise t o new iodine ions, restarts the reaction, which proceeds until it is complete.When the reaction takes place in an electric field, no difference in the rate could be detected. J. McC. Spontaneous Decomposition of Ozone. By EMIL WARBURG (Sitxungsber. K. Acad. Wiss. Berlin, 1901, 48, 11 26--1139).-The spon- taneous decomposition of ozone, where external causes of decomposition are excluded, is a bimoleculur reaction. At the ordinary temperature, the results obtained indicate that the decomposition takes place inINORGANIC CHEMISTRY. 131 rtccordance with the formula for a monomoledar reaction, but this is attributed to the disturbing influence of the glass walls of the contain- ing vessel, The influence of external agents on the speed of decom- position increases much more slowly with rising temperature than does the actual velocity of the birnolecular reaction, The quantity, b, of ozone which is decomposed per minute can be ascertained from dC= - bC2dt, where C is the number of gram-mols.of ozone per litre and t is the time. The value of 6 at 100" is 0.0157, and at 126.9" it is 0.177. The velocity quotient for 10' is 2.47. Shenstone (Trans., 1897, 71, 477) states that a t 26' moist ozone is more stable than dry; theauthor finds that, a t loo", the dry gas is just as stable as the moist . J. McC. Sublimed Sulphur. By NORMAN LEONARD (Andyst, 1901, 26, 319-320).-Although sublimed sulphur B.P. is not supposed to affect blue litmus, the author has found it generally to contain from 0.02 to 0.25 per cent. of sulphuric acid. Although part of the acid may be formed during the process of sublimation, it is also formed by exposure to air and moisture.A sample of sublimed sulphur, after being washed until no longer acid, was put in a moist condition into a stoppered bottle ; after two weeks, i t was found to be faintly acid, and decidedly so after three months, whilst after four years it contained 0.2 per cent. of sulphuric acid ; sulphurous acid could not be detected. A specimen which had been washed, and dried a t loo', only showed 0.0025 per By CH. MALUS (Artn. Chim. Phys., 1901, 24, [vii], 491-574).-Sulphur, when heated for 5-10 minutes at 357', is black and on cooling to 100' becomes pale yellow, The modification of the element produced in this way is indicated by the symbol S, ; it is viscous a t 100" and contains bubbles of sulphur dioxide ; at IS0, it becomes plastic (compare Abstr., 1900, ii, 536). Another modification, S,, is produced when the heating at 357' is prolonged for 3 hours ; this form is lighter in colour than S1, being almost colourless a t 73'; it is not viscous at loo', and contains no gaseous bubbles a t this temperature, and at the ordinary temperature it becomes quite hard.Sulphur heated at 300°, or a t higher temperatures, passes ultimately into the modification S,, the rate of change depending on the temperature ; complete transformation requires 30 hours at 300° but only 15 minutes a t 440'. The modification S, owes its existence t o the presence of sulphur dioxide in the sulphur and its conversion into S, is due to the expulsion of the gas; any causes which tend t o eliminate the gas more rapidly, such as the introduction of thin glass rods or the passage of carbon dioxide, increase the velocity of trans- formation. Moreover, S, is reconverted into S, when heated a t 357' in the presence of sulphur dioxide.On the other hand, the variety S, does not change into S, on prolonged heating at this temperature if it is kept saturated with sulphur dioxide. Sulphur in form of S, is slowly converted into a third modification S,' when maintained in superfused condition at temperatures varying from 72" to 103'; this third variety differs from S, in becoming vis- cous when heated at 180" or at higher temperatures. -This difference is cent. of acid after having been kept for four years. L. DE K. Viscosity of Sulphur.132 ABSTRACTS OF CHEMICAL PAPERS.due t o the fact that, in the transformation of S, into S2',. there is no elimination of sulphur dioxide and therefore the latter modification still contains the dissolved gas which a t higher temperatures promotes the formation of the S, variety. G. T. M. Determination of the Vapour Density of Sulphur by the Dumas Method. By HEINRICH BILTZ and GERHARD PREUNEB (Zeit. physikaZ. Chem., 1901,39, 323--341).-A full account of the apparatus used in determining the vapour density of sulphur a t 448' under vary- ing pressures. The conclusions are t o be found in Abstr., 1901, ii, 649. As the quaternary reaction S , 45, is improbable, the authors believe that the dissociation may take place in the two stages : S, 2S, and s*c 25,.J. McC. By HERMANN WICHELHAUS (Bey., 1901, 34, 4135).-A test-tube widened a t the open end fits concentrically into a cylindrical glass receiver into which sulphur trioxide is distilled. The test-tube is filled with frag- ments of ice and the trioxide condenses on its cooled outer surface. When sufficient of the compound has been collected, the tube is with- drawn and another placed in position. I n this way, samples of sulphur trioxide available for lecture experiments m e readily obtained. Apparatus for Experimenting with Sulphur Trioxide. G. T. M. Sulphuric Acid and its Manufacture by the Contact Process. By RUDOLF KNIETSCH (Bey., 1901, 34, 4069-41 15).-An account of the historical development and recent introduction on a large scale of the contact process of making sulphuric acid.,When the gases obtained by roasting pyrites are freed from mechanical impurities, and passed in a dry state through tubes contain- ing a catalytic agent (for example, platinised asbestos), a practically quantitative yield of sulphur trioxide can be obtained a t first, but the activity of the contact substance, and, consequently, the yield of sulphur trioxide, gradually diminish. It is found that certain substances, notably arsenic, mercury, and phosphorus, have a remarkably deleterious effect on thecatalyticactionof platinum,and the above-mentioned deterior- ation of the contact substance is due to the presence of arsenic in the pyrites gases. It is exceedingly difficult to get rid of the last traces of arsenic. Thus troublesome fogs of finely divided unburnt sulphur particles, containing arsenic and almost unprecipitable, are produced in the pyrites ovens, and the only remedy is to blow in steam, thus securing thorough mixture of the pyrites gases and complete combustion of the sulphur.Finally, by cooling and washing the gases in a very thorough manner, it has been found possible to free .them from all hurtful impurities, and to preserve the contact substance in excellent condition. The tubes containing the contact substance should be heated previous to the passing of the pyrites gases, but, the process having been started, very little external heat is necessary, since the heat of the reaction, 280, + 0, = 2SO,, is very considerable, and the temperature must not be allowed to rise too high, I n the apparatus described inINORGANIC CHEMISTRY.133 the paper, it was found necessary actually to cool the tubes by a current of cold air in order t o procure the best results. I n this contact process, the gases are not under pressure : indeed, the yield is not appreciably affected by diluting the pyrites gases largely with air. The sulphur trioxide produced can be instantaneously and completely absorbed by sulphuric acid of 97-90 per cent., a behaviour shown by sulphuric acid of no other concentration. Acid of this "critical" concentration is peculiar in other respects also, as the author shows by a study of the boiling point curve, the sp. gr., the electrical resistance, and the action on cast and wrought iron. The gas issuing from the contact tubes can be completely freed from sulphur trioxide in a single apparatus, provided the acid in this apparatus is kept of the proper strength by regular addition of water or dilute acid, and removal of the excess of acid formed by the absorption.The contact process does not give a quantitative yield when the sulphur dioxide and oxygen are mixed in the proportion required by the equation: 2SO2+O,=2SO3; the more oxygen there is in pro- portion to the sulphur dioxide, the more productive is the process; nitrogen is without effect on the reaction. When the pyrites gases, which coiitain sulphur dioxide and oxygen approximately in the ratio 2530, : 30, and in addition 83 per cent. of nitrogen, are passed over platinised asbestos in a porcelain tube, and the temperature of the tube is varied, it is found that a t 400-430' 98-99 per cent.of the sulphur dioxide is converted into sulphur trioxide, whilst further rise of temperature has a bad effect on the yield ; thus, a t 700-750°, the yield is only 60 per cent., and at 900-1000" there is practically no reaction at all between sulphur dioxide and oxygen. I n the absence of contact substance, however, sulphur trioxide is stable even a t high temperatures. The formation of trioxide from dioxide and oxygen depends, too, on the rate a t which the gases are passed over the contact substance, and for each temperature there is a certain rate which gives the maximum yield. Platinum alone fulfils the conditions necessary for an effective contact substance. The paper contains also a detailed study of the physical properties of mixtures of water and sulphur trioxide in varying proportions.The melting point curve shows maxima for mixtures of the composition 2H,O + SO,, H,O + SO,, H,O + 2S03, the melting points of these three being respectively So, lo", and 36". When density is plotted against per- centage composition, the resulting curve shows twc, maxima, one at 79.72 per cent. SO, ( = 97.66 per cent. H,SO,) and the other at 92.65 per cent. SO,, the corresponding densities being 1.8434 and 2.020 at 15'; the density of sulphur trioxide is 1.984 at 15' and 1.814 a t 45'. The specific heat falls with increasing percentage of the trioxide to the value 0-339 for an acid containing about 20 per cent. of the free anhydride ; the specific heat of absolute sulphur trioxide is 0.770.The heat of solution varies in a perfectly continuous manner with the percentage, and i t therefore appears that the formation of the varions hydrates is not accompanied by any appreciable heat effect. The observations made on the electrical resistance agree with those of Kohlrausch (Ann. Phys. Chem., 1882, [ii], 17, 69), except that the VOL. LXXXII. ii. 10134 ABSTRACTS OF CEIEIEMICAL PAPERS. author finds a maximum value of the resistance a t 99.9-99.95 per cent. H,SO, instead of at 99.74-99-75. With acids containing more trioxide, there is first a fall of resistance, and finally a steady increase to very high values. The boiling point curve shows a maximum, and the vapour pressure curve a minimum for the composition 80.4 per cent.SO, (=98*5 per cent. H,SO,). By allowing equal volumes of acid of varying concentration t o flow through a narrow opening, it is found that water and absolute sulphur trioxide have approximately the same viscosity ; the maximum viscosity corresponds with the point of maximum density for the fuming acid. The height reached in a capillary tube gradually diminishes with increasing percentage of trioxide, although there are slight peculiarities in the curve at the hydrate H,SO, + H,O, and at the point of maximum density. Finally, a table is appended for converting the percentages of total SO,, found by analysis of the fuming acid, into percentages of free SO,. J. C. P. Allotropy of Tellurium. By DMITRI BELJANKIN (J. Russ. Phys. Chern. Xoc., 1901, 33, 670-676).-The variation in the values given for the specific heats of amorphous tellurium is explained by the author as due to the fact that the modification obtained by Berthelot by precipitation from alkaline solution and described by him as amor- phous, consists in reality of microscopic rhombohedra.For the densities of various modifications of tellurium at 18-22', the author obtains the following numbers : (1) Amorphous tellurium (precipitated from acid solution by means of sulphur dioxide), 6.015 +, 0.031. (2) Ordinary crystalline tellurium, 6.338 -+, 0.025. (3) Berthelot's crystal- line tellurium (obtained from alkaline solution), 6.157 & 0.035. By slowly heating to 430°, the density of (2) is unchanged, but (I) increases and (3) decreases in density; these alterations point to the existence of a third crystalline form of tellurium, which has not, however, been isolated.Other unkiown modifications are also indicated by results obtained by Berthelot (Abstr., 1887, 761) and by T6pler (Abstr., 1895, ii, 5). T. H. P. Telluric Acid. By ALEXANDER GUTBIER (Zed. anorg. Chem., 1 90 1, 29, 22-35. Compare Abstr., 1901, ii, 501)-Telluric acid has been prepared by the method devised by Staudenmaier. No evidence could be found of the existence of an acid of the formula H2Te0,. The acid when heated at 145' loses water and at the same time oxygen, and in the residue both the oxides TeO, and TeO, are to be found. Telluric acid is dimorphous, crystallising in regular and hexagonal- rhombohedric forms, the latter being the more common.The determination of the molecular conductivity shows that the acid is only very slightly dissociated and this is confirmed by the depression of the freezing point of water. The equivalent conductivity of the normal potassium salt differs greatly from that of potassium sulphate, but agrees well with that of potassium carbonate. The formula of telluric acid is, as previously stated (Zoc. cit.), H6Te0,, and not H,TeO, + 2H,O. J. McC.INORGANIC CHEMISTRY. 135 Some Physical Properties of Nitric Acid Solutions. By VICTOR H. VELICY and J. J. MANLEY (Proc. Roy. Xoc., 190.1, 69, 86-1 19).-Details are given of work already reviewed (Abstr., 1901, ii, 447), dealing with the densities and refractive indices of nitric acid solutions. The maximum refractive index observed (1.4061 a t 14.2') is that of a solution containing 70 per cent.of nitric acid ; the refrac- tive index of the anhydrous acid is nearly the same as that of a solution containing equal parts by weight of acid and water. The possible errors involved iu the various physical measurements are discussed and estimated. J. C. P. Action of Hydrogen Sulphide on Arsenic Acid. By LE ROY W. MCCAY (Zeit. anorg. Chesm., 1901, 29, 36-50. Compare Abstr., 1889, 15 ; 1898, ii, 139 ; 1899, ii, 745).-Monothioxyarsenic acid is formed when hydrogen sulphide acts on arsenic acid solution (H,As04 + H,S = H,AsO,S + H20). Dithioxyarsenic acid is also obtained but is not a direct product of the reaction ; it is probably formed from the rnonothioxyarsenic acid (H3As0,S + H2S = H,AsO,S, + H20), Magnesium oxide is a good reagent for the separation of arsenic acid from monothioxyareenic acid, for whilst the magnesium arsenate is insoluble, magnesium monothioxyarsenate is easily soluble, Xodium monothioxyarsenate, Na,AsO,S, 12H20, has been obtained in the pure condition from arsenic acid by passing hydrogen sulphide through a solution of it, filtering, and then leaving the filtrate for 24 hours in contact with excess of magnesium oxide; to the filtrate from the magnesium precipitate, alkali is added in quantity sufficient to precipitate all the magnesium; on adding barium hydroxide to the filtered solution, a precipitate of sodium barium monothioxy- arsenate is formed, which is exactly decomposed with sodium car- bonate or sulphate and the sodium monothioxyarsenate thrown clown in crystals by the addition of alcohol. Sodium dithioxyarsenate, Na,As0,S2,11 H,O, is prepared by allow- ing an excess of hydrogen sulphide to act on a solution of arsenic acid for some time, then expelling the excess of gas, and treating the solu- tion with strontium hydroxide ; the arsenic and monothioxyarsenic acids are then removed and barium hydroxide added to the filtrate to precipitate barium dithioxyarsenate, which is converted into the sodium salt by treatment with sodium sulphate.By PAUL LEBEAU (Compt. rend., 1901, 133, 1008--IOlO).-Nitric acid and cupric potassium chloride have no action on very finely divided amorphous silicon, and hence the fact that these reagents dissolve or oxidise the silicon in cast iron and ferrosilicons containing a low proportion of silicon shows that in these substances the silicon must be in the form of iron silicides.The author has obtained only three definite compounds of iron and silicon, %,Fey SiFe, and SiFe,. The first is found only in presence of excess of silicon and therefore cannot exist in cast iron and similar products, The monosilicide is readily dissociated and cannot exist in a matrix poor in silicon; it is decom- J. McC. Condition of Silicon in Cast Iron and Ferrosilicon. 10-2136 ABSTRACTS OF CHEMICAL PAPERS. posed into silicon and the compound SiFe, when fused with silver. The silicide, SiFe,, which contains the lowest proportion of silicon of any compound of the two elements which the author was able to obtain, is stable even a t 1000° ; i t dissolves in melted silver but is not decomposed.This is the form in which silicon exists in siliceous cast iron and its uniform distribution is due to the ease with which it dissolves in iron, whilst the consequent fine state of division in which it exists in the solidified metal is the reason why it is gradually attacked by nitric acid, which is almost without action on this silicide if it has been produced in the electric furnace, C. H. B. Radium. By MARCELLIN BERTHELOT (Compt. rend., 1901, 133, 973--975).-The decomposition of iodic acid by radium (this VOI., ii, 18) is due t o the phosphorescent rays and does not take place either at 10' or 100' if a screen of black paper is placed between the radium and the iodic acid. The action of radium on glass is more rapid a t 100" than at the ordinary temperature.Preparation and Properties of Potassium Hydride. By HENRI MOISSAN (Compt. rend., 1902, 134, 18--21).-The action of hydrogen on potassium a t 360" yields the hydride, KH, in slender, white, acicular crystals, very readily decomposed by atmospheric moisture and by water, It takes fire at the ordinary temperature in fluorine, chlorine, or oxygen, and when gently heated decomposes carbon dioxide, hydrogen sulphide, and lead and copper oxides, It does not react with liquid ammonia under the ordinary pressure, but in sealed tubes a compouud is formed which dissolves in excess of the liquid ; when heated in ammonia gas at about 400°, potassamide is formed. Potassium hydride is insoluble in terebenthene, benzene, ether, or carbon disulphide.C. H. B. Melting Points of Alloys of Sodium with Potassium. By NICOLAI S. KUBNAKOFF and N. A. PUSHIN (J. Buss. Phys. Chem. Xoc., 1901, 33, 588--592).--The relations between melting point and com- position are given, in the form of curves and tables, for mixtures of sodium and potassium. The melting point curve shows a transition point (6.88") for the alloy of the composition Na,.,,?K and a eutectic point, - 13*5', corresponding with the compound NaK,. By EDUARD VON BERG (Ber., 1901, 34, 4181-4185).-Ru6idium dihydrogen phosphate, RbH,PO,, obtained by evaporating an aqueous solution containing mol. proportions of rubidium hydroxide and phosphoric acid, crystal- lises in large, colourless, anhydrous prisms and is acid to litmus. Dirubidium hydrogen phosphate, Rb,HPO,,H,O, is obtained by con- centrating an aqueous solution of the proper quantities of phosphoric acid and rubidium carbonate, adding ammonia t o precipitate a crys- talline rubidium ammonium phosphate, and drying the latter in a vacuum over sulphuric acid until all the ammonia is removed ; if the treatment with ammonia is not adopted, the salt cannot be obtained C.H. B. T. H. P. Rubidiu-m and C e s i u m Phosphates.INORGANIC CHEMISTRY, 137 crystalline ; its solution is alkaline to litmus. Trirubidium piiosphate, Rb,P0,,4H20, obtained by concentrating an aqueous solution of phos- phoric acid (2 mols.) and rubidium carbonate (3 mols.), crystnllises in short, thick, colourless, hygroscopic prisms. Rubidium metaphosphate, RbPO,, obtained by heating the monorubidium phosphate, is a white powder, which, unlike the analogous sodium and potassium salts, is soluble in water.Rubidium pyrophosp?w,te, Rb4P207, is a white, hygro- scopic mass. Ccesium dihyd~ogeit phosplmte, CsH2P04, forms beautiful, colourless, lustrous, anhydrous plates ; diccesium hydrogen, phosphate, Cs,H P04,H,0, wliich is very soluble in water, is a white, microcrystalline solid, whilst triccesium phosphate, Cs3P04,5H20, forms small, white, deliquescent crystals with an alkaline reaction. Ccesium metaphosphnte and p y ~ o - phosplhate are similar to the analogous rubidium compounds. W. A. D. Combining Weight of Calcium. By F. WILLY HINRICHSEN (Zeit. physikaZ. Chem., 1901, 39, 31 1-382).--The weight of calcium oxide left on ignition of about 30 grams of Iceland spar in an electric furnace of suitable form was determined.The Iceland spar gave 0.032 per cent. of ferric oxide and contained neither silicic acid nor magnesium, and only a trace of aluminium. During the ignition, the spar mas heated in a platinum crucible furnished with a lid through which two tubes passed. A current of purified air was drawn through the apparatus during the experiment, and the tubes were carefully closed during weighing to prevent access of moisture and carbon di- oxide. Four experiments gave a mean value of 40.142 for the atomic weight of calcium when 0 = 16. Formation of Oceanic Salt Deposits, particularly of the S t a s s f u r t Beds. XXIV. Gypsum and Anhydrite. 3. Natural Anhydrite andits Formation at 25'.By JACOBUS H. VAN'T HOFF and FRITZ WEIGERT (Sitxungsber. K. Akad. Wiss. Berlin, 1901, 48, 1140-1148. Compare Abstr., 1901, ii, 506, and this vol., ii, 74).- I n presence of sodium chloride, the transition point of gypsumis lowered ; by dilatometric experiments,it has been found that the transition in this case takes place near 30'. The tension of the gypsum-anhydrite mixture a t this temperature is the same as that of the saturated sodium chloride solution and has been found to be 24 mm. I n presence of sodium bromate, the transition takes place near 50°, and the tension is then 83.3 mm. The tension a t any other temper- ature can be found from the formula log Pg=log P, - 341/5?+ 1.0072, where Pg is the tension of the gypsum and P, that of water at the temperature T.I n concluding the work on the transition of gypsum, the authors sum up the results obtained as follows, Gypsum is transformed (1) into natural anhydrite: (2) Into soluble anhydrite : (3) Into semihydrate : J. McU. A. .At 66'. C. A t 89'. E. A t 107". B. I n presence of sodium chloride a t 30'. D. In presence of sodium chloride at 65'. F, A t 101.5', under atmospheric pressure (boiling138 ABSTRACTS OF CHEMICAL PAPERS. point) G. I n presence of magnesium chloride a t 1 1 O . H. In presence of sodium chloride a t 76O. Solutions containing calcium sulphate which have a tension lower than 17.2 mm. a t 25' deposit it as anhydrite. This is the case in the deposition from sea-water. Metallic Strontium and its Hydride. By ANTOINE GUNTZ (Compt. rend., 1901, 133, 1209-1210.Compare Gautier, following abstract).-Strontium amalgam is very easily prepared when an aqueous solution of strontium chloride is electrolysed, using mercury as cathode. From the amalgam, metallic strontium is obtained by distilling off the mercury in a vacuum. Strontium hydride, SrH,, is prepared by heating strontium or its amalgam in a current of hydrogen, and is a white solid which fuses only a t a red heat. Strontium does not dissolve in liquid ammonia as does barium. I(. J. P. 0. Alloys of Strontium with Zinc and Cadmium, By HENRI GAUTIER (Compt. rend., 1901, 133, 1005--1008).-An alloy of zinc and strontium containing 12-14 per cent. of the latter can be obtained by the action of sodium on a mixture of strontium and zinc chlorides, the excess of sodium being removed by treatment with alcohol.A sim.ilar alloy containing 18 per cent, of strontium is obtained by the action of sodium on strontium iodide in presence of zinc. Attempts to obtain richer alloys by partially volatilising the zinc were unsuccessful, since both metals volatilised together. Cadmium strontium alloys containing 18 to 20 per cent. of strontium were obtained in a similar manner, and by heating these a t 260-300° in a vacuum the strontium is concentrated up t o as much as 45 per cent. The latter alloy can be polished with a file, but the surface rapidly tarnishes ; it burns readily in oxygen, phosphorus vapour, and chlorine, and reacts with sulphur below its boiling point and with iodine at a dull red heat. When heated a t dull redness in hydrogen, a white strontium hydride, SrH,, is formed and can be isolated by volatilising the cadmium in a vacuum.Preparation of Barium, By ANTOINE GUNTZ (Compt. rend., 1901, 133, 872--874).--Rarium amalgam, which is readily obtained by electrolysing a concentrated solution of barium chloride in contact with a mercury cathode, is heated in a porcelain tube by means of an electric current passed through a thin platinum wire until a temper- ature of 1150' is reached, All the mercury is driven off a t lower temperatures, and the final distillate consists of barium containing 97.8 per cent, of the metal. This element, when freshly cut, has a silvery lustre, but it rapidly oxidises and often takes fire in the atmosphere. The metal melts below 1000°, and is readily volatilised a t a bright red heat ; it yields, with liquid ammonia, a compound which seems to be more stable than its lithium and calcium analogues. Barium readily decomposes water, absolute alcohol, and even a solu- tion of barium ethoxide.Preparation of Barium. By EDGAR STANSFIELD (Hem. hhn- Chester Phil. Xoc., 1901, 46, No, 4, 1-6).-A solid, crystalline amal- J. McC. C, H. B. G. T. M.INORGANIC CHEMISTRY. 139 gam, containing nearly 5 per cent. of barium, can be easily obtained by the electrolysis of a saturated solution of barium chloride, using a mercury cathode. An alloy containing 12 per cent. of barium is obtained by heating a mixture of zinc, sodium, barium chloride, and sodium chloride. But in neither case can pure barium be obtained by distillation of the mercury or zinc.A hard, thick, metallic mass con- taining crystalline flakes and nodules of metal is obtained by heating barium peroxide with finely divided aluminium in a vacuum. It con- tains 63.3 to 66.6 per cent. of barium, and 19.3 to 29.3 per cent. of aluminium ; the metallic nodules mentioned above contain 58 per cent. of barium and 42 per cent, of aluminium. The metallic flakes and nodules decompose water very rapidly but are stable when exposed to dry air. The results indicate that the reaction between barium per- oxide and aluminium is a reversible one and that it cannot be used to obtain pure barium. With calcium oxide, the reaction did not take place, and on replacing the aluminium by magnesium, the reaction was too violent and shattered the apparatus. E.C. R. Action of Ammonia and Potassium Hydroxide on Solutions of Zinc Salts. By BASIL B. KURILOFF (Chem. Centr., 1901, ii, 1222 ; from Bull. Acad. St. Petemb., 1901, No. 1, 95--103).-The excess of ammonia or potassium hydroxide which is necessary to dissolve the pre- cipitate formed when the alkali is added to a solution of zinc chloride or sulphate has been determined, and the results show that in both cases the more dilute the solutions of ammonia or potassium hydroxide, the greater must be the actual proportion of alkali to zinc salt. Solutions weaker than decinormal do not appreciably affect the pre- cipitate. The proportion of alkali required is also greater for solu- tions of the sulphate than for those of the chloride, but the data obtained for these two solutions are otherwise very similar.No quantitative determinations to show the influence of the chlorine or sulphate ions are given, but the solid phase which is formed when potassium hydroxide acts on zinc sulphate contains sulphate, and this group cannot be removed by washing with water. E. W. W. Alloys of Thallium. By NICOLAI S. KURNAKOFF and N. A. PUSHIN (J. Russ. Phys. Chern. SOC., 1901, 33,565-588).-The authors have determined the relations between melting point and composition for mixtures of thallium with the following metals : sodium, potass- ium, tin, cadmium, and mercury, the results being expressed both in curves and in tables. It is found that in combination with potassium or sodium, and also with tin or cadmium, thallium behaves similarly to heavy metals having an acid character, such as mercury and lead, which it also resembles physically in the free state; in alloys with mercury, bismuth, or lead, however, thallium plays a part similar to that of the alkali metals.The melting point curves for sodium- thallium, and potassium-thallium show eutectic points corresponding with alloys of the composition NaTl and KT1; the first of these com- pounds melts a t 305.8" and the latter a t 335.0'. The authors' results serve to complete the following series of sodium alloys : NaHg,, NaTl, Na2Pb, Na,Bi, in which it will be seen that corresponding with the140 ABSTRACTS OF CHEMICAL PAPERS. increaseof the atomic weight and acid properties of the heavy metal, a n increase occurs in the relative number of sodium atoms in a molecule of the alloy.T. H. P. Action of Cupric Hydroxide on Aqueous Solutions of Metallic Salts. By AMABLE MAILHE (Compt. rend., 1902, 134, 42--45).-The action of the black hydrate of cupric oxide on aqueous solutions of various metallic sulphates yields the followirig results : with cadmium, at the ordinary temperature, bluish-green, rhombic plates of the compound 2CdS0,,3Cu0,121'i20, and at looo, green, hexa- gonal crystals of the compound 2CdS0,,3Cu0,10Hz0 ; with nickel, strictly analogous compounds, in green crystals ; with cobalt, at t,he ordinary temperature, maroon coloured crystals of the compound 3~oSO4,5Cu0,l 6H20, and at looo, maroon coloured, hexagonal plates of the compound ZCoSOy3Cu0,10H20. With zinc a t the ordinary tem- perature, the composition of the product varies with the concentra- tion of the solution from ZnS0,,3Cu0,5H20 to 2ZnS04,3Cu0, 12H,O, the latter being the sole product at 100".Manganese is not dis- placed from manganous sulphate by cupric oxide, but mercury, aluminium, and iron (ferric) are completely displaced (compare Abstr., 1901, ii, 601). C. H. B. The Oxidising Action of Copper Salts. By EDUARD SCHAER (Arch. l'liurm., 1901,239, 610-626. Compare Abstr., 1900, i, 512 ; ii, 583).-An account of the way in which different substances accelerate the oxidising action of cupric salts, especially its salts with the organic acids, on iodide of starch, guaiacum, indigo, cyanine, pyrogallol, brazilin, aniline, p-phenylenediamine, guaiacol, or aloin. Hydrocyanic acid, soluble ferrocyanidee, ferricyanides, thiocyanates, and nitroprussides, cyanogen iodide, organic cyanides and t hiocarbimides, iodine, bromides and chlorides, ammonia and alkaloids, hydrogen peroxide, sulphurous acid and eulphites, and colloidal platinum and gold are all found to produce a greater or less acceleration.By PETR. G. MELIKOFF and B. E. KLIMENKO (J. Russ. Phys. Chem. Soc., 1901, 33, 663-666). -The basic character of the two oxides of praseodymium, observed by former investigators, indicates that this element cannot be placed in the periodic system between niobium and tantalum. On cautiously adding dilute potassium hydroxide solution t o a hydrogen peroxide solution of the sulphate or nitrate of the metal, a pale green, gelatinous precipitate is formed, having in the first instance the probable formula Pr(02H)$ ; this compound, however, quickly de- composes, yielding free oxygen and the hydrate of praseodyv&m mono- peroxide, Pr(OH),*O,H, which loses water when kept.Under the action of dilute sulphuric acid, this hydrated peroxide yields hydrogen peroxide, whilst with the concentrated acid ozone is formed ; aqueous potassium hydroxide is oxidised by the hydrate t o potassium peroxide, but no conversion of manganese salts into permanganic acid takes place in presence of nitric acid. Praseodymium dioxide, Pro,, yields, with dilute sulphuric acid, no C. F. B. Praseodymium Peroxide and Dioxide.INORGANIC CHEMISTRY. 141 hydrogen peroxide but ozone ; in presence of nitric acid, however, it oxidises manganese sulphate to permanganic acid.The author concludes that the peroxide Pr,05 is a compound of the type H,O,, but that the dioxide cannot be regarded as such. T. H. P. Alloys of Aluminium and Magnesium. By OCTAVE BOUDOUARD (Compt. rend., 1901, 133,1003-1005).-By treating fused mixtures of aluminium and magnesium in various proportions with ammonium chloride solution or dilute hydrochloric acid, the author has isolated three definite crystalline compounds of the two metals: AlMg,, sp. gr. 2.03, from a mixture of 30 parts of aluminium and 70 parts of magnesium; AlMg, sp. gr. 2.15, from mixtures of 40 to 50 parts of aluminium with 60 t,o 50 parts of magnesium, and Al,Mg, sp. gr. 2.58, from mixtures of 70 parts of aluminium and 30 parts of magnesium. All the fused mixtures of the two metals, except that containing equal parts of each, show dendritic crystals in considerable quantity.The existence of the compounds AlMg, and AlRlg was predicted from determinations of the melting points of the two metals (Abstr., 1901, ii, 512). C. H. B. Action of Aluminium on Salt Solutions and on Molten Salts. By CARLO FORMENTI and MARIO LEVI (Chem. Centr., 1901, ii, 1298; from Boll. China. Furm., 1901,40,689-696).-From experiments on the reduction of salts of gold, platinum, palladium, cadmium, lead, tin, beryllium, cerium, niobium, thorium, zirconium, chromium, uranium, thallium, ammonium, zinc, iron, manganese, mercury, antimony, arsenic, bismuth, silver, copper, cobalt, nickel, silicon, and boron by aluminium, this metal is found to be a more powerful reducing agent than the metals commonly used for this purpose. I n many cases, the aluminium does not completely replace the metal which is contained in the salt, and the reduced metal is often mixed with more or less aluminium, forming an alloy.I n other cases, the metal which first separates subsequently forms a basic salt or is oxidised. By the action of aluminium on some sulphates, alums are formed, and the metal even attacks aqueous solutions of aluminium chloride, forming a hydrate of a subchloride and liberating hydrogen. The reduction of metallic chlorides takes place the more readily the greater the difference between the heat of formation of aluminium chloride and 3iht. ,?F SLLp ,-LpSal,li,.ch.lmid~ 2nd SAh& is al&n $A? C&&!? Vith O $ k P sal$&-.E. w. w. Preparation of Crystallised Alumina in the Electric Furnace and some Bye-products of this Process. By WILHELM H. GIETL (Zeit. angew. Chem., 1901, 14, 1173-1 179).-Different specimens of bauxite, with a small amount of powdered coal and a quantity of sodium chloride, were fused in an electric furnace. A 100 volt current was used. After the whole mass had become fused, it was allowed to run o u t ; a t first, a limpid metal flowed out, and was followed by a more viscid slag. The metal is brittle, and i t s density (at 15') varies between 6.75 and 6-78. It consists chiefly of iron (83142 ABSTRACTS OF CHEMICAL PAPERS. per cent.) and silicon (14 per cent.), and small amounts of manganese, aluminium, carbon, phosphorus and titanium.The slag, on cooling, assumes a microcrystalline structure and is of a grey or brownish- grey colour. On breaking up the slag, small quantities of another metal and large blue and brown crystals were obtained; the metal consists mainly of aluminium (61 per cent.), iron (13 per cent.), and silicon (19 per cent.), along with smaller quantities of carbon, titanium, sodium, calcium, copper, and sulphur. The blue and brown crystals were examined crystallographically ; they have the same form, and belong t o the hexagonal-rhombohedric system (0001 : 1011 =57'33', which is nearly identical with the corre- sponding angle on natural corundum), and are uniaxial. The brown crystals (sp. gr. 3.55) contain about 82 per cent. of alumina, about 12.25 per cect. of silica, and small quantities of iron, manganese, sodium, and titanium.The blue crystals (sp. gr. 3.81) contain from 66 to 70 per cent. of alumina, about 16 per cent. of silica, considerable quantities of the oxides of iron and sodium, and smaller amounts of manganese, calcium, magnesium, and titanium oxides. The author believes that the blue colour is due to the presence of a low oxide of titanium, and not to cobalt, because the presence of the former element has been established, but no cobalt could be detected, even when large quantities of the crystals were used. The titanium oxide is reduced by t,he carbon electrode a t the high temperature. It was found that when pure alumina was fused with alkali and a little titanic acid, a blue mass was produced at the place where the carbon electrode m7as in immediate contact with the fused mass.On treating splinters of the crystals with moderately dilute sulphuric acid, they are partially dissolved, and the undissolved portion consists entirely of alumina. I n all probability, the crystals are not homogeneous, but consist of a framework of pure alumina per- meated by thin layers of a sodium aluminosilicate and varying quantities of calcium, magnesium, manganese, and ferrous oxides. The blue colour of the sapphire is also attributed to the presence of a low oxide of titanium, and this is supported by the fact that when the sapphire is heated in air it loses its blue colour and becomes brown. The presence of ruby-red crystals in the bauxite slag has also been observed. J. McC. Compounds of Aluminium Chloride with the Alkali Chlor- ides.By E. BAUD (Compt. rend., 1901, 133, 869-871).-The double chlorides, A1,Cl6,2NaCl and A1,C16,2KC1, have the heats of dissolution, 141 *42 Cal, and 120.44 Cal. respectively, their calculated heats of formation being 11.84 Cal. and 26.38 Cal. The compound AI,C16,2NH,C1, made by fusing together its genera- tors in the theoretical proportions, may be distilled without decomposi- tion ; its heats of dissolution and formation are 120.943 Cal. and 26.53 Cal. respectively, Compounds of the type Al,C1,,3MCl are produced by employing 3 mols. of sodium or potassium chloride at 500° ; the heats of formation of the sodium and potassium salts are 15.29 and 30.53 Cal. respec- tively, these values being calculated from the corresponding heats ofINORGANIC CHEMISTRY. 143 fotniatidn, 138.97 and 112.07 Cal.The addition of the third molecule of alkali chloride to the double salt, A12C1,j2MCl, is accompanied by a development of heat. Double salts of the type Al,C16,6MC1 are obtained by adding the compounds A12c16,2MC1 to the calculated quantity of fused alkali chloride. The heats of dissolution of the sodium and potassium com- pounds are 129.73 and 93.304 Cal. respectively, and from these values the corresponding heats of formation are calculated, namely, 19.45 and 36.636 Cal. It follows therefore that the addition of the last three mols. of alkali chloride is also accompanied by a development of heat. Thermochemical measurements indicate the existence of double salts containing even a larger proportion of alkali chloride, but the heat change is so small that it becomes impossible to determine the exact composition of these compounds.By RUDOLF SCHARIZER (Zed. Kryst. Hk, 1901, 35, 345-356. Compare Abstr., 1899, ii, 30; 1900, ii, 349).- The white powder obtained when a solution of ferrous sulphate is allowed to oxidise and evaporate in the air, as well as many com- mercial samples of ferric sulphate, contain Fe203:S0, in the ratio 1 :4. This excess of sulphuric anhydride over that required for normal ferric sulphate is not due, as often supposed, to the presence of free sulphuric acid, but the substance is a definite acid salt with the composition Fe2S,0,,H6,6H20. It is prepared by adding as much ferric hydroxide as will dissolve to boiling dilute sulphuric acid, dilut- ing, and adding sulphuric acid until the solution contains Fe20, : SO, = 1 : 4; as the solution evaporates, small rhombic crystals of the salt are deposited.Part of the water is given off below looo, and the remain- der with some sulphuric anhydride at 140O. A structural formula represents the substance as a basic, acid salt, Fe,(OH)2(S0,H),,6 H20. G. T. M. Acid Ferric Sulphate. L. J. S. Luteocobdtic Salts. By TIMOTHBE KLOBB (Bull. Soc. Chim., , 1901, [ iii], 25, 1022--1031).-Luteocobaltic chloride is best prepared by dissolving cobaltous chloride and ammonium chloride in water, pouring into cold concentrated ammonia, oxidising first in the cold by means of a current of air, and then by means of lead peroxide on a water-bath. The nitrate and sulphate can be prepared by similar methods.The acid suZphate, ~(CO~NH,)~(SO~)~~~H~SO,,~OH~O, pre- pared by the action of an excess of sulphuric acid on the normal sul- phate, forms birefringent, orthorhombic, octahedral crystals, does nQt lose in weight when heated a t looo, but loses 9H20 at 120-130'; by crystallising from water, i t is reconverted into the normal sulphate. The chloro-sulphte, (Co6NH,)C1S04,3H20, forms orthorhombic prisms and is only very slightly soluble in cold water ; the roseocobaltic salts do not give a chlorosulphate. forms large, orthorhombic prisms, often several grams in weight, and loses 6H20 when left over sulphuric acid ; crystallisation from water reconverts it into the simple sulphate. The double sulphate, (Co6NH~)~~s0,h(NH~)~so~,8H~o, The triple salt, (Co6NH,),(s0,),C12,3(NH,)2S04,6H20,144 ABSTRACTS OF CHEMICAL PAPERS.forms brilliant octahedra belonging to the cubic system, which do not lose weight at, 100' but become opaque at 120'. The chlorochrornate, (Co6NH3)Cr04C1,3H20, forms brilliant needles isomorphous with the crystals of the chlorosulphate. The selenate, (Co6NH,),(Se04),,5H,0, forms large crystals, is very soluble in water, and loses 4H20 a t 100-105°. forms large, glistening, triclinic crystals, rapidly effloresces, loses all its water a t 100--105°, and, unlike the acid sulphate, can be crystal- lised from water. The chloro-selenate, (Co6NH,)Se04C1,3H20, forms small, glistening, striated, orthorhombic crystals isomorphous with those of the chloro- sulphate. The doubb selenate, (COGNH~)~(S~O,),,(NH~)~SO,,~H~O, forms soluble, orthorhombic crystals isomorphous with those of the corresponding sulphate.The double selenate, forms large, monoclinic prisms. The acetate, (Co6NH,)(C,H302),,3H20, forms long prisms or hexa- gonal plates, which do not lose weight a t looo, but are completely de- hydrated at 125' ; it dissolves in less than its own weight of water at 15", and is hygroscopic. The succinate was not obtained in a crystal- line form; a benzoate was obtained in brilliant plates, but was not By PAUL ROHLAND (Zeit. anorg. Chem., 1901, 29, 159--162).--Violet chromic chloride, which is insoluble in water, remains unchanged when hydrogen is passed through the solution below 90°, but at and above this temperature transformation to the green modification and consequent solution takes place.All the metals, except gold and platinum, effect the solution of the violet chromic chloride, and the order of the degree of influence is the same as the electromotive series of the metals. Violet chromic chloride, when shaken with precipitated tin, passes quickly into solution, I n the solution, tin ions are also to be found, because stannous chloride and chromous chloride are formed. It is doubtful whether the cataiysis is to be attributed to the metal 0 1 9 to fJDe rchromnm rhlode f m m d The Number of the Blue Oxides of Molybdenum. By G. BAILHACHE (Compt. rend., 1901, 133, 1210-1213. Compare Abstr., 1901, ii, 243).-A blue substance of indefinite composition is formed when a concentrated solution of the sulphate, Mo20,,2S03 (loc.cit.), is exposed to the air; an oxide, Mo203,2Mo04,6H20, 1s obtained when the sulphate is heated with barium molybdate, BaMoO,, and water a t looo, in a current of carbon dioxide; on evaporating the blue liquid under reduced pressure, the oxide is left as a bluish-black solid. When ordinary barium moly bdate, Ba3M07024, is used, another blue oxide, 3M020,,2M0702,,16H,0, is formed. With alkalis, both oxides are converted into a pale buff -coloured powder. Phosphorus Molybdenum Compounds. 11. By F. MAWROW (Zeit. anorg. Chem., 1901, 29, 156-158. Compare this vol., ii, 25).- The compound Mo,0,,(H3P0,),,H20, previously described, is soluble The acid selenate, (COGN H,)?(Se04)3,H2Se0,,5H20, (Co6NH,)2(Se04)~,(NH4)~se0~,4H20, anal ysed. T. M. Z. Chromic Chloride. J. McC. K. J. P. 0.MINERALOGICAL CHEMISTRY. 145 in water to a blue solution and gives precipitates with solutions of salts of ammonium, barium, lead, and bismuth. The barium salt has the formula B~O,MO~O,~,(H,PO,),,~~H,O. J. McC. By JULES ALOY (Ann. Chiin. Phys., 1901, 24, [vii], 412-432).-The greater portion of this work has been already published (compare Abstr., 1899, ii, 555, 599 ; 1909, ii, 484; 1901, ii, 164, 244, 317). Uranous cldorophosphate, separates in green crystals from a solution of uranoiis phosphate, UH2(P0,),,5 K,O, in concentrated hydrochloric acid. Uranyl iodide, UO,T,, prepared by adding a slight excess of barium iodide t o an ethereal solution of the nitrate, UO2(NO,),,3H,O, separates in red, deliquescent crystals which are very readily decomposed. Potassium uyanyl cyanide, U02(CN),,2KCN, obtained by treating a dilute solution of uranyl acetate with a large excess of solid potassium cyanide, forms a voluminous, bulky precipitate, which subsequently changes into a mass of pale yellow prisms. By A. W. KAPP (Ann. Phys., 1901, [iv], 6, 754--773).-Freezing point determinations have been made at intervals of 10 per cent.. for each binary combination of the metals bismuth, tin, lead, and cadmium. The temperatures at which a solid separated out from the liquid alloy were determined from the halts in the cooling curve. The author finds that in no case does tho eutectic alloy correspond with simple atoFic proportions of the components (compare Guthrie, Abstr., 1885, 329 ; Miolati, Abstr., 1892, 1139 ; Dams, Ann. Pl~ys. Chem., 1895, 54, 486). The eutectic alloys are found t o have the following composition : Tin-bismuth ...... 56 per cent. Bi Cadmium-tin 70 per cent, Sn Lead-bismuth ...... 57 ,, Bi Lead-tin ...... 66 ,, Sn Cadmium-bismuth 60 ,, Bi Lead-cadmium 16 ,, Cd. The values given for the composition of the three eutectic bismuth alloys differ somewhat from those given by Guthrie, especially in the case of tin-bismuth. Uranium and its Compounds. UH,(PO,),,UC4~ G. T. M. Complete Freezing Point Curves of Binary Alloys. J. C. P.

ISSN:0368-1769    

DOI:10.1039/CA9028205130

出版商:RSC    

年代:1902

数据来源: RSC

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MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. 145 Graphite Deposits of Battugol. By L. JACZEWSKI (Jahrb. Min., 1901, ii, Ref. 74-77; from Explorutions gtol. et mini&es Ze long du chemin de f e r de Sibtyie, Livre XI, 1899, 19-56). -The graphite of the Alibert mines at Battugol (Botogolskij-Golez) occurs in limestone and in nepheline-augite-syenite. Under I are the results of an analysis of the latter rock; I1 of the augite from the same rock (also loss on ignition, probably representing graphite, 1.63146 ABSTRACTS OF CHEMICAL PAPERS. per cent.); I11 of augite free from alkalis from a similar rock. Determinations of the sp. gr. and rate of combustion point to the material being mainly the graphitite of Luzi rather than graphite. SiO,. TiO,. AI,O,. Fe,O,. FeO. CaO.MgO. K20. Na,O. Total. I. 55.41 - 19.84 9.50 - 3.86 - 5.29 5.97 99.87. 11. 38.00 - 8-57 11.50 - 0.27 2.80 102.31. 111. 44.15 1.85 - - 34.13 20.17 0.40 - - 100.70. L. J. S. Inflammable Gas in the Netherlands. By J. LORI~ (Jahrb. Bin., 1901, ii, Ref. 84; from Tijdschr. k. Nederl. aardrijkskundig Genotsch. Leiden., 1899, 35 pp.).--It has long been known that inflammable, sometimes self-igniting, gas, is exuded from the ground at many places in North and South Holland and Friesland. The sandy alluvial ground contains remains of plants and shells and there is no doubt that to these substances the gas owes its origin. Bore holes are put down to a depth of 12 to 80 metres to collect the gas, the results of two analyses of which are : CH,. co,. N. 0. H. co. 97.7 10.4 9.0 0.5 0.4 - 74.8 3.4 16.2 0.4 4.6 0.6 L.J. 5. Analysis of Manganese [Minerals] from Sardinia. By C . RIMATORI (Atti Real. Accad. Lincei, 1901, [v], 10, ii, 226-232)- Analyses and physical properties of manganese minerals found in Sardinia. They are mostly varieties of pyrolusite. Two of the samples must, however, be regarded as psilomelane and one, containing 20-68 per cent. YbO, resembles a specimen of wad (Wackenrodite) from Baden. I n all the specimens examined, the manganese was only present in the form of nodules or small fragments. T. H. P. [Chalcopyrite and Bornite as Furnace Products.] By ALEXANDER N. WINCHELL (Amer. Geologist, 1901, 28, 244-246)- The iron rails in the bed of a calciner for copper ores at Butte, Montana, become in a few months converted into chalcopyrite with which is a little bornite.Analyses are given of the chalcopyrite, L. J. S. Manganosphmrite, a new variety of Oligonite. By KARL Busz (Jahrb. Min., 1901, ii, 129--132).-The chalybite vein of the Louise mine at Horhausen, Westerwald, is intersected by a dyke of basalt, the cavities in which are partly or wholly filled with botryoidal aggregates of a fawn-brown mineral resembling sphsrosiderite in appearance. The following analysis shows, however, that the mineral differs from sphsrosiderite (FeCO,) in containing much manganese, and that in composition ( 3FeC0,,2MnC03) it agrees with Breithaupt's oligon-spar, of which crystals only have been previously described.MINERALOGICAL CHEMISTRY. 147 FeO. MnO. CO,. Total. FeCO,. MnCO,. Sp.gr. 36.72 24.76 38.34 99.82 59-71 40.11 3.630 Microscopical examination shows that the mineral is homogeneous, and not a mixture of rhodochrosite (MnCO,) and chalybite (FeCO,). L. J. S. Altered Peridotite in Mysore. By THOMAS H. HOLLAND (Mem. Geol. Xurvey India, 1901, 34, l-g).-Altered peridotites in Southern India are usually penetrated by veins of white magnesite, but in the rock from Huliyar now described this is not the case. Here dark gray crystals of breunnerite from half an inch to an inch across are scattered through a matrix of talc and serpentine. The breunnerite, which encloses talc, serpentine and magnetite, gave on analysis the results under I corresponding with MgCO, : FeCO, = 10 : 1. The matrix of talc, serpentine, magnetite and a little pyrites gave I1 : SiO,.Fe203. FeO. CaO. MgO. GO,. H,O. S. Insol. Total. Sp.gr. I. - 2'93 8.27 trace 39'20 47-01 - - 1.57 98.98 3.168 11. 42-20 13.59 - 30.41 5'30 7.73 0.11 - 99.34 2.853 v L. J. 5. [Datolite from] Canada. By G. CHRISTIAN HOFFMANN (Amer. J. Xci., 1901, [iv], 12, 447-448).-A compact white mineral from the Daisy mica mine, Derry, Ottawa, Co. Quebec, is proved by the following analysis, by R. A. A. Johnston, to be datolite : KO,. B2OP A1,0,. Fe,03. CaO. MgO. H20. Total. Sp.gr. 36.94 22.37 0.12 0.02 34.90 0.05 5-68 100*08 2.985 Associated with it is the rare mineral faujasite. L. J. S. Isomorphism of Plagioclase Felspars. By FRANZ LOEWINSON- LESSINU (Centr. Bin., 1901, 708-709. Compare Abstr., 1900, ii, 354 ; this vol., ii, SO).-The suggestion is put forward that albite and anorthite are not isomorphous, but form a series of double salts, and that these double salts enter into isomorphous mixkure with each other, and perhaps also with the end members of the series.Colourless Chlorite from Aj River, Zlatoust. By PETR A. ZEMJATSCHENSHY (Zeit. Kryst. Min., 1901, 35, 357-360).-This occurs as colourless scales with hornblende and rutile in a white, crystalline, dolomitic limestone. It is optically positive, and the axial angle 2E varies from 0" to 50'. Sp. gr. 2,675-2.744 (mean 2.704). Analysis gave : L. J. S. Si02 A1203. Fe,O,. FeO. CaO. MgO. H,O. 31.053 24.301 0.454 1.776 2.090 24.493 12.391 This chlorite is remarkable in containing very little iron, and, except in the relative amounts of alumina and magnesia, it resembles leuchtenbergite in composition.Formula, 3R0, A1,0, 2SiO,, 3H20, or 2 CaO, 38( Mg,Fe)O, 1 381 203, 2 8SiO,, 3 7H20. According to Tscher- mak's theory of the chlorite group, the composition may be expressed148 ABSTRACTS OF CHEMICAL PAPERS. by Sp,Atl,, but there is a remainder of H6Ca,Si701, amounting to one- tenth of the whole. According to Clarke's theory, the formula is written as Ekeolite-syenites and Corundum-syenites in Madras. By THOMAS H. HOLLAND (LVem. Geol. h'uvuey Indiu, 1901,30, 169-224).- A petrographical description is given of elzeolite-syenites, augite- syenites and corundum-syenites from Sivamalai in the Coimbatore district. 11, of large crystals, sometimes five inches across, of yellow elzeolite from the coarse-grained '' contemporaneous veins " of eholite-syeuite which penetrate the rock of the ordinary type.I11 is of large crystals of grayish felspar from these veins : SiO,. A1,0,. Fe,O,. CaO. MgO. K,O. Na,O. ignition. Total. Sp. gr. Analysis I is of the ordinary type of elzeolite-syenite. LOSS OQ I. 55.68 23.81 4-84 1.69 0-65 5.16 9'23 0.34 101.98 2 5 9 3 II. 43'35 34.32 1'02 0.82 - 5.52 14.62 0.75 100'40 2'62 111. 64-70 22.63 0'43 1'34 0.49 5.86 6'02 0.09 101.56 2'534 Corundum occurs as tabular, well-developed crystals in a rock con- sisting principally of felspar (albite and orthoclase), as in the Urals (Abstr., 1899, ii, 763) and in Eastern Ontario (Abstr., 1900, ii, 552). By HENRY A. WARD (Arne?.. J. Xci., 1901, [iv], 12, 453-459).-This Persian meteorite is one of the Four siderolites which have been seen to fall; i t fell in May, 1850, and weighs 51% kilograms.It consists of 42.3 per cent. of silicates, and 57.7 per cent. of metal. Sp. gr. 4-57. The silicates present are, enstatite, olivine, possibly peckhamite, and a basic felspar. The metal has the following composition (analysis by J. E. Whitfield) : L. J. 5. The Veramin Meteorite. Fe. Ni . co. P. S. Sp. gr. 92.06 6.96 0.73 0.10 0.15 5.56 L. J. S. Red Rain or Blood Rain. By NAPOLEONE PASSERINI (L'Orosi, 1901, 24, 325-332. Compare Abstr., 1901, ii, 322, 456)-Analysis of the red matter falling with rain on March loth, 1901, in various parts of Italy and Central Europe shows that it consists mainly of silica, aluminium and calcium silicates, ferric oxide and organic matter (SiO, 44.3709, CaO 12.3964, Al,O, 23.6159, Fe,O, 6.9764 ; organic and volatile matter 10,4677 per cent.) with small quantities of other silicates, and of carbonates, sulphates, chlorides, nitrates, &c. The red colour is due especially t o the ferric oxide and organic matter. Mineralogical examination of t h e matter by Giovanni D'Achiardi shows it to consist of grains, varying in size but always small; the grains are mostly of quartz, but many other minerals are also present, including felspar, pyroxene, mica, chlorite, haematite, calcite, or dolo- mite, (ec. Tbe matter is probably of cyclonic origin. T. H. P, Traces of Diutomucem may also be detected.

ISSN:0368-1769    

DOI:10.1039/CA9028205145

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

PHYSIOLOOICAL CHEMISTRY. Physiological Chemistry. 149 Influence of External Temperature on Warm-blooded Animals. By ARTHUR FALLOISE (Frau. dzc lab. de L. Fredericq, LiZge, 1901, 6, 183-208; from A ~ c h . de Biol., 17, 761).-In guinea pigs, rats, and pigeons, as the temperature of the air falls from 21' to Oo, the production of carbon dioxide increases, so that it may be doubled or even tripled. Above 2l0, there is also an increase, but it is not so marked. In-man, the same change occurs, but in a less regular manner. W. D. H. Influence of Breathing an Atmosphere rich in Oxygen. By ARTHUR FALLOTSE (Trav. dw lab. de L. Fredericq, LiGge, 1901, 6, 135-182 ; from Arch. de Biol., 17, 713).-The absorption of oxygen, under the influence of respiring an atmosphere rich in that gas, only increases to a slight amount proportional t o the quantity of oxygen which the liquids of the organism dissolve in putting themselves in equilibrium of tension with that of the oxygen of the surrounding air.This equilibrium is rapidly established, so that increase of absorption as rapidly ceases. I f the tension of the atmospheric oxygen returns t o the normal, the excess of oxygen previously absorbed escapes rapidly for corresponding reasons. W. D. H. Respiratory Exchange during the Deposition of Fat. By MARCUS S. PEMBREY (1. Physiol., 1901, 27, 407--417).-During the autumn, the marmot feeds eagerly on carbohydrate food and rapidly deposits fat in its body as a reserve for combustion during its winter- sleep. The respiratory quotient CO, : 0, is greater than unity ; the mean of 22 determinations is 1.21, the maximum being 1.39, the minimum 1.04.These high quotients cannot be explained by a reduc- tion in the absorption of oxygen, for, compared with the condition during fasting, there is a considerable increase, The probable explana- tion is that suggested by Hanriot : during the formation of fat from carbohydrates, a considerable quantity of carbon dioxide is split off from the carbohydrate molecule. Influence of Occlusion of the descending Aorta on the Respiratory Exchanges. By HECTOR RULOT and LEON CUVELIER (Trav. du lab. de L. liredericq, Ligge, 1901, 6, 9-20; from Arch. de Biol., 15, 629),-Bohr and Henriques (Arch. de physiol., 1897) have stated that occlusion of the thoracic aorta exercises no influence on the respiratory exchange ; they therefore conclude that the main seat of combustion in the body is not in the tissues and organs of the body, but in the lungs, thus carrying one back to the ideas which prevailed in the time of Lavoisier.The present experiments on dogs show that these ideas have no foundation, The greater the portion of the body shut off from the circulation, the less is the sum total of the respira- tory interchanges. At the highest level of occlusion, these were W. n. H. YQL. LXXXU. ii, 11150 ABSTRACTS OF CHEMICAL PAPERS. reduced to a half of the normal. The respiratory quotient rises during occlusion ; after occlusion, it generally falls but sometimes rises. W.D. H. Garbon Dioxide as an Excitant of the Respiratory Centre. By HECTOR RULOT and L*ON CUVELIER (Tmv.du lab. de L. Fredericq, ZGge, 1901, 6, 1-8; from A T C ~ . de Biol., 15, 621)-The csymptoms produced by excess of carbon dioxide are very similar to those caused by diminution of oxygen, and some observers doubt whether carbon dioxide is really an excitant of the respiratory centre. The present experiments confirm the classical theory that the gas is an excitant of the respiratory centre, which has also been recently stated to be the case by Zuntx and Loewy (Arch, f. Physiol., 1897, 379-390). W. D. H. Changes in the Composition of Gas injected into the Subcutaneous Tissues. By L i o ~ PLUMIER (Trav. du lab. de 1;. Predericq, Liggge, 1901, 6, 77-98 ; from Arch. de Biol., 16, 323)-Gases introduced into the subcutaneous tissues are absorbed especially quickly in thecase of thosesoluble in the blood.Before absorption, the gases tend to put themselves in equilibrium of tension with the blood gases, and this equilibrium is soonest reached in the case of gases which are most soluble in the blood. The oxygen tension in the blood of the subcu- taneous region is equal to 6-8 per cent. of an atmosphere, the corre- sponding number for carbon dioxide is 5 to 8, and for nitrogen 80 per cent. If the gas injected contains a high percentage of carbon dioxide and oxygen, the tension of the oxygen becomes temporarily greater than that of the oxygen of the atmosphere ; this is simply because the carbon dioxide is more rapidly absorbed than the oxygen. w. D. H. The Gases in Blood a t Different Altitudes during a Balloon Ascent.By J. TISSOT and HALLION (Compt. rend., 1901, 133, 1036-1038. Compare this vol., ii, 92).-Experiments made with the blood of a dog during the ascent of a balloon to a height of 3500 metres and its subsequent descent, the results being corrected for the action of air on the collected blood between the time of its withdrawal from the animal and the analysis, show that the power of hsmoglobin to combine with oxygen increases somewhat with a reduction of pressure, at any rateup to the altitude stated. On the level, 100 C.C. contained 15.5 C.C. of oxygen, a t 3500 metres, 19.97 c.c., and a t 800 metres during the descent, 15.7 C.C. The variations in the quantity of carbon dioxide in the blood are in the opposite direction to those required by the laws of the dissolution of gases, whereas the nitrogen behaves as if it were simply dissolved, 100 C.C.of blood containing 3.25 C.C. at the l e ~ e l and only 0525 C.C. at 3.500 metres. The total quantity of gases con- tained in the blood increases with the altitude, and the quantities of carbon dioxide and oxygen likewise increase with the altitude. The pressure of the blood in the femoral artery of the dog remained con- stant throughout the ascent. C. H. B.PHYSIOLOCTICAL CHEMISTRY, 151 8ugars of the Blood and Glycolysis. By RAPHAEL LEPINE and BOULUD (Compt. rend., 1901, 133, 720--721).-Horse’s blood possessing the same reducing power as dog’s blood is less dextrorotatory or may even be laworotatory. If dog’s blood is kept for an hour a t 39’ while oxygen is passed through it, the fermentable sugar disappears, and the dextrorotatory power decreases or the laevorotatory power increases. This is believed to be due to the glycolysis of the sugar, and the appearance of conjugated glycuronic acid.The presence of chloroform somewhat hinders the change. W. D. H. Physiology of the Gill, and Osmotic Pressure of the Blood in the Crayfish. By LEON FREDERICQ (Trav. du lab. de L. Fredericq, Ligge, 1901, 6, 61-63 ; from Bull. de Z’Acud. roy. de Belg., 1898, [iii], 35, 831--833).-The amount of salt in crab’s blood can be increased or lessened by altering the amount inthe water in which they live. It is quite different in the fresh-water crayfish. Although the gill membrane is so thin, it does not play the inert r8Ze of a membrane in a dialyser, but is a barrier which effectually separates the internal medium, the blood, from the external, so far as salts are concerned, although it is naturally traversed by the gases of respiration.The osmotic tension of the blood is equal to that exerted by a 1.3 per cent. solution of sodium chloride (A = 0.8’) ; this is higher than is found in vertebrate blood. W. D. H. By JACQUES LOEB, MARTIN FISCHER, and HUGH NEILSON (P’iiger’s Archiv, 1901, 8’7, 594-596. Compare Abstr., 1900; ii, 608 ; 1901, ii, 177).-Further experiments in support of those previously published. By ARTHUR W. GREELEY (Amer. J. Physiol., 1902, 6, 296-304).-After maturation has been completed, the unfertilised eggs of the starfish, Asterias forbesii, can be made to dovelop regularly into bipinnaria by an exposure to a temperature of 4Oto ‘7” for from 1 to 9 hours.Segmentation of the Asterias egg cannot be produced by raising the temperature of the sea-water. This is due to conjugated glycuronic acid. Artiflcial Parthenogenesis. W. D. H. Artificial Parthenogenesis. W. D. H. Prolongation of the Life of Sea Urchins’ Eggs by Potassium Cyanide. By JACQUES LOEB and WARREN H. LEWIS (Amer. J. Physiol., 1902, 6, 305-317).--The life of the unfertilised eggs of the sea urchin can be materially prolonged by adding to the sea-water a small quan- tity of potassium cyanide. Sexual as well as parthenogenetic develop- ment is prolonged. So long as death is considered as something merely negative (namely, the cessa- tion of life processes), it must appear paradoxical that a deadly poison will prolong life.The paradox disappears if it is assumed that certain active (mortal) processes occur so as to cause death. These specific processes (possibly enzymatic) are in unfertilised eggs checked or modified by sexnal or osmotic fertilisation, and also by potassium cyanide, which substitutes for the destructive action of these processes a condition of suspension of life. Lack of oxygen has little or no influence. W. I). H. 11-2152 AESTRACTS OF CHEMICAL PAPERS. Eggs of Rana Temporaria. By HEINZ KOLB (Chern. Centr., 1901, ii, 1233 ; from Inaug. Diss.-Zurich, 1901) -The amount of glycogen, water, sulphur, phosphorus, and fat were estimated a t different periods during the development of the eggs of the common frog. Glycogen shows periodical variations, being a t its minimum when the egg is ripe.Sulphur increases, and phosphorus diminishes, during development ; fat shows a slight increase, water a marked oue. W. D. H. Composition of Egg-Yolk. By JOHN MALCOLM ( J . PhysioZ., 1901, 27, 356--359).-The percentages of proteid, fat, and phosphorus in the yolk of eggs from the same hen are in closeagreement. There are, however, very considerable differences in eggs from a number of hens, even of the same breed. The percentage of lecithin varies considerably. Analytical details are given [compare Thorpe, this vol., ii, 951. w. D. I€. The Osmotic Pressure of Dog's Submaxillary Saliva. By PIERRE NOFL (Trau. du Zab. de L. Fredei*icp, Lizge, 1901, 6, 225-239 ; from A ~ c h de Bid,, 18)-The osmotic pressure of the sub- maxillary saliva of the dog, obtained by stimulation of the chorda tympani is variable (A = 0.193-0.396).The saliva from the same gland, secreted spontaneously, is more dilute (A = 0*109-0*266). The tension is due all but exclusively to the salts of the saliva. The osmotic tension rises when the duct is obstructed ; this is explicable by supposing that absorption of water occurs in the excretory tubules W. D. H. Clonversion of Pancreatic Zymogens into Enzymes. By HORACE M. VERNON (J. Physiol., 1901, 2'7, 269--322).-Extracts of fresh pancreas show usually no ferment activity for some days, and then suddenly develop nearly their maximum power. After maintain- ing this power for some days or weeks, they gradually deteriorate. When the glands from several animals are minced together and extracted, the ferment activity begins to develop a t once, As regards trypsin, glycerol extracts are the most powerful ; the rennetic value is but little influenced by the nature of the extracting liquid.As a rule, however, tryptic and rennetic values vary together. Diluting glycerol extracts with water develops tryptic power increasing with the degree of dilution. The conversion of zymogens with enzyme is enormously increased by the addition of an active extract. It, is the tryptic ferment which liberates both the ferments, The products of tryptic digestion have the same power to a less degree. Bubbling oxygen or carbon dioxide through the glycerol extract at 38' has no influence, but if active extract is added as well, oxygen increases, and carbon dioxide diminishes, enzyme formation.I n order to obtain an active tryptic extract, the plan advised is to use pig's pancreas, and extract it with 50-75 per cent. glycerol and test its proteolytic power every few days. After it bas risen considerably, and before much auto-digestion has occurred, the glycerol should be filtered off and kept separate. Its activity would still further increase, and then remain nearly constant for months and perhaps years. One part of thePHYSIOLOGICAL CHEMISTRY. 153 finely minced gland, and four parts of the extracting liquid by volume EhQuld hs emt$ged, W, D.. H Production of the Tryptic Ferment from its Zymogen. By HENRY F. BELLAMY (J. PhysioZ., 1901, 27, 323-335).-The dog’s pancreas presents two phases of activity ; (1) a slow and continuous one, feebly evident after digestion, and reaching its height during complete fast ; during this period, the principal material in the gland cells is zymogen : (2) a rapid and intermittent phase coincident with the period of gastric activity, in which, as advocated by Herzen, the inactive zymogen receives an ‘ internal secretion ’ from the spleen, which liberates the trypsin.The blood is the vehicle by means of which this is conveyed to the pancreas ; it is not present in the serum ; if it is in the plasma, it is destroyed when the blood clots ; it probably is conveyed by the blood corpuscles. If a dog is deprived of its spleen, no trypsin is formed, but trypsinogen continues to be formed and is secreted as such; i t can, however, be rendered useful by sub- sequent conversion into trypsin by an agency other than splenic, namely, by the secretion of the mucous membrane of the small intestine, especially of the jejunum.W. D. H. Proteolytic Enzyme of the Thymus. By FR. KUTSCHER (Xeit. physiol. Chem., 1901, 34, 114--118).-The thymus gland contains a proteolytic enzyme, which leads to auto-digestion in extracts of the gland. Among the products of proteolytic action, ammonia and lysine are found ; arginine, aspartic acid, glutamic acid and tyrosine are absent. The presence of histidine and leucine is doubtful. Whether this action is due to trypsin, or to another hitherto unknown enzyme, is for the present left uncertain. W. D. H. Nutrition of the Suckling Infant. By KARL OPPENHEIMER (Zeit.Bid., 1901, 42, 147--160).-The varying needs of an adult for food are comparatively easy to understand. It is more difficult to realise why infants during suckling, in which the amount of muscular exercise is uniformly small, should also take different amounts of food. The amount of milk taken may be ascertained by weighing the child before and after each meal. I n cases previously recorded, the total milk sucked during the first ten weeks of life varies from 30 to 53 kilograms. I n the present paper, careful observations are given in connection with a child prematurely born a t the eighth month, and the results are compared with the figures previously given by others, and an attempt made to find a general rule to account for the variations. In two children, there was a constant relation between amount of food and body weight, but this does not hold throughout.The con- stant relat’ionship is between food and body surface (Rubner’s law). W. D. H. Energy Value of Diet in Man. By MAX RUBNER (Zeit. Biol., 1901, 42, 261--308).-A general view is given of the author’s well known work on this subject. The nutrition value of a few important food stuffs is as follows : meat, 76.8 ; bread, 82-1 ; milk, 89.8 ; potatoes,154 ABSTRACTS OF CHEMICAL PAPERS, 92.1. for use in the body. reckon the value of mixed dietaries. statistical. W. D. H. These numbers are the percentage of the total energy available These and other numbers are employed t o The facts given are mainly By LBON FREDERICQ (Frau, dzc lab. de L. Fkedericp, Lizge, 1901, 6, 64-66 ; from Bull.de Z’Acad. roy. de Belg., 1898, [El, 35, 834--836).-Bunge states that sodium chloride is chiefly used by those who take abundance of vegetable food in order to combat the harmful influence of potassium salts which predominate in vegetables and which would otherwise tend to replace the sodium salts of the blood and tissues. Lapicque, on the other hand, believes that the function of salt is simply to accentuate the flavours of foods, and that this purely gustative action can equally well be carried out by salts of other metals. The observations recorded in the present paper support the latter view. An examination of the salt prepared by the natives of the Congo State by burning aquatic plants show it to consist mainly of potassium chloride and sulphate.W. D. H. The Physiological Significance of Salt. Action of Alcohol on Man. By R. 0. NEUMANN (Arch. Hyg., 1901, 41,85-118).-Polemical against Rosemann. The author maintains his original contention that alcohol acts as a proteid-sparer. By MAX CREMER (Zeit. Biol., 1901, 42, 428--467).-The paper is largely con- cerned with theoretical considerations on carbohydrate metabolism. One of the most important is the assertion, which rests on experimental proofs, that proteids which are free from a carbohydrate radicle do not lead to glycogen formation. Rhamnose does not lead to glycogen formation, but comparatively small amounts leave the body as such. It has a calorific value, and its combustion leads t o a sparing effect on other constituents of the body, especially of fat, Numerical data of experiments on one dog and four rabbits, mainly relating to gaseous metabolism, are given. The Origin of Glycogen from Proteid.By BERNHARD SCHONDORFF (PfEuger’s Archiv, 1901, 88, 339-345).-Polemical. A reply to Cremer. W. D. H. W. D. H. The Value of Rhamnose in the Animal Organism. W. D. H. Behaviour of Xylan in the Animal Body. By B. SLOWTZOFF (Zeit. physiol. Chem., 1901, 34, 181--193).-1n rabbits, if xylan is given with the food, part is absorbed (33 to 83 per cent.), and the remainder passes away with the fsces. A small portion (1.5 to 4.6 per cent.) of that which is absorbed appears in the urine; the rest is used by the organism, although it is uncertain if this has any nutritive value. The urine contains a furfuraldehyde-forming substance of undetermined composition.If the animal is killed a short time after injection of xylan, that material is found in the blood, liver, and muscles, Xylan undergoes putrefaction, but not so readily as xylose ; its destruction in the intestines by putrefactive agencies is improbable. W, D. H.PHYSIOLOGICAL CHEMISTRY. 155 Changes in the Carbohydrates in the Body of Ascaris. An Animal Fermentation Process. By ERNST WEINLAND (Zeit. Biol., 1901, 42, 55-90).-The author has previously called attention to the large amount of glycogen in the body of various parasitic worms. It often amounts t o from a third to nearly a half of the total dry material. The present experiments were made on the common round worm Ascaris. This animal requires no free oxygen, and can be kept alive in boiled saline solution for several days; bubbling oxygen through the salt solution does not prolong its life; but bubbling carbon dioxide through the solution almost doubles its period of life.The daily loss per 100 grams of body weight is 0.7 gram of glycogen, 0.1 gram of dextrose, and 0.07 gram of nitrogen. The relative amount of water to solids increases, but the fat undergoes practically no change. The normal alkalinity of the animal’s tissues diminishes, and may even be replaced by faint acidity. The daily production of carbon dioxide (during hydrogen respiration) is 0.38 gram per 100 grams of body weight. The animal acquires a rancid odour, and this is due to two fatty acids, butyric and valeric, 0.3 gram of valeric acid being produced daily for every 100 grams of body weight; this is not due to micro- organisms, but is a product of the animal’s metabolism.‘l‘he nitrogen found in the salt solutiion in which the animal lives amounts to 0.0015 gram per 100 grams of body weight daily; the form in which the nitrogen leaves the body was not ascertained. On comparing the loss of weight to the products excreted, the former is found t o be the greater ; probably some of the lost material is used in the production of ova and spermatozoa. Provisional formulz are given to account for the breakdown of carbohydrate material. Particular attention is drawn to the fact that this breakdown is not oxidation, but an action of a fermentative nature similar to that which occurs in certain micro- organisms and fungi, W.D. ’H. Formation of Fat from Carbohydrate. By EARL B. LEHUANN and ERWIN VOIT (Zeit. B i d , 1901, 42, 619-671).-The experiments show that a carbohydrate diet causes a considerable but variable putting on of carbon in the body, W. D. H. [Fat Absorption.] By EDUARD PFL~GER (Pjiiyer’s Archiu, 1901, 88, 299-338, 431--452).-These are two further contributions to a much debated question. Details are given regarding the melting points of Fatty mixtures; the existence of a form of oleic acid in horse’s fat with a high iodine number; the solubilities of fats and fatty acids in various mixtures of bile and sodium carbonate; the importance of sodium carbonate for the bringing of oleic and other fatty acids into a form which is soluble in water ; the importance of the bile circulation both for the digestion and absorption of fat, and, in the second paper, the importance of the presence of soaps for enabling fatty acids to enter into solution.W. D. H. The Physiological Proteid Minimum. By MAX CREMER and M. HENDERSON (Zeit. Biol., 1901, 42, 612--617).-Two experiments are described on dogs, which are similar to those performed by E. Yoit156 ABSTRACTS OF CHEMICAL PAPERS. Resting. and Korkunoff (Zeit. Biol., 32, 58). these authors were not obtained. The extreme values given by W. D. H. Work- ing. Proteid Metabolism. By MAX GRUBER (Zeit. Biol., 1901, 42, 407--427).-The subject of proteid metabolism is treated mainly from the theoretical standpoint ; Pettenkoferand Voit's old distinction between the organ proteid, which undergoes but little and that a constant change, and the proteid derived directly from the food, which is subject to great variations, is insistedon.The influence of water in increasing the excretion of waste nitrogenous products, and the fact that different proteids after absorption vary in their yield of katabolic products, are supported by experiments. Decomposition of Proteids in Men during the Performance of Hard Work. By C. JACKSON ( A t t i Real. Accad. Lincei, 1901, [v], 10, ii, 186--188).-The author has compared the urine of five persons while a t rest and while undergoing vigorous exercise on a mountain climb. The results are given in the following table : (1) mas a porter of 35 years; (2), (3), and (4) men of 26,32, and 62 years respectively; and (5) a youth of 17 years : W.D. H. Resting. Specific gravity. Eik- Resting. -4- Tiek- 0.65 1.13 0.94 1.27 1.32 Total nitrogen. 0.99 0.92 1.18 0.69 1-82 0.83 0.80 0.82 0.88 0.87 0.77 0.56 0'66 0.42 0-86 Nitrogen as urea and ammonia. 1024 1023 1024 1021 1023 1023 1028 1024 1026 1030 I- 0.78 1'41 1.14 1-43 1-51 1-28 1-65 1.79 1'65 2-11 Ratio of nitrogen as urea and am- monia t o total. -I- I Thus in all cases, more nitrogen was eliminated in the urine during work, a fact perhaps depending to some extent on the increased amount of food taken; (1) and (5) ate very well, whilst (4) took scarcely any food. Except for ( 5 ) , the proportion of the total nitrogen present as urea was diminished by working. It is probable that fatigue is a pathological condition in which the matter eliminated from the body is not only increased, but changes in a manner that indicates a solution of the tissues, probably of the muscles.By exeqcise, the same work becomes possible without destruction of the muscles. T. H. P. The Change produced in Albumoses by the Gastric Mucous Membrane. By KARL GLAESSNER (Beitr. chem. Physiol. Puth., 1901, 1, 328--338).-A regeneration of proteid from its hydrolytic products occurs in the gastric mucous membrane; this, however, relates exclu- sively to the albumoses, The change in tbe dog commences SOOD afterPHYSIOLOGICAL CHEMISTRY. 157 digestion starts, reaches its maximum five or six hours later, and then subsides. This power of proteid synthesis is a property of the mucous membrane. It is not considered that rennin plays any part in the process; the formation of plastein by rennin in vitro is probably not analogous to what occurs in viwo.Nutritive Value of Gelatin, W. D. H. By OTTO KRUMMACHER (Zeit. Biol., 1901, 42, 242-260).-The heat-value of gelatin, as obtained by the use of the ca.lorimeter, was found to be 5.3676 Cal. in one preparation, 5.3779 in another. I n order to obtain its physiological heat value, several deductions have t o be made, principally for unburnt products in urine and faeces ; after the deductions, the heat value is 3.8835 Cal., or 72.35 per cent. of the total energy ; Rubner’s numbers for meat and proteid are 74.9 and 76.8 per cent. respectively. I n experiments on dogs, the proteid decomposition during gelatin feeding is 62.6 per cent.of that which is broken down during inanition. This proba,bly represents the maximal action of gelatin. I n a man of mean body weight, the amount of proteid which undergoes katabolism per diem is 70 grams. If gelatin is given to exert the maximal effect, it being assumed that the same relationship holds for man as for dogs, 33 grams of gelatin will reduce the katabolised proteid to 56 grams, or 33 grams of gelatin will spare 14 grams of proteid. W. D. H. The Nutritive Value of Meat and Meat Preparations in Man. By WILHELM PRAU~NITZ (Zeit. BioZ., 1901, 42, 377--406).-A research carried out i n the usual manner, in which the utility of various forms of meat food is compared. The main result is that fresh meat cooked in the usual way is much more easily digested than various preparations in which drying of the meat is part of the method employed.Roast fresh meat is almost entirely absorbed, and leads to only a small formation of faeces. Among the various patent preparations, there are differences, but in every case the amount of faxes is large, and contains much unused nutriment. W. D. H. The Place of Purine Substances in Metabolism. By OTTO (Pcfiiger’s Archiv, 1901, 88, 296-’298).-Polemical against LOEWI Burian and Schur (this vol., ii, 33). W. D. H. Relationship of Iron and Pigments in the Liver and Skin. By N. FLORESCO (Compt. Tend., 1901, 133, S28--830).-From observa- ntions made at first on snails, but later on dogs, cats, and rabbits, the conclusion is reached that there is a relation between the liver and the skin and also the fur, in point of view of the amount of iron and of pigments.The liver, and the skin of dark-coloured animals contain nearly double the quantity of iron and of pigment which those with white fur possess. Intermediate cases occur in those lightly-coloured. W. D. H. The Ammonia removing Function of the Liver. By ARTHUR BIEDL and HEINRICH WINTERBERG (P’iiger’s Archiv, 1901, 88, 140--199).-The statement made by previous observers that the blood158 ABSTRACTS OF CHEMICAL PAPERS. entering the liver contains more ammonia than that which leaves it is confirmed. The power of the liver to remove ammonia is in the present research investigated on animals which have been poisoned by ammonia and certain ammonium salts. I n some experiments, the liver was thrown out of gear by an Eck's fistula.The liver appears to be able t o cope with increased quantities of ammonia produced in certain pathological states; the proof is not, however, clear that this alone will explain the autointoxication produced when the liver is thrown out of the circulation. W. D. H. Formation of Free Iodine from Iodoform. By FRITZ ALTEN- BERG (Chem. Centr., 1901, ii, 1213 ; from A d i . int. Pharmukodyn. Thev., 8, 106).-Urine, blood, and pus cannot decompose iodoform with the formation of free iodine. Cellular organs in the absence of micro- organisms can do so, however; this power is especially found in secreting glands, particularly the testis. Formation of Ethereal Sulphate in the Animal Body. By GUSTAV EMBDEN and KARL GLAESSNER (Beitr. chem.Physiol. Puth., 1901, 1, 310-327).-'J!he experiments were performed on dogs by the perfusion method. The liver was found to be the principal place where the synthesis leading to the formation of ethereal sulphates takes place. They are not formed by the muscles or intestine, but small quantities are manufactured by the kidneys and lungs. W. D.-H. W. D. H. Effect of Freezing on Milk. By FRED. BORDAS and &a. DE RACZKOWSKI (Compt. Tend., 1901, 133, 759--760).--On freezing milk, the upper portion of the block is soft and contains most f a t ; the peripheral portion is transparent ; the centre forms a white nucleus and is chiefly casein and sugar; the lower portion contains even a larger proportion of cbsein and sugar, The following are the analyses (per cent.) of the four portions : Peripheral.Upper. Central. Lower. Ash ......... 0.46 0.61 2*10 2.78 Fat ......... 1.54 21.68 1-58 0-79 Lactose.. .... 2.81 3.52 10.64 18.65 Casein ...... 1-72 6.40 12.43 19.31 W. D. H. The Diurnal Curve of Sweat Formation. By LBON FREDERICQ (Frau. du lub. de L, FTedericp, Ligye, 1901, 6, 209-212).-By determ- inations on the author'sown person, it is shown that the curve of sweat formation in the day very accurately follows that of the diurnal changes of temperature. The increased formation of sweat during muscular activity is mainly due to elevation of the internal body temperature. The rise of temperature acts on the nervous centres concerned in the process. W. D. H. By ROBERT ARNSTEIN (Zed. physiol. Chem., 1901,34, 1--27).-The methods investigated were those Estimation of Acidity in Urine.PHYSIOLOGICAT, CHEMISTRY. 159 of Freund-Lieblein and of Jager.acidity is also studied. accurate method is promised. The influence of various salts on the Further investigation in order to find an W.D. H. Investigation of Feces. By HANS URY (Chem. Cent?'., 1901, ii, 1233-1234 ; from DeiLtsch. rned. Woch., 27, 718--723).--The paper mainly relates to methods, and especially to those which have for their object the estimation of nitrogen, phosphorus, and nuclein in the faxes. W. D. H. Reactions of Infusoria with Carbonic and other Acids. By HERBERT S. JENNINGS and E. M. MOORE (Amer. J. Physiol., 1902, 6, 233--250).-Many infusoria collect in solutions of carbon dioxide and other acids, just as Faramdurn does.The spontaneous collections formed by these organisms may therefore be due to their excretion of carbon dioxide ; nevertheless there are other infusorians which, although they form spontaneous collections, do not gather in acids, and others still which rindoubtedly produce carbon dioxide, but do not form spontaneous collections a t all, W. D. H. 'fransformation of Glycerol into Sugar by Testicular Tissues. By GABRIEL BERTRAND (Cornpt. rend., 1901, 133, 887--890).-The testiculsr tissues, obtained under aseptic conditions from the dog, rabbit, guinea-pig, and cock, do not transform glycerol, in 10 per cent. aqueous solution, into a reducing sugar. The change is brought about by the addition of a trace of a solution containing microbes. The sugar obtained under these conditions reduces Fehling's solution in the cold and is iden tical with dihydroxyacetone yielding the osazone melting at 130" (compare Berthelot, Ann, Chim.Phys., 1857, 369). G. T. M. Cyclic Terpenes and Camphor in the Animal System. I. By EMIL FROMM and HERMANX HILDEBRANDT (Zeit. physiol. Chem.,lSOl, 33, 579-594. Compare Schmiedeberg and Meyer, ibid., 3,422 ; Pellacani, Arch. exp. Path. and Pkarrn., 1883, 17, 376 ; Schmiedeberg, ibid., 1881, 14, 308 ; Rimini, Rend. Accad. Lincei., [ v], 10, 244).--Cyclic terpenes and camphors are transformed in tha animal system, by a process of oxidation or hydration, into monohydroxyl derivatives, which are eliminated in the form of glycuronic acid derivatives. When a hydroxyl group is already present, as in sabinol, the com- pound of the original substance with glycuronic acid is eliminated.Pinene yields pinenolglycuyonic acid, but neither acid nor salts have been obtained in a crystalline form ; on treatment with hydrochloric acid, it yields a hydrocarbon, C10H,4, boiling at 175-176". PheZland.l.e~oSZycuronic acid and its salts are non-crystalline and when hydrolysed yield a phenol, C10H1402, melting at 1 4 2 O , and a hydro- carbon, C10H14, distilling at 1 7 5 O . Camphenolglycuronic acid, on hydrolysis, yields camphenol, CloH1,~OH', boiling at 202-2049160 ABSTRACTS OF CHEMICAL PAPERS, Sabinenolglyctwonic acid yields cyrnene on hydrolysis, and on oxida- tion, gives a mixture of two acids, the one melting at 220°, and the other remaining solid even at 320". Sabinolglycuyonic acid, on hydrolysis, yields cymene and on oxidation gives benzoic acid together with an acid, C,,H,,O, or C,,H,,O,, melt- ing a t 198'.Thu~onehydrateglycuronic acid yields a crystalline potussium salt, C,,H,,O,K, which on hydrolysis yields glycuronic acid and a hydro- cai*bon boiling at 170-180". Borneol- and Menthol-glycuronic Acids. By A. BONANNI (Baitr. chem. Physiol. Path., 1901, 1, 304-309).-1n dogs, if borneol is given by the mouth, i t is excreted in the urine in combination with glycuronic acid. Borneolglycuronic acid, C,,H2,07,H20, which crystallises in needles, is soluble in water, alcohol, ether, acetone, or chloroform ; when boiled with dilute sulphuric acid, it is resolved into its components. The potassium, zinc, and copper salts are crystalline, the calcium and barium salts amorphous. Mentholglycuronic acid was only obtained as a syrup, neither could crystalline salts be obtained.Certain Biological Characters of Phenylhydrazine. By LOUIS LEWIN (Zeit. Biol., 1901, 42, 10'7--146).-Chemists who work much with phenylhydrazino suffer from ill-health, of which the most prominent siga is a kind of eczema. The substance is also poisonous t o animals, and the pathological signs produced are described in full. Particular attention is directed to the action on the blood ; especially on living blood ; here a green derivative of hsmoglobin, called hsmo- verdin, is produced (compare this vol., i, 67). Metabolism in Acute Gout. By HANS VOGT (Chem. Centr., 1901, ii, 1212; from Arch. klin. Ned., 71, 21--28).-1n gout, there is retention of nitrogen, which is not due t o putting on of flesh.It appears to be explained by katabolism of nuclein, the phosphorus of which is excreted and the nitrogen retained. Whether this is purine nitrogen or proteid nitrogen must be decided by further work on the fate of uric acid and purine during the gouty condition. If nuclein is given in the food, it appears to be absorbed and excreted normally, the phosphorus soon, the uric acid later. By MIDORI ITO (Chem. Centr., 1901, ii, 1212-1213 ; from Arch. klin. Med., 71, 29-36).-Some rare cases are described in which true peptone (in Kuhne's sense) was found in the urine. Alcaptonuria. By FRANZ MITTELBACH (Chem. Centr., 1901, ii, 1213 ; from Arch. Klin. Med., 71, 50--72).-The theory that alcapto~l originates from tyrosine is confirmed.Phenylpropionic acid does not influence the excretion, phenylacetic acid does. I n the estimation of alcaptoir, it is necessary t o remove the uric acid first by saturation with ammonium chloride, J. J. S. The same is true for menthol. W. D. H. W. D. H. W. D. .H. Peptone in the Urine. The cases were those of lung disease. W. D. H. W. D, H,PHYSIOLOUICAL CHEMISTRY 1GZ Bornpounds of Arsenic in the Human Liver. B~RICHARD VON ZETNEK (Chenz. Centr., 1901, ii, 1232; from Centi'. f. Phgsiol., 15, 405--408).-1n arsenic poisoning (two cases), arsenic was found in a 0.1 sodium carbonate extract of the liver and in the insoluble residue after extraction with 10 per cent. solution of sodium chloride. After peptic digestion, the arsenic is found in the insoluble residue [Slowtzoff made similar observations (this vol., ii, 34)].Excretion of Cacodylic Acid and its Detection in Cases of Poisoning. By DIOSCORIDE VITALI (Chem. Centr., 1901, ii, 12 12 ; from Boll. Chirn. Fawn., 40, 657-665).-Cacodylic acid is sometimes used therapeutically; it passes as such into the urine, and not in an organic compound, A method of detecting it in the urine is described. W. D. H. W. D. H. The Influence of Carbon Monoxide on the amount of Carbon Dioxide in Arterial Blood, By T. SAIKI and G. WAKAYAMA (Zeit. physiol. Chem., 1901, 34, 96--107).-The experiments were made on rabbits and dogs, Under the influence of carbon monoxide poisoning, the amount of oxygen and carbon dioxide in the blood is greatly diminished ; the amount of lactic acid increases.Amyl nitrite has the same effect on the carbon dioxide. W. D. H. The Influence of Certain Poisons on the Synthesis of Phenol- sulphuric Acid in the Animal Organism. By K. KATsUYAMA Zeit. physiol. Chern., 1901, 34, 83-95).-1n rabbits oisoning with carbon monoxide produces an increase of the combined sulphates. The reaction of the urine, which is normally alkaline in these animals, becomes acid or neutral. Amyl nitrite inhibits the formation of p henol-sulp huric acid. By OTTO FRANK and FRITZ VOIT (Zeit. Biol., 1901,42, 309-362).-Metabolism pursues the same course when the muscular system is rendered inactive by curare. Large doses of curare upset metabolism, mainly by paralysing the muscular portion of the circulatory system and lowering blood- pressure; the lessening of the metabolism which then occurs is partly due to lowering of the body temperature.When a moderate dose is given so that only the voluntary muscles are affected, meta- bolism is so regular that the smallest changes produced by other agencies are markedly noticeable. The total metabolic exchanges are probably in the main greater in a curarised animal than in one simply at rest, in order t o maintain the normal body temperature. Curarised animals, except during lactation, follow Rubner's law of a fixed relationship between surfacearea and the amount of katabolism. About 85 per cent. of the total heat produced comes from fat metabolism, The metabolism both of proteid and fat in curarised, and in absolutely resting animals, is almost the same as under normal conditions., P W. D. H. Metabolism during Curare-poisoning. W. D. H. Toxicological Studies on the Selachian Heart. By WALTRER STRAUB (Zeit. Biol., 1901, 42, 363-376).-0bservations are recorded162 ABSTRACTS OF CHEMICAL PAPERS. regarding the action of antiarin and strophanthin on the heart of the ray, dogfish, and other selachians, and the results compared with those found in experiments with the frog’s heart (Arch. exp. Path. €’harm., 1901, 45, 346). These digitalis glucosides show, towards the fishes’ heart, a smaller toxicity than in the frog ; the effect on auricle and ventricle is about equal. W. D. H. Ergot of Rye. By MARCEL GUBDRAS (Compt. rend., 1901, 133, 1314)-The therapeutic action of ergot of rye is due to sphacelinic acid, cornutine, and the salts formed by their combination, Theii* sep- aration presents great difficulty because their solubilities are practically equal.A good sample of ergot should contain a high percentage of sphacelinic acid and cornutine, and a low percentage of sclerotic acid and other inert substances. C. H. B. Physiology of the Hypophysis. By E. VON CYON (P’iiyer’s Archiv, 1901, 87,565-593).-Hypophysin (not chemically identified) is placed with thyroiodin and suprarenin (or epinephrin) as a physio- logical heart poison. Removal of the hypophysis interferes with general metabolism, and produces not only acromegaly but also sterility. The main part of the paper has but little chemical interest. W. D. H. Phloridnin Diabetes. By GRAHAM LUSK (Zeit.Biol., 1901, 42, 31-44. Compare Abstr., 1900, ii, 55S).-In phloridzin diabetes, no sugar originates from fat. The number of calories which are lost by the excretion of sugar are made good by the increased decomposition of proteid. The relationship between dextrose and nitrogen in the urine of the fasting phloridzin diabetic dog is 3.75 : 1 ; in the rabbit, goat, and cat, it is 2.8 : 1. W. D. H. The Influence of Valency in the Antitoxic Action of Ions. By JACQUES LOEB (Pjiiger’s Archiv, 1901, 88, 68--78).-The poison- ous action of ions differs for various embryos and for different forms of contractile tissue, Certain other ions have an antagonistic action. The antitoxic action is confined to cations, and in this relation valency is a factor of importance.The poisonous action of a univalent cation can be neutralised by minimal quantities of a bivalent, and probably still smaller quantities of a tervalent, cation. The toxic action of a bivalent cation can be neutralised by a small quantity of another bivalent, or a relatively larger quantiti of a univaient cation, W. D. H. Natural Immunity against Alkaloids. By A LEXANDER ELLIN- GER (Zeit. Bid., 1901, 42, 228--241).-1t is well known that certain animals are not affected by poisonous alkaloids. The rabbit in relation to atropine is one of the best known examples. Calmette has, how- ever, shown that if 2 milligrams of atropine sulphate are injected directly into the brain of a rabbit, it dies in a few hours; yet it is unaffected by 0-2 gram injected into its blood. He believes the leucocytes ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. 163 this animal have the power of combining with the alkaloid and so pro- tecting the animal. It is now pointed out that this theory is not sup- ported by analyses of leucocytes, plasma, and brain, and that there is a want of certain control experiments. Attempts to show that the leucocytes contain more atropine than the plasma were not successful, although it is admitted that the methods of estimation of minute quan- tities of the alkaloid are not a t present very accurate. Protective Substances of Immune Sera. By E. W. AINLEY WALKER (J. Hygiene, 1902, 2, 85-loo).- From experiments with BaciZlzcs typhosus, conclusions are reached which differ somewhat from Ehrlich’s, especially in relation to the part played by the ‘ addi- ment.’ The amount of the ‘immune substance’ needed for protec- tion against n minimum lethal doses of a bacterium is contained in (n d - e)/(d - e ) C.C. of its immune serum, where d is the minimum lethal dose, and e the largest dose, invariably not fatal, and the serum equiva- lent of one minimum lethal dose. The addiment is a leucocytic ferment whish is not extremely special to the species, and is inzreased during and by immunisation. Agglutinins assist the phagocytic process of ingestion. W. D. H. By ERNST P. PICK (Beit?*. &em. Physiol. Path., 1901, 1, 351-444).-This is an attempt t o isolate various They are associated with the globulin of the serum, usually with the eu- globulin fraction. The property of preventing the action of ‘ coagu- lins’ is also possessed by euglobulin, whilst antirennin action is a property of pseudo-globulin. Calcium salts and phosphates have no influence on the former action. W. D. H. Immune Substances. immune substances ’ of the antitoxic blood in various diseases, W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9028205149

出版商:RSC    

年代:1902

数据来源: RSC